JP2016099438A - Pattern formation method, actinic ray-sensitive or radiation-sensitive resin composition used therefor, electronic device using them, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern formation method which can form patterns with shapes having excellent exposure latitude, development properties and pattern profiles.SOLUTION: The pattern formation method comprises: (a) forming a film from an actinic ray-sensitive or radiation-sensitive resin composition, which contains a compound represented by the general formula (A-1) and a resin with a repeating unit represented by the general formula (nI) whose polarity increases by an action of an acid so as to reduce solubility in a developer containing an organic solvent; (b) irradiating the film with an actinic ray or radiation; and (c) developing the film irradiated with the actinic ray or radiation using the developer containing the organic solvent.SELECTED DRAWING: None

Description

  The present invention relates to a pattern forming method, an actinic ray-sensitive or radiation-sensitive resin composition used therefor, an electronic device manufacturing method using the same, and an electronic device. More specifically, the present invention relates to a pattern forming method suitable for a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and other photofabrication lithography processes, and the pattern forming method. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a method for producing an electronic device using these, and an electronic device. In particular, the present invention relates to an ArF exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, a pattern forming method suitable for exposure in an ArF immersion projection exposure apparatus, and an actinic ray used in the pattern forming method. The present invention relates to a photosensitive or radiation-sensitive resin composition, a method for producing an electronic device, and an electronic device.

Conventionally, in a manufacturing process of a semiconductor device such as an IC or LSI, fine processing by lithography using a photoresist composition has been performed.
In recent years, a pattern formation method using a developer (organic developer) containing an organic solvent has been developed (Patent Document 1).

JP 2011-123469 A

On the other hand, in recent years, various electronic devices have been required to have higher functions, and accordingly, further improvement in characteristics of resist patterns used for microfabrication has been required. In particular, when a finer contact hole pattern is to be formed, problems such as insufficient exposure latitude (EL), development defects, pattern profile deterioration, etc. are likely to occur, and it is required to improve these resist performances. Yes.
The present inventors evaluated the above various characteristics using the pattern forming method described in Patent Document 1. As a result, although the conventional required level was satisfied, the level required recently is not satisfied, and further improvement is necessary. It was.

In view of the above circumstances, an object of the present invention is to provide a pattern forming method capable of forming a pattern having a shape with favorable exposure latitude, development characteristics, and pattern profile.
Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition used therefor, an electronic device using these, and a method for producing the same.

As a result of intensive studies on the problems of the prior art, the present inventors have developed an organic solvent using an actinic ray-sensitive or radiation-sensitive resin composition containing a predetermined resin and a predetermined photoacid generator. It has been found that the above-mentioned problems can be solved by performing development processing with a liquid.
That is, it has been found that the above object can be achieved by the following configuration.

(1) (a) A step of forming a film with an actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B):
(A) Compound that generates acid upon irradiation with actinic ray or radiation represented by general formula (A-1) described later (B) Action of acid having repeating unit represented by general formula (nI) described later Resin in which the polarity is increased and the solubility in a developer containing an organic solvent is reduced. (A) A step of irradiating the film with actinic rays or radiation, and
(C) A pattern forming method comprising: developing a film irradiated with actinic rays or radiation using a developer containing an organic solvent.
(2) The pattern formation method as described in (1) whose compound represented by general formula (A-1) is a compound represented by general formula (A-2) mentioned later.
(3) The pattern forming method according to (1) or (2), wherein Y is a polycyclic aliphatic group.
(4) The pattern formation method according to any one of (1) to (3), wherein in general formula (nI), at least one of R ₁₃ ′ to R ₁₆ ′ is a group having an acid-decomposable group.
(5) The pattern forming method according to (4), wherein the group having an acid-decomposable group is a group represented by * ¹ -L ³ -AD. L ³ represents an alkylene group. AD represents an acid-decomposable group. * ¹ represents the bonding position with the resin.
(6) The pattern formation method in any one of (1)-(5) in which resin (B) has a repeating unit represented by general formula (VIII) mentioned later.
(7) The actinic ray-sensitive or radiation-sensitive resin composition further contains a hydrophobic resin, and the content of the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive resin composition is 0.01 on a solid basis. The pattern formation method in any one of (1)-(6) which is 10 mass%.
(8) The hydrophobic resin has at least one selected from the group consisting of a fluorine atom, a silicon atom, and a CH ₃ partial structure contained in a side chain portion of the hydrophobic resin. Pattern forming method.
(9) The pattern forming method according to (7) or (8), wherein the hydrophobic resin has a repeating unit represented by the general formula (nI) described later.
(10) The pattern forming method according to any one of (1) to (9), wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a chain or cyclic ketone solvent.
(11) The pattern forming method according to any one of (1) to (10), wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a lactone solvent.
(12) The pattern according to any one of (1) to (11), wherein Z ¹⁺ is any one of cations represented by general formulas (C-1) to (C-3) described later. Forming method.
(13) The actinic ray-sensitive or radiation-sensitive resin composition is an actinic ray or radiation that is different from a compound that generates an acid upon irradiation with an actinic ray or radiation represented by the general formula (A-1) described later. The pattern formation method in any one of (1)-(12) containing the compound which generate | occur | produces an acid by irradiation.
(14) An actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to (1), further including a hydrophobic resin.
(15) The actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to (1), further including a chain or cyclic ketone solvent,
An actinic ray-sensitive or radiation-sensitive resin composition in which Z ¹⁺ is any one of cations represented by formulas (C-1) to (C-3) described later.
(16) The actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to (1), further including a lactone solvent,
An actinic ray-sensitive or radiation-sensitive resin composition in which Z ¹⁺ is any one of cations represented by formulas (C-1) to (C-3) described later.
(17) An actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to (1), further comprising an actinic ray or radiation represented by the general formula (A-1) described later. An actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with an actinic ray or radiation different from a compound that generates an acid upon irradiation.
(18) An electronic device manufacturing method including the pattern forming method according to any one of (1) to (13).
(19) An electronic device manufactured by the method for manufacturing an electronic device according to (18).

ADVANTAGE OF THE INVENTION According to this invention, the pattern formation method which can form the pattern of a favorable shape with exposure latitude, a development characteristic, and a pattern profile can be provided.
Moreover, according to this invention, the actinic-ray-sensitive or radiation-sensitive resin composition used for it, the electronic device using these, and its manufacturing method can also be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
Unless otherwise specified, “exposure” in the present specification is not limited to exposure to deep ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers, but also particles such as electron beams and ion beams. Line drawing is also included in the exposure.
In this specification, "(meth) acrylic monomer" means at least one monomer having the structure of "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " To do. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

  In this specification, the “organic group” means a functional group containing at least one or more carbon atoms (for example, an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof). , A heteroatom (for example, an oxygen atom) may be contained.

  A feature of the present invention is that development is performed in an organic solvent using a composition containing a resin containing a repeating unit having a norbornane skeleton in the main chain and a predetermined photoacid generator. More specifically, first, since the resin contains a norbornane skeleton in the resin, the resin becomes rigid, the diffusibility of the photoacid generator in the film is suppressed, and a desired effect is obtained as a result. In addition, if the fluorine atom content in the photoacid generator is less than or equal to a predetermined value, the driving force for uneven distribution of the photoacid generator on the resist film surface is reduced, so that the photoacid generator is uniformly present in the resist film. As a result, the pattern shape and EL are improved. Further, when the above resin containing a repeating unit having a norbornane skeleton in the main chain and the photoacid generator are combined, a synergistic effect of reducing the diffusibility of the acid generator, the pattern shape at the time of contact hole pattern formation And EL are significantly improved. In addition, the aspect by which the hydrophobic resin mentioned later is contained in the actinic-ray-sensitive or radiation-sensitive resin composition by the point which the said various characteristics are more excellent is mentioned.

The pattern forming method of the present invention includes the following steps (a) to (c).
(A) Step of forming a film with an actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B) (A) Actinic ray or radiation represented by formula (A-1) Compound (B) which generates acid upon irradiation Resin having repeating unit represented by general formula (nI) whose polarity is increased by the action of acid and its solubility in a developing solution containing an organic solvent is reduced. Step of irradiating actinic rays or radiation to (c) Step of developing a film irradiated with actinic rays or radiation using a developer containing an organic solvent In the following, first, the activity used in step (a) The components contained in the light-sensitive or radiation-sensitive resin composition (hereinafter simply referred to as “composition”) are described in detail, and then the procedure of each step is described in detail.

<Compound capable of generating acid upon irradiation with actinic ray or radiation represented by general formula (A-1)>
The composition is a compound (hereinafter referred to as “photoacid generator (A)” or “general formula (A-1)” that generates an acid upon irradiation with an actinic ray or radiation represented by the general formula (A-1). Also referred to as “compound”.
Hereinafter, each group in the compound represented by the general formula (A-1) will be described in detail.

In general formula (A-1), Q ¹ and Q ² each independently represent a hydrogen atom, a fluorine atom or an organic group, and at least one of Q ¹ and Q ² is a fluorine atom or at least one fluorine An alkyl group substituted with an atom is represented.
Preferred examples of the organic group represented by Q ¹ and Q ² include CF ₃ .
Among these, Q ¹ and Q ² are independently independent from the point that at least one of exposure latitude, development characteristics, and pattern profile is more excellent (hereinafter also referred to as “the effect of the present invention is more excellent”). It is preferably a fluorine atom or an alkyl group substituted with at least one fluorine atom, more preferably a fluorine atom or a C 1-4 perfluoroalkyl group, and a fluorine atom or CF _3. Is more preferable, and it is particularly preferable that both are fluorine atoms.
In addition, it is preferable that carbon number of the said alkyl group is 1-10, and it is more preferable that it is 1-4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Examples of the alkyl group include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , and CH ₂ CF _3. CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , or CH ₂ such as CH ₂ C ₄ F can be mentioned.

L ¹ represents a single bond, —O—, —COO—, or OCO—. Among them, in terms of the effect of the present invention is more excellent, a single bond, or, * ¹ -COO- * ² group (* in ¹ (CQ ¹ Q ²⁾ coupled with _p, at * ² (CR ¹ R ²⁾ It is preferable that it is bonded to _q ).

R ¹ and R ² each independently represents a hydrogen atom or an organic group.
Examples of the organic group represented by R ¹ and R ² include an alkyl group and a cycloalkyl group.
Especially, it is preferable that R < ¹ > and R < ² > are respectively independently a hydrogen atom and an alkyl group at the point which the effect of this invention is more excellent, and it is more preferable that both are hydrogen atoms.
The alkyl group may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group having a substituent for R ¹ and R ² include groups exemplified as the alkyl groups for Q ¹ and Q ² .

L ² represents a single bond or a divalent linking group. Examples of the divalent linking group include —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, and an alkylene group. (Preferably having 1 to 6 carbon atoms), cycloalkylene group (preferably having 3 to 10 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms) or a divalent linking group in which a plurality of these are combined. . Among these, —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —SO ₂ —, —COO-alkylene group—, —OCO-alkylene group—, —CONH— alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable. In particular, L ² is more preferably a * ¹ —OCO— * ² group (bonded to (CR ¹ R ² ) _q at * ¹ and bonded to Y at * ² ).

Y represents a group having a cyclic structure having 3 to 18 carbon atoms which may have a substituent. Examples of the group having a cyclic structure include a cyclic aliphatic group, an aryl group, and a group having a heterocyclic structure.
In addition, 6-15 are preferable and 10-12 are more preferable from the point which the effect of this invention is more excellent.

The cyclic aliphatic group (alicyclic hydrocarbon group) as Y may have a monocyclic structure or a polycyclic structure. As the cyclic aliphatic group having a monocyclic structure, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are preferable. Examples of the cyclic aliphatic group having a polycyclic structure (polycyclic aliphatic group) include polycyclic cyclic groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. A cycloalkyl group is mentioned.
In particular, as Y, a polycyclic aliphatic group is preferable and an adamantyl group is more preferable in that the effect of the present invention is more excellent.

p represents an integer of 1 to 3. Especially, 1 or 2 is preferable and 1 is more preferable at the point which the effect of this invention is more excellent.
q represents the integer of 1-8. Especially, 1-3 are preferable at the point which the effect of this invention is more excellent, 1 or 2 is more preferable, and 1 is especially preferable.

In the anion (sulfonic acid anion) in the general formula (A-1), the fluorine atom content is 0 to 20% by mass. Especially, 1-18 mass% is preferable and, as for the content rate of a fluorine atom, the 3-15 mass% is more preferable at the point which the effect of this invention is more excellent.
When the fluorine atom content is outside the above range, the effect of the present invention is poor.
In addition, the said anion (sulfonic acid anion) intends parts (anion parts) other than Z ^{<1+> in} general formula (A-1).
The fluorine atom content is intended to be the ratio of the total molecular weight of fluorine atoms in the anion to the total molecular weight of the anion (total molecular weight of fluorine atoms / total molecular weight of anions). For example, when the molecular weight of the whole anion is 380 and two fluorine atoms are contained in the anion, the fluorine atom content is 10% by mass [(19 × 2/380) × 100].

Z ¹⁺ represents a cation.
Examples of the cation include an onium cation, a sulfonium cation, an iodonium cation, an ammonium cation, a benzothiazolium cation, and a phosphonium cation. Among these, a sulfonium cation and an iodonium cation are preferable, and an arylsulfonium cation is more preferable.
Especially, the cation represented by the following general formula (C-1)-(C-3) is preferable at the point which the effect of this invention is more excellent. Hereinafter, general formulas (C-1) to (C-3) will be described in detail.

In general formula (C-1), R < ³ > -R < ⁹ > represents a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom, or an organic group each independently. In addition, at least one of R ^{3 to} R ⁹ represents a hydroxyl group, a carboxyl group, a halogen atom, or an organic group.
Among these, R ^{3 to} R ⁷ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen, It preferably represents an atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.
R ⁸ and R ⁹ each independently preferably represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
R ¹⁰ and R ¹¹ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group. Represent.

Any two of R ^{3 to} R ⁷ may be bonded to each other to form a ring. R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ may be bonded to each other to form a ring. Note that the ring structure may include an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

R ^{3 to} R ¹¹ may further have a substituent. Examples of such a substituent include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cyclo group. Alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, arylcarbonyl group, alkoxyalkyl group, aryloxyalkyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, etc. Can be mentioned.

  Hereinafter, Formula (C-2) will be described in detail.

In General Formula (C-2), R ¹² and R ¹³ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. R ¹² and R ¹³ may be bonded to each other to form a ring, and the atoms constituting the ring may include heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom. These groups may have a substituent.
R ¹⁴ preferably represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a group having a monocyclic or polycyclic cycloalkyl group, or an alkylene oxide chain.
R ¹⁵ represents a hydroxyl group, a carboxyl group, a halogen atom or an organic group. Among them, R ¹⁵ represents a group having a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. preferable. In addition, when there are a plurality of R ^{15 s} , they may be the same or different.

The alkyl group for R ^{12 to} R ¹⁵ is linear or branched and preferably has 1 to 10 carbon atoms.
Examples of the cycloalkyl group represented by R ^{12 to} R ¹⁵ include a monocyclic or polycyclic cycloalkyl group.
The alkoxy group for R ^{14 to} R ¹⁵ is linear or branched and preferably has 1 to 10 carbon atoms.
The alkoxycarbonyl group for R ^{14 to} R ¹⁵ is linear or branched and preferably has 2 to 11 carbon atoms.
Examples of the group having a cycloalkyl group as R ¹⁵ include a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.
Specific examples of the alkyl group of the alkylcarbonyl group represented by R ¹⁵ include the same examples as the above alkyl group.
The alkylsulfonyl group and cycloalkylsulfonyl group represented by R ¹⁵ are linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms.

  Examples of the substituent that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Etc.

R ¹² and R ¹³ may combine with each other to form a ring, and the formed ring structure includes a 5-membered or 6-membered ring formed by R ¹² and R ¹³ together with a sulfur atom, particularly preferably a 5-membered ring. (That is, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. This ring structure may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxy group. A carbonyloxy group etc. can be mentioned. There may be a plurality of substituents for the ring structure, or they may be bonded to each other to form a ring.
The R ¹² and R ^13, a methyl group, an ethyl group, a naphthyl group, and the like divalent group R ¹² and R ¹³ form a tetrahydrothiophene ring structure bonded to together with the sulfur atom to each other are preferable, R ¹² and A divalent group in which R ¹³ is bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom is particularly preferable.

r represents an integer of 0-2. Especially, 0 or 1 is preferable and 1 is more preferable.
m15 represents an integer of 0 to 8. Especially, 0-2 are preferable.

  Below, the cation represented by general formula (C-2) is illustrated.

  Hereinafter, General Formula (C-3) will be described in detail.

In General Formula (C-3), R ^{16 to} R ¹⁸ each independently represent a hydroxyl group, a carboxyl group, a halogen atom, or an organic group.
Especially, it is preferable that R < ¹⁶ > -R < ¹⁸ > represents a methyl group, a tert- butyl group, a methoxy group, a fluorine atom, and a chlorine atom.
Any two of R ^{16 to} R ¹⁸ may be bonded to each other to form a ring. The ring structure may include an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.

m16 to m18 each independently represents an integer of 0 to 5. Especially, 1-3 are preferable and 1 is more preferable.
Note that at least one of m16 to m18 represents an integer of 1 or more.

  Below, the cation represented by general formula (C-3) is illustrated.

  As a suitable aspect of the compound represented by the said general formula (A-1), the compound (photoacid generator) represented by the following general formula (A-2) is the point which the effect of this invention is more excellent. Can be mentioned.

  In addition, the definition and suitable aspect of each group in the said general formula (A-2) are as above-mentioned.

The photoacid generator (A) can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.
A photo-acid generator (A) can be used individually by 1 type or in combination of 2 or more types.

The content of the photoacid generator (A) in the composition is not particularly limited, but is preferably 12 to 30% by mass with respect to the total solid content in the composition in terms of more excellent effects of the present invention. -20 mass% is more preferable.
The total solid content means the total mass of components constituting the resist film described later, and other components excluding the solvent.

<Resin having a repeating unit represented by the general formula (nI) whose polarity is increased by the action of an acid and its solubility in a developer containing an organic solvent is reduced>
The composition has a repeating unit represented by the general formula (nI), a resin (hereinafter referred to as an “acid-decomposable resin” or a resin whose polarity is increased by the action of an acid and its solubility in a developer containing an organic solvent decreases. (Also referred to as “resin (B)”).
Resin (B) is a group (hereinafter also referred to as “acid-decomposable group”) that decomposes by the action of an acid to generate a polar group in the main chain or side chain of the resin, or in both the main chain and the side chain. It is preferable to have.
Hereinafter, the repeating unit represented by the general formula (nI) will be described in detail first.

In general formula (nI):
R ₁₃ ′ to R ₁₆ ′ each independently have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, or a lactone structure. Represents a group or a group having an acid-decomposable group.
X ₁ and X ₂ each independently represents a methylene group, an ethylene group, an oxygen atom or a sulfur atom. Preferably, it represents a methylene group.
n represents an integer of 0 to 2. Preferably, 0-1 are represented.

As described above, the acid-decomposable group in the group having an acid-decomposable group as R ₁₃ ′ to R ₁₆ ′ is a group that is decomposed by the action of an acid to generate a polar group. It preferably has a structure protected with a group capable of decomposing and leaving.
The polar group is not particularly limited as long as it is a group that is hardly soluble or insoluble in a developer containing an organic solvent, but a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group. , Sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkyl Sulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group and other acidic groups (2.38 mass% tetra, conventionally used as a resist developer) Methylan Group dissociates in onium hydroxide aqueous solution), or alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). An aliphatic alcohol substituted with a functional group (for example, a fluorinated alcohol group (such as a hexafluoroisopropanol group)) is excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of 12 or more and 20 or less.
Preferred polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Group, octyl group and the like.
The cycloalkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and the polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
The aryl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms.
The alkenyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms.
The ring formed by combining R ₃₆ and R ₃₇ is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.

Preferred examples of the acid-decomposable group include a cumyl ester group, an enol ester group, an acetal ester group, and a tertiary alkyl ester group, and more preferably —C (═O) —O—R ₀ . It is a tertiary alkyl ester group represented.
In the formula, R ₀ is a tertiary alkyl group such as t-butyl group or t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy. 1-alkoxyethyl group such as ethyl group, 1-methoxymethyl group, alkoxymethyl group such as 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- An oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue and the like can be mentioned.

The group having an acid-decomposable group is preferably a group represented by * ¹ -L ³ -AD from the viewpoint of further inhibiting the diffusion of the generated acid.
L ³ represents an alkylene group which may have a substituent. Although carbon number contained in an alkylene group is not specifically limited, 1-10 are preferable and 2-8 are more preferable. Examples of the substituent include a hydroxyl group and an alkoxy group.
Further, the alkylene group represented by L ³ may contain a hetero atom. That is, it may be a hetero atom-containing alkylene group. The type of hetero atom contained is not particularly limited, and examples thereof include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a tellurium atom. For _{example, -Y 1 H, -Y 1 -} , - N (R a) -, - C (= Y 2) -, - CON (R b) -, - C (= Y 3) Y 4 -, - SO _t— , —SO ₂ N (R _c ) —, a halogen atom, or a group in which two or more of these are combined is included.
Y _{1 to} Y ₄ are each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Of these, an oxygen atom and a sulfur atom are preferred because they are easier to handle.
R _a , R _b and R _c are each independently selected from a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. t represents an integer of 1 to 3.
AD represents an acid-decomposable group. The definition of the acid-decomposable group is as described above.
* ¹ represents the bonding position with the resin.

From the viewpoint of improving the dissolution contrast, at least one of R ₁₃ ′ to R ₁₆ ′ is preferably a group having an acid-decomposable group.
Examples of the halogen atom in R ₁₃ ′ to R ₁₆ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
The alkyl group represented by R ₁₃ ′ to R ₁₆ ′ is more preferably a group represented by the following general formula (F1).

In general formula (F1),
R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Rx is a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, an alkyl group, a cycloalkyl group, an acyl group or an alkoxycarbonyl group), preferably a hydrogen atom.
R _{50 to} R ₅₅ are preferably all fluorine atoms.

  The content of the repeating unit represented by the general formula (nI) is not particularly limited, but is 5 to 50 mol% with respect to all the repeating units in the resin (B) in that the effect of the present invention is more excellent. It is preferably 10 to 40 mol%, more preferably 15 to 35 mol%.

  Specific examples of the repeating unit represented by the general formula (nI) include the following specific examples, but the present invention is not limited to these compounds. Especially, the repeating unit represented by (II-f-16)-(II-f-19) is preferable.

  The resin (B) preferably has a repeating unit represented by the following general formula (VIII) from the viewpoint of substrate adhesion.

In the general formula (VIII),
Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, or —OSO ₂ —R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.
The content of the repeating unit represented by the general formula (VIII) is not particularly limited, but is 5 to 60 mol% with respect to all the repeating units in the resin (B) in that the effect of the present invention is more excellent. Preferably, it is 15 to 55 mol%, more preferably 30 to 50 mol%.

The resin (B) preferably contains the above-described repeating unit represented by the general formula (nI) and the repeating unit represented by the general formula (VIII). This improves the adhesion of the resist film to the substrate.
Examples of the repeating unit represented by the general formula (VIII) include the following specific examples, but the present invention is not limited thereto.

  The resin (B) may contain a repeating unit other than those described above, and for example, may contain a repeating unit represented by the following general formula (AI) (a repeating unit having an acid-decomposable group).

In general formula (AI):
Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the alkyl group which may have a substituent represented by Xa ₁ include a group represented by a methyl group or —CH ₂ —R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group. In one embodiment, Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group or the like.

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.
The alkyl group of Rx _{1 to} Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.

Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group A polycyclic cycloalkyl group such as a group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
The cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It may be replaced.

The repeating unit represented by the general formula (AI) preferably has, for example, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group.
Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, An alkoxycarbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.
The total content of repeating units having an acid-decomposable group is preferably 20 to 80 mol%, more preferably 25 to 75 mol%, based on all repeating units in the resin (B), 30 More preferably, it is -70 mol%, and it is most preferable that it is 20-50 mol%.
As the resin (B), specifically, specific examples disclosed in [0265] of US Patent Application Publication No. 2012/0135348 can be used, but the present invention is not limited thereto. .

  The resin (B) has, for example, at least one of a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably, it is a resin.

In formulas (I) and (II), R ₁ and R ₃ each independently represent a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R _11. . R ₁₁ represents a monovalent organic group.
R ₂ , R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with the carbon atom to which R ₂ is bonded.
R ₁ and R ₃ preferably represent a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. Specific examples and preferred examples of the monovalent organic group in R ₁₁ are the same as those described for R ₁₁ in formula (AI).

The alkyl group in R ₂ may be linear or branched, and may have a substituent.
The cycloalkyl group in R ₂ may be monocyclic or polycyclic and may have a substituent.
R ₂ is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group, an ethyl group, or an isopropyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R together with the carbon atom is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, more preferably 5 or 6.
R ₃ is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

The alkyl group in R ₄ , R ₅ and R ₆ may be linear or branched and may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.

The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

Examples of the substituent that each of the groups may have include the same groups as those described above as the substituent that each group in the general formula (AI) may have.
The resin (B) is a resin containing a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferred.

  One type of repeating unit having an acid-decomposable group contained in the resin (B) may be used, or two or more types may be used in combination. When used together, the specific examples disclosed in paragraph [0287] of US Patent Application Publication No. 2012/0135348 can be used, but the present invention is not limited thereto.

The resin (B) preferably contains a repeating unit having a lactone structure or a sultone (cyclic sulfonate ester) structure.
Any lactone group or sultone group can be used as long as it has a lactone structure or a sultone structure, but it is preferably a 5- to 7-membered lactone structure or a sultone structure, and a 5- to 7-membered lactone A structure in which another ring structure is condensed to form a bicyclo structure or a spiro structure in the structure or sultone structure is preferable. Any of the general formulas (LC1-1) to (LC1-17) and the following general formulas (SL1-1) and (SL1-2) disclosed in paragraph [0318] of US Patent Application Publication No. 2012/0135348 It is more preferable to have a repeating unit having a lactone structure or a sultone structure represented by: A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures or sultone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), and more preferably (LC1-4). By using a specific lactone structure or sultone structure, LWR and development defects are improved.

The lactone structure part or sultone structure part may or may not have a substituent (Rb ₂ ). When n ₂ is 2 or more, the plural substituents (Rb ₂ ) may be the same or different, and the plural substituents (Rb ₂ ) may be bonded to form a ring. .

  The resin (B) preferably has a repeating unit having a hydroxyl group or a cyano group other than the general formula (AI). This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferred.

In general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. In general formula (VIIa), it is more preferable that _two members out of R ₂ c to R ₄ c are hydroxyl groups and the remaining are hydrogen atoms.
Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ (VIIc), same meanings as R ₂ c~R ₄ c.
The content of the repeating unit having a hydroxyl group or a cyano group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (B).
Specific examples of the repeating unit having a hydroxyl group or a cyano group include the repeating unit disclosed in paragraph [0340] of US Patent Application Publication No. 2012/0135348, but the present invention is not limited thereto.

Resin (B) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general necessary characteristics of resist, in addition to the above repeating structural units. For this purpose, various repeating structural units can be included.
Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
Thereby, the performance required for the resin (B) used in the composition of the present invention, in particular, (1) solubility in a coating solvent, (2) film formability (glass transition point), (3) alkali developability (4) Slip film (selection of hydrophilicity / hydrophobicity, alkali-soluble group), (5) Adhesion of unexposed part to substrate, (6) Dry etching resistance, etc. can be finely adjusted.

As such a monomer, for example, it has one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like. A compound etc. can be mentioned.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin (B), the content molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and the general required performance of the resist, resolving power, heat resistance, sensitivity. It is set appropriately in order to adjust etc.

When the composition of the present invention is used for ArF exposure, the resin (B) used in the composition of the present invention preferably has substantially no aromatic group from the viewpoint of transparency to ArF light. . More specifically, the repeating unit having an aromatic group is preferably 5% by mole or less, more preferably 3% by mole or less, and more preferably 3% by mole or less of the entire repeating unit of the resin (B). More preferably, it is 0 mol%, that is, it does not have a repeating unit having an aromatic group. The resin (B) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
In addition, it is preferable that resin (B) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin mentioned later.

  The resin (B) in the present invention can be synthesized according to a conventional method (for example, radical polymerization). Specifically, synthetic methods disclosed in paragraphs [0126] to [0128] of US Patent Application Publication No. 2012/0164573 can be used.

The weight average molecular weight of the resin (B) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and even more preferably 3,000 to 15 as a polystyrene-converted value by the GPC method. 1,000, particularly preferably 3,000 to 11,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
The dispersity (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. Those in the range are used. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

  As for the content rate in the whole composition of resin (B), 30-99 mass% is preferable in a total solid, More preferably, it is 55-95 mass%. In addition, the resins of the present invention may be used alone or in combination.

<Other ingredients>
In the composition, components other than the photoacid generator (A) and the resin (B) may be contained.
Below, arbitrary components are explained in full detail.

(Compound capable of generating acid upon irradiation with actinic ray or radiation (B2))
The composition in the present invention comprises a compound (B2) that generates an acid upon irradiation with an actinic ray or radiation different from the compound represented by the general formula (A-1) (hereinafter referred to as “photoacid generator” or “ Compound (B2) ”).
The compound (B2) is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation.
The compound (B2) may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
When the compound (B2) is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
When the compound (B2) is in a form incorporated into a part of the polymer, it may be incorporated into a part of the acid-decomposable resin described above, or may be incorporated into a resin different from the acid-decomposable resin. .
In the present invention, the compound (B2) is preferably in the form of a low molecular compound.

As the compound (B2), a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecoloring agent for dyes, a photochromic agent, an actinic ray or radiation used for a microresist, etc. Known compounds that generate an acid upon irradiation and mixtures thereof can be appropriately selected and used.
Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Preferred examples of the compound (B2) include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Z ⁻ represents a non-nucleophilic anion.
Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. Thereby, the temporal stability of the actinic ray-sensitive or radiation-sensitive resin composition is improved.
Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.
Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.
The aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cyclohexane having 3 to 30 carbon atoms. An alkyl group,
The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.
The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent.
Examples of other non-nucleophilic anions include fluorinated phosphorus (for example, PF ₆ ⁻ ), fluorinated boron (for example, BF ₄ ⁻ ), fluorinated antimony and the like (for example, SbF ₆ ⁻ ). .

Examples of the non-nucleophilic anion of Z ⁻ include an aliphatic sulfonate anion in which at least α position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, an alkyl group Is preferably a bis (alkylsulfonyl) imide anion substituted with a fluorine atom, or a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.
Among the compounds (B2), particularly preferable examples include the compounds exemplified in paragraph [0143] of US2012 / 0207978A1.

Compound (B2) can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.
When using 2 or more types of compounds (B2) together, the total content in the composition of the compound (B2) is preferably 0.1 to 30% by mass, more preferably based on the total solid content of the composition. It is 0.5-25 mass%, More preferably, it is 3-20 mass%, Most preferably, it is 3-15 mass%.

(Acid diffusion control agent)
The composition of the present invention preferably contains an acid diffusion controller. The acid diffusion controller acts as a quencher that traps the acid generated from the photoacid generator or the like. Examples of the acid diffusion controller include a basic compound, a low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, a basic compound whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, light An onium salt that is a weak acid relative to the acid generator can be used.

  Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
Specific examples of preferred compounds include those exemplified in paragraph [0379] of US Patent Application Publication No. 2012/0219913.

  Preferable basic compounds further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, or an ammonium salt compound having a sulfonic acid ester group.

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably C6-C12) may be bonded to a nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable.
The following compounds are also preferable as the basic compound.

As basic compounds, in addition to the above-mentioned compounds, paragraphs [0180] to [0225] of JP 2011-22560 A, paragraphs [0218] to [0219] of JP 2012-137735 A, International Publication Pamphlet The compounds described in paragraphs [0416] to [0438] of WO2011 / 158687A1 can also be used.
These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

The composition of the present invention may or may not contain a basic compound, but when it is contained, the content of the basic compound is usually 0.001 to 10 relative to the total solid content of the composition. % By mass, preferably 0.01 to 5% by mass.
The use ratio of the photoacid generator (A) and the basic compound in the composition is preferably photoacid generator (A) / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing resolution from being reduced due to the thickening of the resist pattern over time until post-exposure heat treatment. The photoacid generator (A) / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

A low molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter, also referred to as compound (C)) has an acetal group, a carbonate group, a carbamate group, A tertiary ester group, a tertiary hydroxyl group, and a hemiaminal ether group are preferable, and a carbamate group and a hemiaminal ether group are particularly preferable.
100-1000 are preferable, as for the molecular weight of a compound (C), 100-700 are more preferable, and 100-500 are especially preferable.
As the compound (C), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

  Compound (C) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
Rb each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group ( Preferably it represents C1-C10) or an alkoxyalkyl group (preferably C1-C10). Rb may be connected to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are substituted with a functional group such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, alkoxy group, or halogen atom. It may be. The same applies to the alkoxyalkyl group represented by Rb.

Rb is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
Examples of the ring formed by connecting two Rb to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
Specific examples of the group represented by the general formula (d-1) include a structure disclosed in paragraph [0466] of US Patent Application Publication No. 2012/0135348, but are not limited thereto. Is not to be done.

  It is particularly preferable that the compound (C) has a structure represented by the following general formula (6).

In the general formula (6), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.

In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are described above as the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb may be substituted. It may be substituted with a group similar to the group.
Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above groups) include Rb The same group as the specific example mentioned above about is mentioned.

  Specific examples of preferred compound (C) include, but are not limited to, compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012/0135348.

The compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
In the present invention, the compound (C) can be used singly or in combination of two or more.
Although content in particular of the compound (C) in the composition of this invention is not restrict | limited, It is preferable that it is 0.001-20 mass% with respect to the total solid of a composition, More preferably, it is 0.001-10. It is 0.01 mass%, More preferably, it is 0.01-5 mass%.

  A basic compound whose basicity decreases or disappears upon irradiation with actinic rays or radiation has a proton acceptor functional group, and decomposes upon irradiation with actinic rays or radiation, resulting in a decrease or disappearance of proton acceptor properties. Or a compound that changes from proton acceptor properties to acidic properties. Hereinafter, it is also referred to as compound (PA).

  The proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron. For example, a functional group having a macrocyclic structure such as a cyclic polyether or a π-conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.

  Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.

  The compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Means that when a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.

  Proton acceptor property can be confirmed by measuring pH.

  In the present invention, the acid dissociation constant pKa of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation preferably satisfies pKa <−1, more preferably −13 <pKa <−1. And more preferably −13 <pKa <−3.

In the present invention, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is described in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.) The lower the value, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the following software package 1, Hammett The values based on the substituent constants and the database of known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.
Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

  The compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition upon irradiation with actinic rays or radiation. Since the compound represented by the general formula (PA-1) has an acidic group together with the proton acceptor functional group, the proton acceptor property is reduced or disappeared compared to the compound (PA), or from the proton acceptor property. It is a compound that has changed to acidic.

In general formula (PA-1),
Q represents -SO ₃ H, -CO ₂ H, or -W ₁ NHW ₂ R _f. Here, R _f represents an alkyl group, a cycloalkyl group, or an aryl group, and W ₁ and W ₂ each independently represent —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or —N (R _x ) R _y —. Here, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x may be bonded to R _y to form a ring, or may be bonded to R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.
Specific examples of the compound (PA) include the compounds exemplified in paragraph [0280] of US Patent Application Publication No. 2011/0269072.

  Moreover, in this invention, compounds (PA) other than the compound which generate | occur | produces the compound represented by general formula (PA-1) can also be selected suitably. For example, an ionic compound that has a proton acceptor moiety in the cation moiety may be used. More specifically, a compound represented by the following general formula (7) is exemplified.

In the formula, A represents a sulfur atom or an iodine atom.
m represents 1 or 2, and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3, and when A is an iodine atom, m + n = 2.
R represents an aryl group.
R _N represents an aryl group substituted with a proton acceptor functional group.
X ⁻ represents a counter anion.
Specific examples of X ⁻ include the same as the anion moiety of the photoacid generator.
Specific examples of the aryl group of R and R _N is a phenyl group are preferably exemplified.

Specific examples of the proton acceptor functional group R _N are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).
Specific examples of the ionic compound having a proton acceptor site in the cation moiety include the compounds exemplified in paragraph [0291] of US Patent Application Publication No. 2011/0269072.
Such a compound can be synthesized with reference to methods described in, for example, JP-A-2007-230913 and JP-A-2009-122623.

A compound (PA) may be used individually by 1 type, and may be used in combination of 2 or more type.
0.1-10 mass% is preferable with respect to the total solid of a composition, and, as for content of a compound (PA), 1-8 mass% is more preferable.

In the composition of the present invention, an onium salt that becomes a weak acid relative to the photoacid generator (A) can be used as an acid diffusion controller.
When the photoacid generator (A) and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the photoacid generator (A) are mixed and used, actinic radiation or radiation irradiation When the acid generated from the photoacid generator (A) collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

  The onium salt that is a weak acid relative to the photoacid generator (A) is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

In the formula, R ⁵¹ represents a hydrocarbon group which may have a substituent, and Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S). R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. Each of the M ⁺ is independently a sulfonium or iodonium cation.
Preferred examples of the sulfonium cation or iodonium cation represented by M ⁺ include the sulfonium cation represented by S ⁺ (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ) described above, I ⁺ (R ₂₀₄ ) (R ₂₀₅ ). The iodonium cation represented by these is mentioned.
Preferable examples of the anion moiety of the compound represented by the general formula (d1-1) include a structure exemplified in paragraph [0198] of JP2012-242799A.
Preferable examples of the anion moiety of the compound represented by the general formula (d1-2) include the structure exemplified in paragraph [0201] of JP2012-242799A.
Preferable examples of the anion moiety of the compound represented by the general formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.

An onium salt that is a weak acid relative to an acid generator is a compound that has a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety are linked by a covalent bond. Good.
The compound is preferably a compound represented by any one of the following general formulas (E-1) to (E-3).

In general formulas (E-1) to (E-3), R ₁ , R ₂ and R ₃ represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond linking the cation moiety and the anion moiety.
-X ^- it is, -COO ^-, -SO ₃ ^- represents an anion portion selected from ^{_{-R 4 -, -SO 2 -,}} -N. R ₄ has a carbonyl group: —C (═O) —, a sulfonyl group: —S (═O) ₂ —, and a sulfinyl group: —S (═O) — at the site of connection with the adjacent N atom. Represents a valent substituent.
R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In (E-3), two of R _{1 to} R ₃ may be combined to form a double bond with the N atom.
Examples of the substituent having 1 or more carbon atoms in R _{1 to} R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino group. A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.

L ₁ as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L ₁ is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

Preferable examples of the compound represented by the general formula (E-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [2013] of JP2013-8020A. The compounds exemplified in [0029] can be mentioned.
Preferable examples of the compound represented by the general formula (E-2) include compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.
Preferable examples of the compound represented by the general formula (E-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP 2012-252124 A.
The content of the onium salt that is a weak acid relative to the photoacid generator is preferably 0.5 to 10.0% by mass with respect to the total solid content of the composition, and is preferably 0.5 to 8%. More preferably, it is 0.0 mass%, and it is still more preferable that it is 1.0-8.0 mass%.

(Hydrophobic resin)
The composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (D)” or simply “resin (D)”), particularly when applied to immersion exposure. The hydrophobic resin (D) is preferably different from the resin (B).
As a result, the hydrophobic resin (D) is unevenly distributed in the film surface layer, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to.
The hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface as described above. However, unlike the surfactant, the hydrophobic resin (D) does not necessarily need to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.

The hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and it is more preferable to have two or more.
When the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin. , May be contained in the side chain.

When the hydrophobic resin (D) contains a fluorine atom, it is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. Preferably there is.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further a fluorine atom It may have a substituent other than.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .

  Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). However, at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ , and at least one of R _{65 to} R ₆₈ are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms).
R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include those exemplified in paragraph [0500] of US Patent Application Publication No. 2012/0251948.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH are preferred.
The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more.

The hydrophobic resin (D) may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in paragraph [0519] of US Patent Application Publication No. 2012/0251948.

Further, as described above, the hydrophobic resin (D) preferably includes a CH ₃ partial structure in the side chain portion.
Here, CH ₃ partial structure contained in the side chain moiety in the hydrophobic resin (D) (hereinafter, simply referred to as "side chain CH ₃ partial structure") The, CH ₃ partial structure an ethyl group, and a propyl group having Is included.
On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) is caused by the influence of the main chain on the surface of the hydrophobic resin (D). Since the contribution to uneven distribution is small, it is not included in the CH ₃ partial structure in the present invention.

More specifically, the hydrophobic resin (D) is a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In the case where R _{11 to} R ₁₄ are CH ₃ “as is”, the CH ₃ is not included in the CH ₃ partial structure of the side chain moiety in the present invention.
Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it has “one” CH ₃ partial structure in the present invention.

In the general formula (M),
R _{11 to} R ₁₄ each independently represents a side chain portion.
Examples of R _{11 to} R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.
Examples of monovalent organic groups for R _{11 to} R ₁₄ include alkyl groups, cycloalkyl groups, aryl groups, alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, cycloalkylaminocarbonyls. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The hydrophobic resin (D) is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (III).

  Hereinafter, the repeating unit represented by formula (II) will be described in detail.

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, more specifically, the organic group that is stable against an acid is preferably an organic group that does not have the “acid-decomposable group” described in the resin (B).

The alkyl group for X _b1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
X _b1 is preferably a hydrogen atom or a methyl group.

Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent.
R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.

  Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.

  The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

  Hereinafter, the repeating unit represented by formula (III) will be described in detail.

In the general formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an acid-stable organic group having one or more CH ₃ partial structures, n represents an integer of 1 to 5.
The alkyl group for X _b2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable. X _b2 is preferably a hydrogen atom.

Since R ₃ is an organic group that is stable against acid, more specifically, R ₃ is preferably an organic group that does not have the “acid-decomposable group” described in the hydrophobic resin (B).
R ₃ includes an alkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.

  n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

  Preferred specific examples of the repeating unit represented by the general formula (III) are shown below. Note that the present invention is not limited to this.

  The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

In the case where the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II), and The content of at least one repeating unit (x) among the repeating units represented by the general formula (III) is preferably 90 mol% or more based on all repeating units of the hydrophobic resin (D). More preferably, it is 95 mol% or more. The content is usually 100 mol% or less with respect to all repeating units of the hydrophobic resin (D).

  The hydrophobic resin (D) comprises at least one repeating unit (x) among the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III). ), The surface free energy of the hydrophobic resin (D) increases. As a result, the hydrophobic resin (D) is less likely to be unevenly distributed on the surface of the resist film, and the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved. it can.

Further, the hydrophobic resin (D) includes the following (x) to (z) even when (i) contains a fluorine atom and / or silicon atom, and (ii) contains a CH ₃ partial structure in the side chain portion. ) May have at least one group selected from the group of
(X) an acid group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
(Z) a group decomposable by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
As for content of the repeating unit which has an acid group (x), 1-50 mol% is preferable with respect to all the repeating units in hydrophobic resin (D), More preferably, it is 3-35 mol%, More preferably, it is 5- 20 mol%.

Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.

Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the acid-decomposable resin (B).
The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin (D). It is more preferably 3 to 98 mol%, and further preferably 5 to 95 mol%.

  In the hydrophobic resin (D), examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group exemplified in the resin (B). The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin (D), the content of the repeating unit having a group (z) that decomposes by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the resin (D). More preferably, it is 10-80 mol%, More preferably, it is 20-60 mol%.

  The hydrophobic resin (D) may further have a repeating unit represented by the following general formula (III).

In general formula (III):
R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a fluorine atom or a silicon atom.
L _c3 represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an alkylene group (preferably having a carbon number of 1 to 5), an ether bond, a phenylene group, or an ester bond (a group represented by —COO—).
The content of the repeating unit represented by the general formula (III) is preferably 1 to 100 mol%, and preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin (D). Is more preferable, and it is still more preferable that it is 30-70 mol%.

  It is also preferable that the hydrophobic resin (D) further has a repeating unit represented by the following general formula (CII-AB).

In general formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).
The content of the repeating unit represented by the general formula (CII-AB) is preferably 1 to 100 mol% with respect to all repeating units in the hydrophobic resin (D), preferably 10 to 90 mol%. More preferably, it is more preferably 30 to 70 mol%.

Specific examples of the repeating unit represented by the general formulas (III) and (CII-AB) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

When the hydrophobic resin (D) has a fluorine atom, the content of the fluorine atom is preferably 5 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin (D), and is 10 to 80% by mass. More preferably. Moreover, it is preferable that it is 10-100 mol% in all the repeating units contained in hydrophobic resin (D), and, as for the repeating unit containing a fluorine atom, it is more preferable that it is 30-100 mol%.
When the hydrophobic resin (D) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass, and 2 to 30% by mass with respect to the weight average molecular weight of the hydrophobic resin (D). More preferably. Moreover, it is preferable that the repeating unit containing a silicon atom is 10-100 mol% in all the repeating units contained in hydrophobic resin (D), and it is more preferable that it is 20-100 mol%.

On the other hand, particularly in the case where the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion, the hydrophobic resin (D) preferably has a form containing substantially no fluorine atom and silicon atom. Specifically, the content of the repeating unit having a fluorine atom or a silicon atom is preferably 5 mol% or less, preferably 3 mol% or less, based on all repeating units in the hydrophobic resin (D). Is more preferably 1 mol% or less, and ideally 0 mol%, that is, it does not contain a fluorine atom and a silicon atom. Moreover, it is preferable that hydrophobic resin (D) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is 95 mol% or more in all the repeating units of the hydrophobic resin (D). It is preferably 97 mol% or more, more preferably 99 mol% or more, and ideally 100 mol%.

The hydrophobic resin (D) may have a repeating unit represented by the general formula (nI) described in the resin (B) in that the effect of the present invention is more excellent.
The definition of the repeating unit represented by the general formula (nI) is as described above.
When the hydrophobic resin (D) contains a repeating unit represented by the general formula (nI), the content of the repeating unit represented by the general formula (nI) is the total repeating unit of the hydrophobic resin (D). The amount is preferably 10 to 60 mol%, more preferably 20 to 50 mol%.

The weight average molecular weight of the hydrophobic resin (D) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. is there.
In addition, the hydrophobic resin (D) may be used alone or in combination.
The content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, with respect to the total solid content in the composition, 7 mass% is still more preferable.

  The hydrophobic resin (D), like the resin (B), naturally has few impurities such as metals, and the residual monomer and oligomer components are preferably 0.01 to 5% by mass, more preferably. Is more preferably 0.01 to 3% by mass and 0.05 to 1% by mass. Thereby, a composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

  As the hydrophobic resin (D), various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.

  Specific examples of the hydrophobic resin (D) are shown below. The following table shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

(solvent)
The composition may contain a solvent.
Examples of the solvent that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, and lactone (preferably having 4 to 10 carbon atoms). ), An organic solvent such as a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate and the like.
Among these, a chain or cyclic ketone solvent or a lactone solvent is preferable because the effects of the present invention are more excellent. A cyclic ketone solvent or a lactone solvent is more preferable, and cyclohexanone or γ-butyrolactone is particularly preferable.
Specific examples of these solvents include those described in paragraphs [0441] to [0455] of US Patent Application Publication No. 2008/0187860.

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
The solvent containing a hydroxyl group and the solvent not containing a hydroxyl group can be selected as appropriate, but the solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether, alkyl lactate or the like, and propylene glycol monomethyl ether (PGME, also known as 1- Methoxy-2-propanol), ethyl lactate, and methyl-2-hydroxybutyrate are more preferable. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2 -Heptanone is most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.
As the solvent, it is preferable to use a solvent having a reduced peroxide content, thereby improving the storage stability of the resist composition. The content of the peroxide in the solvent is preferably 2.0 mmol% or less, more preferably 1.0 mmol% or less, still more preferably 0.5 mmol% or less, and the peroxide. It is particularly preferable that substantially no is contained.

(Surfactant)
The composition may or may not further contain a surfactant. When it is contained, fluorine and / or silicon surfactant (fluorine surfactant, silicon surfactant, fluorine atom and silicon atom It is more preferable to contain either one or two or more surfactants having both.

When the composition contains a surfactant, it is possible to provide a resist pattern with less adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph [0276] of US Patent Application Publication No. 2008/0248425.
In the present invention, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 may be used.

  These surfactants may be used alone or in several combinations.

When the composition contains a surfactant, the amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. is there.
On the other hand, by making the addition amount of the surfactant 10 ppm or less with respect to the total amount of the composition (excluding the solvent), the surface unevenness of the hydrophobic resin is increased, thereby making the resist film surface more hydrophobic. It is possible to improve water followability at the time of immersion exposure.

(Other)
The composition of the present invention may or may not contain a carboxylic acid onium salt. Examples of such carboxylic acid onium salts include those described in paragraphs [0605] to [0606] of US Patent Application Publication No. 2008/0187860.
These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

When the composition contains a carboxylic acid onium salt, the content is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably based on the total solid content of the composition. Is 1-7 mass%.
If necessary, the composition may further include an acid proliferator, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound that promotes solubility in a developer (eg, molecular weight). 1000 or less phenolic compounds, alicyclic or aliphatic compounds having a carboxyl group) and the like can be contained.

Such phenolic compounds having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.
Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

The composition of the present invention is preferably a resist film having a thickness of 80 nm or less from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
The solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and still more preferably 2.0 to 5.3% by mass. By setting the solid content concentration in the above range, the composition can be uniformly applied on the substrate, and further, a resist pattern having excellent line width roughness can be formed. The reason for this is not clear, but it is likely that the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, thereby aggregating the material in the resist solution, particularly the photoacid generator (A). As a result, it is considered that a uniform resist film was formed.
The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the composition.

  The composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably a mixed solvent, filtering the solution, and then applying the solution on a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.

  The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon irradiation with actinic rays or radiation. More specifically, the present invention relates to semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, production of imprint mold structures, and other photofabrication processes, lithographic printing plates, acid-curing properties. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used in the composition.

<Pattern formation method>
Next, the pattern forming method according to the present invention will be described.
The pattern forming method according to the present invention includes at least the following steps.
(A) Film forming step for forming a film (hereinafter also referred to as a resist film) with the composition (a) Exposure step for irradiating the film with actinic rays or radiation (c) Using the developer, the actinic rays or radiation Development process to develop the irradiated film

The exposure in the step (ii) may be immersion exposure.
The pattern formation method of the present invention preferably includes (i) a heating step after (b) the exposure step.
The pattern forming method of the present invention may include (a) an exposure step a plurality of times.
The pattern forming method of the present invention may include (d) a heating step a plurality of times.

The resist film of the present invention is formed from the above-described composition of the present invention, and more specifically, is preferably a film formed by applying the above composition to a substrate. In the pattern forming method of the present invention, the step of forming a film of the composition on the substrate, the step of exposing the film, and the developing step can be performed by generally known methods.
In the present invention, the substrate on which the film is formed is not particularly limited, and silicon, SiN, inorganic substrates such as SiO ₂ and SiN, coated inorganic substrates such as SOG, semiconductor manufacturing processes such as IC, liquid crystal, and thermal head For example, a substrate generally used in a circuit board manufacturing process or other photofabrication lithography process can be used. Furthermore, if necessary, an antireflection film may be formed between the resist film and the substrate. As the antireflection film, a known organic or inorganic antireflection film can be appropriately used.

It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
The heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

Although there is no restriction | limiting in the light source wavelength used for the exposure apparatus in this invention, Infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, an electron beam, etc. can be mentioned, Preferably it is 250 nm or less. More preferably 220 nm or less, particularly preferably far ultraviolet light having a wavelength of 1 to ₂₀₀ nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., KrF excimer laser, ArF excimer laser, EUV or electron beam are preferable, and ArF excimer laser is more preferable.

In the exposure process of the present invention, an immersion exposure method can be applied. The immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method.
When performing immersion exposure, (1) after forming the film on the substrate, before the exposure step and / or (2) after exposing the film via the immersion liquid, Prior to the heating step, a step of washing the surface of the membrane with an aqueous chemical may be performed.
The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
When water is used, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist film on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.
As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained.

On the other hand, when an opaque material or impurities whose refractive index is significantly different from that of water are mixed with 193 nm light, the optical image projected on the resist film is distorted. . Further, pure water filtered through an ion exchange filter or the like may be used.
The electrical resistance of the water used as the immersion liquid is preferably 18.3 MΩcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

The receding contact angle of the film (resist film) formed using the composition in the present invention is preferably 70 ° or more at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%, and when exposed through an immersion medium. It is more preferable that it is 75 degrees or more, and it is still more preferable that it is 75-85 degrees.
If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to achieve a preferable receding contact angle, it is preferable to include the hydrophobic resin (D) in the composition. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the resist film. The resin composition for forming a top coat preferably contains the above-described hydrophobic resin (D). The resin composition for forming a top coat may contain additives such as the photo acid generator and the basic compound described above. The exposure latitude is improved by adding a basic compound to the resin composition for forming a top coat.

  In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form an exposure pattern. The contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

As a developer used in the step of developing the resist film formed using the composition of the present invention, a developer containing an organic solvent (hereinafter also referred to as an organic developer) is used.
As the organic developer, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.

  Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

  Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, acetic acid Examples include isoamyl, butyl butanoate, and methyl-2-hydroxybutyrate.

  Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.

  Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.

  Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and undecane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used relative to the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.

In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .
The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-334540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

  The developer containing the organic solvent may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as those described above for the basic compound that can be contained in the composition.

  As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.

When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is preferably 2mL / sec / mm ² or less, more preferably 1.5mL / sec / mm ^2, more preferably not more than 1mL / sec / mm ^2. Although there is no particular lower limit of the flow rate, 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.

The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.
Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
Moreover, you may implement the process of stopping image development, after substituting with another solvent after the process developed using the developing solution containing an organic solvent.

It is preferable to include the process of wash | cleaning using a rinse liquid after the process developed using the developing solution containing an organic solvent.
The rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. . As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents should be used. Is preferred.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.

  More preferably, it contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents after the step of developing using a developer containing an organic solvent. A step of washing with a rinsing liquid is performed, more preferably, a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent is carried out, and particularly preferably, a rinsing liquid containing a monohydric alcohol is used. And, most preferably, the step of cleaning with a rinse solution containing a monohydric alcohol having 5 or more carbon atoms is performed.

  Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It can be.

A plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

  The vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

An appropriate amount of a surfactant can be added to the rinse solution.
In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The pattern forming method of the present invention uses both a step of developing using an alkali developer (alkali developing step) and a step of developing using an organic solvent-containing development (organic solvent developing step). can do. Thereby, a finer pattern can be formed.
In the present invention, a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by further performing the alkali development step. In this way, by the multiple development process in which development is performed a plurality of times, only the intermediate exposure intensity region can be left as a pattern without being dissolved, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975). The same mechanism as in paragraph [0077] of the publication).
The alkali development step can be performed either before or after the organic solvent development, but is more preferably performed before the organic solvent development step.

The present invention also relates to an electronic device manufacturing method including the above-described negative pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

  Examples are shown below, but the present invention is not limited thereto.

<Preparation of composition (resist composition)>
The components shown in Table 3 below are dissolved in the solvent shown in Table 3 in a solid content of 3.5% by mass, and each is filtered through a polyethylene filter having a pore size of 0.03 μm to obtain an actinic ray-sensitive or radiation-sensitive resin composition. A product (resist composition) was prepared.

The various components used in Table 3 are summarized below.
Various compounds such as the following resins A-1 to A-5, PAG-1 to PAG-5 are known literatures (for example, JP2011-252148, JP2009-258586, JP2010-256879). Etc.) and synthesized.

  In the said table | surface, a composition ratio shows the molar ratio of the repeating unit contained in resin A-1 to A-5 mentioned above, and shows the composition ratio of the repeating unit in chemical formula shown above in order from the left.

  In the above chemical formula, “F” represents the content of fluorine atoms in the anion [(total molecular weight of fluorine atoms / total molecular weight of anions) × 100].

  In the said table | surface, a composition ratio shows the molar ratio of the repeating unit contained in resin HR-1-HR-3 mentioned above, and shows the composition ratio of the repeating unit in chemical formula shown above in order from the left.

[solvent]
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: cyclohexanone SL-3: γ-butyrolactone

[Surfactant]
W-1: PF656 (made by OMNOVA)

<Evaluation>
(Pattern formation)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto the silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. The actinic ray-sensitive or radiation-sensitive resin composition shown in Table 3 was applied thereon and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.
The obtained wafer was used with an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection), and the hole portion was 45 nm. Pattern exposure was performed through a square array halftone mask having a pitch between holes of 90 nm (here, a portion corresponding to the holes was shielded for forming a negative image). Ultra pure water was used as the immersion liquid. Then, it heated at 105 degreeC for 60 second (PEB: Post Exposure Bake). Next, the film was developed by paddle with an organic solvent developer (butyl acetate) for 30 seconds, and rinsed by paddle with a rinse liquid (4-methyl-2-pentanol) for 30 seconds. Subsequently, the contact hole pattern with a hole diameter of 45 nm was obtained by rotating the wafer for 30 seconds at a rotational speed of 4000 rpm. In Example 14, a topcoat composition containing 2.5% by mass of the resin shown below, 0.5% by mass of the nitrogen-containing compound shown below, and 97% by mass of a 4-methyl-2-pentanol solvent was used. Using this, a top coat layer having a thickness of 100 nm was provided on the resist film, and then exposure and development were performed.

(Development defect evaluation)
For the silicon wafer on which the contact hole pattern was formed by the above-described method, the number of development defects was measured by a defect inspection apparatus KLA2360 (manufactured by KLA Tencor Co., Ltd.), and the number of development defects per unit area [cm ² ] was calculated. . A smaller value means better. The results are summarized in Table 3.

(Exposure latitude (EL))
The hole size is observed with a length-measuring scanning electron microscope (SEM, Ltd., Hitachi, Ltd. S-9380II), and the optimum exposure dose when resolving a contact hole pattern with a hole portion of 45 nm is expressed as sensitivity (E _opt ) (mJ / cm ² ). Based on the determined optimum exposure dose (E _opt ), the exposure dose when the hole size is the target value of 45 nm ± 10% (that is, 40.5 nm and 49.5 nm) was determined. Then, the exposure latitude (EL,%) defined by the following equation was calculated. The larger the value of EL, the better the performance change due to the change in exposure amount. The results are summarized in Table 3.
[EL (%)] = [[(exposure amount at which the hole portion is 40.5 nm) − (exposure amount at which the hole portion is 49.5 nm)] / E _opt ] × 100

(Pattern shape evaluation)
The cross-sectional shape of the contact hole pattern obtained by the method described above was observed using a scanning electron microscope, and the hole diameter Lb at the bottom of the resist pattern and the hole diameter La at the top of the resist pattern were measured. As the ratio of La to Lb (La / Lb) is closer to 1, the pattern shape is more preferable. Evaluation was performed by distinguishing the ratio between La and Lb (La / Lb) and the absolute value of 1 in the following five stages. The results are summarized in Table 3.
A: | 1- (La / Lb) | ≦ 0.05
B: 0.05 <| 1- (La / Lb) | ≦ 0.1
C: 0.1 <| 1- (La / Lb) | ≦ 0.15
D: 0.15 <| 1- (La / Lb) | ≦ 0.2
E: 0.2 <| 1- (La / Lb) |

As shown in Table 3, it was confirmed that when the pattern forming method of the present invention was used, a pattern having a shape with good exposure latitude, development characteristics, and pattern profile was formed.
Moreover, as understood from the comparison of Examples 1 to 4, when the resin (B) has a repeating unit represented by the general formula (VIII) (Example 4), it was confirmed that the above characteristics were more excellent.
As can be seen from a comparison between Example 1 and Examples 5 to 6, when the cation in the photoacid generator is a cation represented by formulas (C-2) to (C-3), It was confirmed that the characteristics were more excellent.
Further, as can be seen from a comparison between Example 1 and Example 7, a compound represented by the general formula (A-1) and a compound that generates an acid upon irradiation with an actinic ray or radiation different from the compound. When used in combination (Example 7), it was confirmed that the above properties were more excellent.
Further, as can be seen from the comparison between Example 1 and Example 10, it was confirmed that the above characteristics were more excellent when the solvent contained a lactone solvent (Example 1).
Further, as can be seen from a comparison between Example 1 and Example 11, it was confirmed that the above characteristics were more excellent when the solvent contained a ketone solvent (Example 1).
In addition, as can be seen from a comparison between Example 1 and Examples 12 to 13, as a basic compound, an onium salt that is relatively weak with respect to the photoacid generator (A), or a compound represented by the general formula (d- When using a basic compound having a protecting group constituting the carbamate group represented by 1) (Examples 12 and 13), it was confirmed that the above characteristics were more excellent.

  On the other hand, in Comparative Examples 1 and 2 in which the predetermined photoacid generator was not used and in Comparative Example 3 in which the predetermined resin (B) was not used, the above characteristics were inferior.

Claims (19)

(A) forming a film with an actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B):
(A) Compound that generates acid upon irradiation with actinic rays or radiation represented by general formula (A-1) (B) It has a repeating unit represented by general formula (nI), and the polarity is increased by the action of acid. A resin whose solubility in a developer containing an organic solvent is reduced (a) a step of irradiating the film with actinic rays or radiation, and
(C) A pattern forming method including a step of developing the film irradiated with the actinic ray or radiation using a developer containing an organic solvent.
(In General Formula (A-1), Q ¹ and Q ² each independently represent a hydrogen atom, a fluorine atom or an organic group, at least one of which is a fluorine atom or an alkyl substituted with at least one fluorine atom. P represents an integer of ^{1 to 3.} R ¹ and R ² each independently represents a hydrogen atom or an organic group, q represents an integer of 1 to 8. L ¹ represents a simple group. Represents a bond, —O—, —COO—, or —OCO—, L ² represents a single bond or a divalent linking group, and Y represents an optionally substituted cyclic group having 3 to 18 carbon atoms. (Z ¹⁺ represents a cation. In the anion in the general formula (A-1), the fluorine atom content is 0 to 20% by mass.)
(In the general formula (nI), R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, An alkylcarbonyl group, a group having a lactone structure, or a group having an acid-decomposable group, X ₁ and X ₂ each independently represents a methylene group, an ethylene group, an oxygen atom or a sulfur atom, and n is Represents an integer of 0 to 2.) The pattern formation method of Claim 1 whose compound represented by general formula (A-1) is a compound represented by the following general formula (A-2).
(In General Formula (A-2), R ¹ and R ² each independently represents a hydrogen atom or an organic group not substituted with fluorine. Q represents an integer of 1 to 8. L ² represents Represents a single bond or a divalent linking group, and Y represents a group having a cyclic structure having 3 to 18 carbon atoms which may have a substituent, a fluorine atom in the anion in formula (A-2) The content of is 0 to 20% by mass or less.Z ¹ represents a cation.)   The pattern forming method according to claim 1, wherein Y is a polycyclic aliphatic group. The pattern formation method according to claim 1, wherein in general formula (nI), at least one of R ₁₃ ′ to R ₁₆ ′ is a group having an acid-decomposable group. The pattern forming method according to claim 4, wherein the group having an acid-decomposable group is a group represented by * ¹ -L ³ -AD. L ³ represents an alkylene group. AD represents an acid-decomposable group. * ¹ represents a bonding position with the resin. The pattern formation method of any one of Claims 1-5 in which resin (B) has a repeating unit represented by the following general formula (VIII).

In (formula (VIII), Z ₂ represents, -O- or -N (R ₄₁₎ - .R ₄₁ representing a represents a hydrogen atom, a hydroxyl group, .R ₄₂ representing an alkyl group or -OSO ₂ -R ₄₂ is Represents an alkyl group, a cycloalkyl group, or a camphor residue, and the alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.   The actinic ray-sensitive or radiation-sensitive resin composition further contains a hydrophobic resin, and the content of the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive resin composition is 0.01 on a solids basis. The pattern formation method of any one of Claims 1-6 which is 10 mass%. The hydrophobic resin has at least one selected from the group consisting of a fluorine atom, a silicon atom, and a CH ₃ partial structure contained in a side chain portion of the hydrophobic resin. Pattern forming method. The pattern formation method of Claim 7 or 8 in which the said hydrophobic resin has a repeating unit represented by general formula (nI).
(In the general formula (nI), R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, An alkylcarbonyl group, a group having a lactone structure, or a group having an acid-decomposable group, X ₁ and X ₂ each independently represents a methylene group, an ethylene group, an oxygen atom or a sulfur atom, and n is Represents an integer of 0 to 2.)   The pattern forming method according to claim 1, wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a chain or cyclic ketone solvent.   The pattern forming method according to claim 1, wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a lactone solvent. The pattern forming method according to claim 1, wherein the Z ¹⁺ is any one of cations represented by general formulas (C-1) to (C-3).

(In General Formula (C-1), R ^{3 to} R ⁹ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom, or an organic group. Note that at least one of R ^{3 to} R ⁹ is R ¹⁰ and R ¹¹ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, a hydroxyl group, a carboxyl group, a halogen atom or an organic group. Represents an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group, and any two of R ^{3 to} R ⁷ may be bonded to each other to form a ring, and R ⁸ and R ⁹ , Or, R ¹⁰ and R ¹¹ may be bonded to each other to form a ring.)

(In the general formula (C-2), R ¹² and R ¹³ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. R ¹⁴ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, or a cycloalkyl group. R ¹⁵ represents a group, an alkoxy group, an alkoxycarbonyl group, a group having a monocyclic or polycyclic cycloalkyl skeleton, or an alkylene oxide chain, R ¹⁵ represents a hydroxyl group, a carboxyl group, a halogen atom, or an organic group. And represents an integer of 0 to 2. m15 represents an integer of 0 to 8. R ¹² and R ¹³ may be bonded to each other to form a ring.

(In General Formula (C-3), R ^{16 to} R ¹⁸ each independently represent a hydroxyl group, a carboxyl group, a halogen atom or an organic group. M16 to m18 each independently represents an integer of 0 to 5. Any two of R ^{16 to} R ¹⁸ may be bonded to each other to form a ring, and at least one of m 16 to m 18 represents an integer of 1 or more.)   The actinic ray-sensitive or radiation-sensitive resin composition is different from the compound that generates an acid upon irradiation with an actinic ray or radiation represented by the general formula (A-1). The pattern formation method of any one of Claims 1-12 containing the compound which generate | occur | produces.   The actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to claim 1, further comprising a hydrophobic resin. The actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to claim 1, further comprising a chain or cyclic ketone solvent,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein Z ¹⁺ is any one of cations represented by general formulas (C-1) to (C-3).

(In General Formula (C-1), R ^{3 to} R ⁹ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom, or an organic group. Note that at least one of R ^{3 to} R ⁹ is R ¹⁰ and R ¹¹ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, a hydroxyl group, a carboxyl group, a halogen atom or an organic group. Represents an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group, and any two of R ^{3 to} R ⁷ may be bonded to each other to form a ring, and R ⁸ and R ⁹ , Or, R ¹⁰ and R ¹¹ may be bonded to each other to form a ring.)

(In the general formula (C-2), R ¹² and R ¹³ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. R ¹⁴ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, or a cycloalkyl group. R ¹⁵ represents a group, an alkoxy group, an alkoxycarbonyl group, a group having a monocyclic or polycyclic cycloalkyl skeleton, or an alkylene oxide chain, R ¹⁵ represents a hydroxyl group, a carboxyl group, a halogen atom, or an organic group. And represents an integer of 0 to 2. m15 represents an integer of 0 to 8. R ¹² and R ¹³ may be bonded to each other to form a ring.

(In General Formula (C-3), R ^{16 to} R ¹⁸ each independently represent a hydroxyl group, a carboxyl group, a halogen atom or an organic group. M16 to m18 each independently represents an integer of 0 to 5. Any two of R ^{16 to} R ¹⁸ may be bonded to each other to form a ring, and at least one of m 16 to m 18 represents an integer of 1 or more.) The actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to claim 1, further comprising a lactone solvent,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein Z ¹⁺ is any one of cations represented by general formulas (C-1) to (C-3).

(In General Formula (C-1), R ^{3 to} R ⁹ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom, or an organic group. Note that at least one of R ^{3 to} R ⁹ is R ¹⁰ and R ¹¹ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, a hydroxyl group, a carboxyl group, a halogen atom or an organic group. Represents an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group, and any two of R ^{3 to} R ⁷ may be bonded to each other to form a ring, and R ⁸ and R ⁹ , Or, R ¹⁰ and R ¹¹ may be bonded to each other to form a ring.)

(In the general formula (C-2), R ¹² and R ¹³ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. R ¹⁴ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, or a cycloalkyl group. R ¹⁵ represents a group, an alkoxy group, an alkoxycarbonyl group, a group having a monocyclic or polycyclic cycloalkyl skeleton, or an alkylene oxide chain, R ¹⁵ represents a hydroxyl group, a carboxyl group, a halogen atom, or an organic group. And represents an integer of 0 to 2. m15 represents an integer of 0 to 8. R ¹² and R ¹³ may be bonded to each other to form a ring.

(In General Formula (C-3), R ^{16 to} R ¹⁸ each independently represent a hydroxyl group, a carboxyl group, a halogen atom or an organic group. M16 to m18 each independently represents an integer of 0 to 5. Any two of R ^{16 to} R ¹⁸ may be bonded to each other to form a ring.)   It is the said actinic-ray-sensitive or radiation-sensitive resin composition used for the pattern formation method of Claim 1, Comprising: Furthermore, it is acid by irradiation of the actinic ray or radiation represented by the said general formula (A-1). An actinic ray-sensitive or radiation-sensitive resin composition containing a compound capable of generating an acid upon irradiation with an actinic ray or radiation different from the compound that generates an acid.   The manufacturing method of an electronic device containing the pattern formation method of any one of Claims 1-13.   An electronic device manufactured by the electronic device manufacturing method according to claim 18.