KR20160059951A - Method for forming pattern, actinic-ray-sensitive or radiation-sensitive resin composition used therefor, and, method for producing the electronic device using them - Google Patents

Abstract

The present invention provides a method for forming a pattern having good light exposure latitude, developing properties, and pattern profile, an actinic ray-sensitive or radiation-sensitive resin composition used for the same, an electronic device using the same, and a method for producing the electronic device. The method for forming a pattern comprise the steps of: (A) forming a film by an actinic ray-sensitive or radiation-sensitive resin composition containing a resin in which solubility with respect to a developing solution including an organic solvent is decreased because polarity is increased by reaction of a compound represented by formula (A-1) and acid having a recurring unit represented by formula (n I); (B) irradiating actinic light or radiation onto the film; and (C) developing the film onto which actinic light or radiation is irradiated by using a developing solution including an organic solvent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming method, a pattern forming method using the same, a sensitizing actinic radiation or radiation-sensitive resin composition used therefor, and a manufacturing method of an electronic device using the same. PRODUCING THE ELECTRONIC DEVICE USING THEM}

The present invention relates to a pattern forming method, a sensitizing actinic ray or radiation-sensitive resin composition used therefor, a method of producing an electronic device 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 IC, a process for producing a circuit substrate such as a liquid crystal and a thermal head, or a lithography process for other photofabrication, Or radiation-sensitive resin composition, a method of manufacturing an electronic device using the same, and an electronic device. Particularly, the present invention relates to a pattern forming method suitable for exposure in an ArF exposure apparatus and an ArF immersion projection exposure apparatus using a deep ultraviolet light having a wavelength of 300 nm or less as a light source, a method of forming a light- A resin composition, a method for producing an electronic device, and an electronic device.

BACKGROUND ART [0002] In the manufacturing process of a semiconductor device such as an IC or an LSI, microfabrication by lithography using a photoresist composition is conventionally performed.

Recently, a pattern forming method using a developing solution (organic developing solution) containing an organic solvent has also been developed (Patent Document 1).

Japanese Patent Application Laid-Open No. 2011-123469

On the other hand, in recent years, various kinds of electronic devices have been required to be highly functional, and accordingly, there is a further demand for improvement in the characteristics of resist patterns used for microfabrication. In particular, when attempting to form a finer contact hole pattern, problems such as insufficient exposure latitude (EL: Exposure Latitude), development defects, pattern profile deterioration, etc. are likely to occur, and it is required to improve the resist performance.

As a result of evaluating the various characteristics using the pattern forming method described in Patent Document 1, the present inventors satisfied the conventional required level, but the required level was not satisfied, and further improvement was required.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a pattern forming method capable of forming a pattern having good exposure latitude, development characteristics, and pattern profile in consideration of the above-described circumstances.

It is another object of the present invention to provide a sensitizing actinic radiation-sensitive or radiation-sensitive resin composition used therefor, an electronic device using the same, and a process for producing the same.

The inventors of the present invention have made intensive investigations into the problems of the prior art. As a result, the present inventors have found that a developing solution containing an organic solvent can be used for developing treatment by using a sensitizing actinic ray or radiation-sensitive resin composition containing a predetermined resin and a predetermined photoacid generator The above problems can be solved.

That is, it has been found that the above object can be achieved by the following constitution.

(1) A process for producing a film comprising the steps of: (A) forming a film by a sensitizing actinic ray or radiation-sensitive resin composition containing (A) and (B)

(A) a compound capable of generating an acid by irradiation with an actinic ray or radiation represented by the following general formula (A-1)

(B) a resin having an increased polarity due to the action of an acid having a repeating unit represented by the following general formula (nI) and having reduced solubility in a developer containing an organic solvent

(B) a step of irradiating the film with an actinic ray or radiation, and

(C) a step of developing the film irradiated with an actinic ray or radiation using a developer containing an organic solvent.

(2) The pattern forming method according to (1), wherein the compound represented by the general formula (A-1) is a compound represented by the general formula (A-2) described later.

(3) The pattern forming method according to (1) or (2), wherein Y is a polycyclic aliphatic group.

(4) The pattern forming method according to any one of (1) to (3), wherein at least one of R ₁₃ 'to R ₁₆ ' in the general formula (nI) is a group having an acid-

(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 indicates the bonding position with the resin.

(6) The pattern forming method according to any one of (1) to (5), wherein the resin (B) has a repeating unit represented by the following general formula (VIII).

(7) The photosensitive resin composition according to any one of (1) to (6), wherein the sensitizing actinic ray or radiation-sensitive resin composition further comprises a hydrophobic resin, and the hydrophobic resin in the actinic ray- Wherein the content is 0.01 to 10% by mass based on the solid content.

(8) The pattern forming method according to (7), wherein 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 the side chain portion of the hydrophobic resin.

(9) The pattern forming method according to (7) or (8), wherein the hydrophobic resin has a repeating unit represented by the following general formula (nI).

(10) The pattern forming method according to any one of (1) to (9), wherein the sensitizing actinic radiation-sensitive or radiation-sensitive resin composition further comprises 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 comprises a lactone solvent.

(12) The pattern forming method 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) .

(13) The photosensitive resin composition according to any one of (1) to (12), wherein the actinic ray-sensitive or radiation-sensitive resin composition generates an acid by irradiation of an actinic ray or radiation represented by the following general formula (A- A compound capable of generating an acid upon irradiation with an actinic ray or radiation different from the compound which causes the compound to form a pattern.

(14) The actinic ray-sensitive or radiation-sensitive resin composition for use in the pattern-forming method according to (1), further comprising a hydrophobic resin.

(15) The actinic ray-sensitive or radiation-sensitive resin composition for use in the pattern forming method according to (1), further comprising a chain or cyclic ketone solvent,

And Z < ^{1 +} > is any one of cations represented by the following general formulas (C-1) to (C-3).

(16) The actinic ray-sensitive or radiation-sensitive resin composition for use in the pattern forming method according to (1), further comprising a lactone-based solvent,

And Z < ^{1 +} > is any one of cations represented by the following general formulas (C-1) to (C-3).

(17) A sensitizing actinic radiation-sensitive or radiation-sensitive resin composition for use in the pattern forming method according to (1), which comprises an acid generator which generates an acid by irradiation with an actinic ray or radiation represented by the general formula (A- Wherein the composition further contains a compound capable of generating an acid upon irradiation with an actinic ray or radiation different from the compound.

(18) A method of manufacturing an electronic device, comprising 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).

(Effects of the Invention)

According to the present invention, it is possible to provide a pattern forming method capable of forming a pattern having a good pattern of exposure latitude, development characteristics, and pattern profile.

Further, according to the present invention, it is possible to provide a sensitizing actinic ray or radiation-sensitive resin composition used therefor, an electronic device using the same, and a process for producing the same.

Hereinafter, embodiments of the present invention will be described in detail.

In the present specification, the notation in which the substituent and the non-substituent are not described in the notation of the group (atomic group) includes those having no substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term " active ray " or " radiation " in this specification means, for example, a line spectrum of a mercury lamp, far ultraviolet ray represented by an excimer laser, extreme ultraviolet ray (EUV light), X ray, electron beam (EB) In the present invention, light means an actinic ray or radiation.

"Exposure" in this specification refers to not only exposure by deep ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers but also drawing by particle lines such as electron beams and ion beams, .

In this specification, "(meth) acrylic monomer" means and at least one kind of monomer having a structure of "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- ". 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 the present specification, the term "organic group" means a functional group containing at least one carbon atom (for example, an alkyl group, a cycloalkyl group, an aryl group or a group formed by combining these), and includes a hetero atom , Oxygen atom) may be included.

The characteristic feature of the present invention is that a resin containing a repeating unit having a norbornane skeleton in its main chain and a composition containing a predetermined photoacid generator are used for development with an organic solvent. More specifically, first, the norbornane skeleton is contained in the resin so that the resin becomes rigid, and the diffusibility of the photoacid generator in the film is suppressed, resulting in a desired effect. When the content of fluorine atoms in the photoacid generator is less than the predetermined value, the photoacid generator is uniformly dispersed in the resist film because the driving force for localizing the photoacid generator on the surface of the resist film becomes small, and the pattern shape and EL are improved. When the above-mentioned resin containing a repeating unit having a norbornane skeleton in the main chain and the photoacid generator are combined, the pattern shape at the time of the formation of the contact hole pattern and the EL It is remarkably improved. In addition, embodiments in which the hydrophobic resin to be described later is included in the actinic ray-sensitive or radiation-sensitive resin composition are more excellent in all of the above characteristics.

The pattern forming method of the present invention has the following steps (a) to (c).

(A) a step of forming a film by a sensitizing actinic ray-sensitive or radiation-sensitive resin composition containing (A) and (B)

(A) a compound which generates an acid by irradiation with an actinic ray or radiation represented by the general formula (A-1)

(B) a resin having an increased polarity due to the action of an acid having a repeating unit represented by the general formula (nI) and having reduced solubility in a developer containing an organic solvent

(B) a step of irradiating the film with an actinic ray or radiation

(C) a step of developing the film irradiated with an actinic ray or radiation using a developer containing an organic solvent

Hereinafter, the components contained in the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, simply referred to as "composition") used in the step (A) will be described in detail and then the order of each step Will be described in detail.

≪ Compounds which generate an acid by irradiation with an actinic ray or radiation represented by the general formula (A-1)

The composition is also referred to as a compound which generates an acid by irradiation of an actinic ray or radiation represented by the general formula (A-1) (hereinafter referred to as a "photoacid generator (A)" or "a compound represented by the general formula (A- Quot;).

Hereinafter, each group in the compound represented by formula (A-1) will be described in detail.

In 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 represents an alkyl group substituted by a fluorine atom or at least one fluorine atom.

As organic groups represented by Q ¹ and Q ² , CF ₃ and the like are preferably used.

Of these, Q ¹ and Q ² each independently represent a fluorine atom or at least one (preferably one or more) fluorine atoms from the point of superiority of at least one of exposure latitude, developing property and pattern profile (hereinafter also appropriately referred to as " More preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ , particularly preferably a fluorine atom.

The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Examples of the alkyl groups, for example _{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, 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 CH ₂ C ₄ F, and the like.

L ¹ represents a single bond, -O-, -COO- or OCO-. Among them, a single bond or * ¹ -COO- * ² group (* ¹ is bonded to (CQ ¹ Q ² ) _p and * ² is bonded to (CR ¹ R ² ) _q from the point of more excellent effects of the present invention ).

R ¹ and R ² each independently represent a hydrogen atom or an organic group.

Examples of the organic groups represented by R ¹ and R ² include an alkyl group and a cycloalkyl group.

Of these, R ¹ and R ² are each independently a hydrogen atom or an alkyl group, and more preferably a hydrogen atom, in that the effect of the present invention is more excellent.

The alkyl group may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent of R ¹ and R ² include the groups exemplified as the alkyl groups of 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 -, an alkylene group (Preferably having from 1 to 6 carbon atoms), a cycloalkylene group (preferably having from 3 to 10 carbon atoms), an alkenylene group (preferably having from 2 to 6 carbon atoms), or a divalent linking group combining a plurality of these groups have. Of these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO- alkylene-, -CONH- - or -NHCO-alkylene group is preferable, and -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene group or -OCO-alkylene group is more preferable. Particularly, it is more preferable that L ² is * ¹ -OCO- * ² group (bonded to (CR ¹ R ² ) _q at * ¹ and bound 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.

The number of carbon atoms is preferably from 6 to 15, more preferably from 10 to 12, since the effect of the present invention is more excellent.

The cyclic aliphatic group (alicyclic hydrocarbon group) as Y may have a monocyclic structure or may have a polycyclic structure. As the cyclic aliphatic group having a monocyclic structure, monocyclic cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cyclooctyl group are preferable. Examples of the cyclic aliphatic group (polycyclic aliphatic group) having a polycyclic structure include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

Particularly, Y is preferably a polycyclic aliphatic group and more preferably an adamantyl group because the effect of the present invention is more excellent.

p represents an integer of 1 to 3; Among them, 1 or 2 is preferable, and 1 is more preferable because the effect of the present invention is more excellent.

q represents an integer of 1 to 8; Among them, 1 to 3 is preferable, 1 or 2 is more preferable, and 1 is particularly preferable because the effect of the present invention is more excellent.

The content of fluorine atoms in the anion (sulfonic acid anion) in the general formula (A-1) is 0 to 20 mass%. Among them, the fluorine atom content is preferably from 1 to 18 mass%, more preferably from 3 to 15 mass%, from the viewpoint that the effect of the present invention is more excellent.

If the content of fluorine atoms is outside the above range, the effect of the present invention is inferior.

The anion (sulfonic acid anion) is intended to ^mean a moiety other than Z ¹⁺ (anion moiety) in the general formula (A-1).

The content of fluorine atoms is intended to mean the ratio of the total molecular weight of the fluorine atoms in the anion to the total molecular weight of the anions (total molecular weight of fluorine atoms / total molecular weight of anions). For example, when the total molecular weight of the anion is 380 and two fluorine atoms are contained in the anion, the content of the fluorine atom is 10 mass% [(19 x 2/380) x 100].

Z ¹⁺ represents a cation.

The cation includes, for example, an onium cation, a sulfonium cation, an iodonium cation, an ammonium cation, a benzothiazolium cation, and a phosphonium cation. Among them, a sulfonium cation and an iodonium cation are preferable, and an arylsulfonium cation is more preferable.

Among them, the cation represented by the following general formulas (C-1) to (C-3) is preferable in that the effect of the present invention is more excellent. Hereinafter, general formulas (C-1) to (C-3) will be described in detail.

In the general formula (C-1), R ³ to R ⁹ each independently represent a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom or an organic group. At least one of R ³ to R ⁹ represents a hydroxyl group, a carboxyl group, a halogen atom or an organic group.

R ³ to R ⁷ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, A nitro group, an alkylthio group or an arylthio group.

Also, it is preferable that R ⁸ and R ⁹ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

R ¹⁰ and R ¹¹ each independently represent 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.

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. In addition, the ring structure may contain an oxygen atom, a sulfur atom, a ketone group, an ester bond or an amide bond.

Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. The ring structure may be a 3- to 10-membered ring, preferably a 4- to 8-membered ring, more preferably a 5-membered or 6-membered ring.

R ³ to R ¹¹ may further have a substituent and 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 cycloalkyl group, An alkoxy group, an aryloxy group, an acyl group, an arylcarbonyl group, an alkoxyalkyl group, an aryloxyalkyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonyloxy group, and an aryloxycarbonyloxy group.

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

In the general formula (C-2), R ¹² and R ¹³ each independently represent 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 contain a hetero atom 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 preferably 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. When there are a plurality of R < ¹⁵ >, they may be the same or different.

The alkyl group of R ¹² to R ¹⁵ is preferably a linear or branched alkyl group having 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 groups represented by R ¹⁴ to R ¹⁵ are preferably linear or branched and preferably have 1 to 10 carbon atoms.

The alkoxycarbonyl group represented by R ¹⁴ to R ¹⁵ is preferably linear or branched and preferably has 2 to 11 carbon atoms.

The group having a cycloalkyl group represented by R ¹⁵ includes a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

As the alkyl group of the alkylcarbonyl group of R ¹⁵ , specific examples similar to the above alkyl groups can be mentioned.

The alkylsulfonyl group and cycloalkylsulfonyl group for R ¹⁵ are preferably linear, branched or cyclic, and preferably have 1 to 10 carbon atoms.

Examples of the substituent which 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.

R ¹² and R ¹³ may be bonded to each other to form a ring, and as the ring structure to be formed, 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 , A tetrahydrothiophene ring or a 2,5-dihydrothiophene ring), and may be ring-fused with an aryl group or a cycloalkyl group. The cyclic 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 alkoxycarbonyloxy group . A plurality of substituents for the ring structure may be present, or they may be bonded to each other to form a ring.

R ¹² and R ¹³ as methyl group, an ethyl group, a naphthyl group, and R ¹² and R ¹³ are combined with each other and are a divalent group, and the like to form a tetrahydro-thiophene-ring structure with a sulfur atom, preferably, R ¹² and R ¹³ are each Particularly preferred are divalent groups which combine to form a tetrahydrothiophene ring structure together with the sulfur atom.

r represents an integer of 0 to 2; Among them, 0 or 1 is preferable, and 1 is more preferable.

m15 represents an integer of 0 to 8; Of these, 0 to 2 are preferred.

The cations represented by the general formula (C-2) are exemplified below.

Hereinafter, general formula (C-3) will be described in detail.

In the 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.

Among them, R ¹⁶ to R ^{18 preferably} represent 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. In addition, the ring structure may contain 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; Among them, 1 to 3 is preferable, and 1 is more preferable.

At least one of m16 to m18 represents an integer of 1 or more.

The cations represented by the general formula (C-3) are exemplified below.

As a preferable embodiment of the compound represented by the above-mentioned general formula (A-1), a compound represented by the following general formula (A-2) (photo acid generator) is more excellent in the effect of the present invention.

In addition, the definitions and suitable forms of each group in the above general formula (A-2) are as described above.

The photoacid generator (A) can be synthesized by a known method, and can be synthesized in accordance with the method described in, for example, Japanese Patent Application Laid-Open No. 2007-161707.

The photoacid generators (A) may be used singly or in combination of two or more.

The content of the photoacid generator (A) in the composition is not particularly limited, but is preferably 12 to 30% by mass, more preferably 12 to 20% by mass, based on the total solid content in the composition, Do.

Further, the total solids is intended to mean the total mass of components constituting the resist film to be described later, and other components excluding the solvent.

<Resins whose polarity is increased by the action of an acid having a repeating unit represented by formula (nI) and the solubility in a developer containing an organic solvent is reduced>

(Hereinafter referred to as &quot; acid-decomposable resin &quot; or &quot; resin (B) &quot;) in which the polarity increases due to the action of an acid having a repeating unit represented by formula (nI) &Quot;).

It is preferable that the resin (B) has a group which is decomposed by the action of an acid to generate a polar group (hereinafter also referred to as &quot; acid decomposable group &quot;) in both the main chain or side chain or the main chain and side chain of the resin.

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

In the general formula (nI)

R ₁₃ 'to R ₁₆ ' each independently represents a group having 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, Lt; / RTI &gt;

X ₁ and X ₂ each independently represent a methylene group, an ethylene group, an oxygen atom or a sulfur atom. Preferably a methylene group.

and n represents an integer of 0 to 2. Preferably 0 to 1.

The acid-decomposable group in the group having an acid-decomposable group as R ₁₃ 'to R ₁₆ ' is a group which is decomposed by the action of an acid to generate a polar group and is protected by a group capable of decomposing and leaving the polar group by the action of an acid Is preferable.

The polar group is not particularly limited as long as it is a group which is hardened or insolubilized in a developing solution containing an organic solvent. However, the polar group is preferably a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, (Alkylsulfonyl) methylene group, a bis (alkylcarbonyl) methylene group, a bis (alkylcarbonyl) imide group, a bis (Alkyl sulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group and tris (alkylsulfonyl) methylene group A group dissociated in an aqueous tetramethylammonium hydroxide solution) or an alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring. An aliphatic alcohol having a hydroxyl group substituted with an electron-attracting group such as a fluorine atom , Fluorinated alcohol group (hexafluoroisopropanol group, etc.)) are excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of 12 or more and 20 or less.

Preferable examples of the polar group include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

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 by an acid.

The group that desorbed by an acid, for example, _{-C (R 36) (R 37} ) (R 38), -C (R 36) (R 37) (OR 39), -C (R 01) (R 02 ) (OR ₃₉ ).

In the formula, R ₃₆ to R ₃₉ each independently represent 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 represent 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, and examples thereof include a methyl group, ethyl group, propyl group, n-butyl group, sec- .

The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. As the monocyclic group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and a polycyclic group is preferably a cycloalkyl group having 6 to 20 carbon atoms. Further, at least one carbon atom in the cycloalkyl group may be substituted by a hetero atom 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). As the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group are preferable. 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.

As the acid-decomposable group preferably a cumyl ester group, an enol ester group, an acetal ester group, a group and the like of the tertiary alkyl ester, a third that is more preferably represented by -C (= O) -OR ₀ Lt; / RTI &gt; alkyl ester group.

Examples of R _{0 in the} formula include a tertiary alkyl group such as a t-butyl group and a t-amyl group, an isobornyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, a 1-cyclohexyloxyethyl group, An alkoxymethyl group such as a 1-alkoxyethyl group, a 1-methoxymethyl group and a 1-ethoxymethyl group, a 3-oxoalkyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a trialkylsilyl ester group, a 3-oxocyclohexyl ester group , 2-methyl-2-adamantyl group, mevalonic lactone residue and the like.

The group having an acid-decomposable group is preferably a group represented by * ¹ -L ³ -AD in view of further inhibiting the diffusion of the generated acid.

L ³ represents an alkylene group which may have a substituent. The number of carbon atoms contained in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 2 to 8. Examples of the substituent include a hydroxyl group and an alkoxy group.

The alkylene group represented by L ³ may contain a hetero atom. That is, a hetero atom-containing alkylene group. The kind of the heteroatom 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 _{2 t} -, -SO ₂ N (R _c ) -, a halogen atom, or a combination of two or more of these groups.

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 preferable from the viewpoint of easier handling.

Each of R _a , R _b and R _c is independently selected from a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. and 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 indicates the bonding position with the resin.

From the standpoint of improving the dissolution contrast, it is preferable that at least one of R ₁₃ 'to R ₁₆ ' is 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 oxo atom.

The alkyl group represented by R ₁₃ 'to R ₁₆ ' is more preferably a group represented by the following formula (F1).

Among the general formula (F1)

Each of R ₅₀ to R ₅₅ independently represents a hydrogen atom, a fluorine atom or an alkyl group. Provided that 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), and is preferably a hydrogen atom.

It is preferable that all of R ₅₀ to R ₅₅ are a fluorine atom.

The content of the repeating unit represented by the general formula (nI) is not particularly limited, but is preferably 5 to 50 mol%, more preferably 10 to 40 mol% based on the total repeating units in the resin (B) Mol, more preferably 15 to 35 mol%.

The following specific examples can be given as the repeating unit represented by the above general formula (nI), but the present invention is not limited to these compounds. Among them, the repeating units represented by (II-f-16) to (II-f-19) are 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 preferably 5 to 60 mol%, more preferably 15 to 55 mol% based on the total repeating units in the resin (B) Mol, more preferably from 30 to 50 mol%.

The resin (B) preferably contains a repeating unit represented by the general formula (nI) and a repeating unit represented by the general formula (VIII). This improves the adhesion of the resist film to the substrate.

As the repeating unit represented by the above general formula (VIII), there may be mentioned the following specific examples, but the present invention is not limited thereto.

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

In the 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 represent an alkyl group (straight chain or branched chain) 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 methyl group or a group represented by -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 not more than 5 carbon atoms and an acyl group having not more than 5 carbon atoms, Alkyl group, more preferably a methyl group. In one embodiment, Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

Examples of the divalent linking group of T include an alkylene group, -COO-Rt- group, -O-Rt- group and the like. Wherein Rt represents an alkylene group or a cycloalkylene group.

T is a single bond or -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 preferably has 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.

As the cycloalkyl group represented by R x ₁ to R x ₃ , a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group is preferable .

Examples of the cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ include a monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group Cycloalkyl groups are preferred. And 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 may be substituted with a group in which one of the methylene groups constituting the ring is a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

The repeating unit represented by formula (AI) is preferably an embodiment wherein Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above cycloalkyl group.

Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms) And the number of carbon atoms is preferably 8 or less.

The content of the repeating units having an acid-decomposable group is preferably 20 to 80 mol%, more preferably 25 to 75 mol%, and more preferably 30 to 70 mol%, based on the total repeating units in the resin (B) , And most preferably 20 to 50 mol%.

As specific examples of the resin (B), there may be mentioned the specific examples disclosed in U.S. Patent Application Publication No. 2012/0135348 [0265], but the present invention is not limited thereto.

The resin (B) is a resin having a repeating unit represented by the general formula (AI), for example, a resin having at least any one of a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) More preferable.

In the 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 represent 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 &lt; _{2 &gt;} is bonded.

R ₁ and R ₃ preferably represent a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. Specific examples of the monovalent organic group in R ₁₁ examples and preferable examples are the same as those described in R ₁₁ in the formula (AⅠ).

The alkyl group in R ₂ may be linear or branched or may have a substituent.

The cycloalkyl group for 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 from 1 to 10 carbon atoms, more preferably from 1 to 5 carbon atoms, 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 number of carbon atoms 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, branched or 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. As the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group are preferable.

Examples of the substituent which each group may have include the same groups as described above as the substituent which each group in general formula (AI) may have.

It is more preferable that 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).

The number of the repeating units having an acid-decomposable group contained in the resin (B) may be one or two or more. When used in combination, the specific examples disclosed in paragraph [0287] of the specification of U.S. Patent Application Publication No. 2012/0135348 may 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 sulfonic acid ester) structure.

The lactone or sultone group may be any lactone structure or sultone structure as long as it has a lactone structure or a sultone structure, but preferably has a lactone structure or sultone structure of a 5- to 7-membered ring, and has a lactone structure or sultone structure of a 5- to 7- It is preferable that the other ring structure is coordinated in the form of forming the structure. (LC1-1) to (LC1-17) disclosed in paragraph [0318] of United States Patent Application Publication No. 2012/0135348 and any one of the following general formula (SL1-1) and general formula (SL1-2) It is more preferable to have a repeating unit having a lactone structure or a lactone structure. The lactone structure or the sultone structure may be bonded directly 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 a sultone structure, LWR and development defects are improved.

The lactone structure moiety or the sultone structure moiety may or may not have a substituent (Rb ₂ ). When n ₂ is 2 or more, the plurality of substituents (R b ₂ ) present may be the same or different, and a plurality of substituents (R b ₂ ) present may bond to each other to form a ring.

The resin (B) preferably has a repeating unit having a hydroxyl group or cyano group other than the general formula (AI). This improves substrate adhesion and developer affinity. 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. Preferred examples of the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group are partial structures represented by the following general formulas (VIIa) to (VIId).

In the general formulas (VIIa) to (VIIc)

R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. However, R ₂ at least one of c ~ R ₄ c represents a hydroxyl group or a cyano group. Preferably two of R _2, R ₄ c ~ c a hydroxyl group, and the remaining is a hydrogen atom. In formula (VIIa), _two of R ₂ c to R ₄ c are more preferably a hydroxyl group and the remainder are hydrogen atoms.

Examples of the repeating unit having a partial structure represented by formulas (VIIa) to (VIId) include repeating units represented by the following formulas (AIIa) to (IId).

In the formulas (AIIa) to (IId)

R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c ~ R ₄ c are the same as R ₂ c ~ c R ₄ in the formula (Ⅶa) ~ (Ⅶc).

The content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, and still more preferably 10 to 25 mol% based on the total repeating units in the resin (B) .

Specific examples of the repeating unit having a hydroxyl group or a cyano group include the repeating units disclosed in United States Patent Application Publication No. 2012/0135348 [0340], but the present invention is not limited thereto.

The resin (B) may have various repeating structural units in addition to the above repeating structural units in order to control dry etching resistance, standard developer suitability, substrate adhesion, resist profile and resolution, which are generally required properties of resist, such as resolution, heat resistance and sensitivity .

Such repeating structural units include repeating structural units corresponding to the following monomers, but are not limited thereto.

(1) the solubility in a coating solvent, (2) the film formability (glass transition point), (3) the developability of the alkali, (4) (5) the adhesion of the unexposed portion to the substrate, and (6) the dry etching resistance can be finely adjusted.

Examples of such monomers include monomers having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, Compounds and the like.

In addition, an addition-polymerizable unsaturated compound capable of copolymerizing with the monomer corresponding to the various repeating structural units may be copolymerized.

The molar ratio of the repeating structural units in the resin (B) is appropriately set so as to control the dry etching resistance of the resist, the standard developer aptitude, the substrate adhesion, the resist profile, and the general required performance of the resist, such as resolution, heat resistance and sensitivity .

From the viewpoint of transparency to ArF light 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. More specifically, the repeating unit having an aromatic group in the entire repeating unit of the resin (B) is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally 0 mol% It is more preferable that it does not have. The resin (B) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

From the viewpoint of compatibility with a hydrophobic resin to be described later, it is preferable that the resin (B) does not contain a fluorine atom and a silicon atom.

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

The weight average molecular weight of the resin (B) is preferably from 1,000 to 200,000, more preferably from 2,000 to 20,000, even more preferably from 3,000 to 15,000, particularly preferably from 3,000 to 11,000, in terms of polystyrene as measured by GPC . By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, deterioration of developability or viscosity and deterioration of film formability can be prevented.

The dispersion degree (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. The smaller the molecular weight distribution, the better the resolution and the resist shape, the better the sidewall of the resist pattern, and the better the roughness.

The content of the resin (B) in the whole composition is preferably from 30 to 99% by mass, more preferably from 55 to 95% by mass, based on the total solid content. The resin of the present invention may be used singly or in combination.

<Other ingredients>

The composition may contain components other than the above-mentioned photoacid generator (A) and resin (B).

Hereinafter, arbitrary components will be described in detail.

(Compound (B2) that generates an acid upon irradiation with an actinic ray or radiation)

The composition of the present invention is a compound (B2) that generates an acid upon irradiation with an actinic ray or radiation different from the compound represented by the aforementioned general formula (A-1) (hereinafter referred to as &quot; (B2) ").

The compound (B2) is preferably a compound which generates an organic acid upon irradiation with an actinic ray or radiation.

The compound (B2) may be in the form of a low molecular weight compound or may be contained in a part of the polymer. The form of the low-molecular compound and the form contained in a part of the polymer may be used in combination.

When the compound (B2) is in the form of a low-molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

When the compound (B2) is in a part of the polymer, it may be introduced into a part of the above-mentioned acid-decomposable resin or may be introduced 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 weight compound.

As the compound (B2), a known compound which generates an acid upon irradiation with an actinic ray or radiation used for photocatalytic polymerization, photoinitiator for photo-radical polymerization, photo-discoloring agent for dye, photo-discoloring agent or micro- And a mixture thereof can be appropriately selected and used.

Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oxime sulfonates, diazodisulfone, disulfone and o-nitrobenzylsulfonate.

As preferred compounds in the compound (B2), there may be mentioned the compounds represented by the following general formulas (ZI), (ZII) and (ZIII).

In the above general formula (ZI)

R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The number of carbon atoms of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.

Also, R ₂₀₁ ~ R by combining two of the dog ₂₀₃ may be bonded to form a ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, a carbonyl group may be in the ring. The group R is ₂₀₁ ~ ₂₀₃ R 2 combine to form a dog may be in the alkylene group (e.g., a butylene group, a pentylene group).

Z ^- represents an unconjugated anion.

Examples of the non-nucleophilic anion as Z ^- include a sulfonic acid anion, a carboxylic acid anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

The non-nucleophilic anion is an anion having a remarkably low ability to cause a nucleophilic reaction, and is an anion capable of inhibiting aging degradation due to an intramolecular nucleophilic reaction. As a result, the stability with time of the active ray-sensitive or radiation-sensitive resin composition is improved.

Examples of the sulfonic acid anion include an aliphatic sulfonic acid anion, an aromatic sulfonic acid anion, and a camphorsulfonic acid anion.

Examples of the carboxylic acid anion include an aliphatic carboxylic acid anion, an aromatic carboxylic acid anion, and an aralkylcarboxylic acid anion.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be either an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms,

The aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid 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 sulfonic acid anion and the aromatic sulfonic acid anion may have a substituent.

Examples of other non-nucleophilic anions include fluorinated phosphorus (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), and antimony fluoride (for example, SbF ₆ ^- ).

Examples of the non-nucleophilic anion of Z ^- include an aliphatic sulfonic acid anion in which at least the alpha position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion in which the alkyl group is substituted with a fluorine atom or a fluorine atom, a bis (alkylsulfonyl) , And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoro aliphatic 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, Benzenesulfonic acid anion, and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

Particularly preferred examples of the compound (B2) include the compounds exemplified in paragraph [0143] of US2012 / 0207978A1.

The compound (B2) can be synthesized by a known method and can be synthesized in accordance with, for example, the method described in Japanese Patent Application Laid-Open No. 2007-161707.

When two or more compounds (B2) are used in combination, the total content of the compound (B2) in the composition is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 25% by mass, Preferably 3 to 20% by mass, and particularly preferably 3 to 15% by mass.

(Acid diffusion control agent)

The composition of the present invention preferably contains an acid diffusion control agent. The acid diffusion control agent acts as a quenching agent for trapping an acid generated from a photoacid generator or the like. Examples of the acid diffusion controlling agent include a basic compound, a low molecular compound having a nitrogen atom and having a group which is cleaved by the action of an acid, a basic compound whose basicity is lowered or eliminated by irradiation with an actinic ray or radiation, Can be used.

The basic compound is preferably a compound having a structure represented by the following formulas (A) to (E).

Among the general formulas (A) and (E)

R ^200, R ²⁰¹ and R ^202, which may be the same or different, a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number of 6-20 ), Wherein R ²⁰¹ and R ²⁰² may be bonded to 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.

The alkyl group having a substituent for the alkyl group is preferably an aminoalkyl group having from 1 to 20 carbon atoms, a hydroxyalkyl group having from 1 to 20 carbon atoms, or a cyanoalkyl group having from 1 to 20 carbon atoms.

The alkyl groups in the general formulas (A) and (E) are more preferably indeterminate.

Preferred examples of the compound include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like. More preferred compounds include imidazole, diazabicyclo, A compound having an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / .

Specific examples of preferred compounds include the compounds exemplified in paragraph [0379] of U.S. Patent Application Publication No. 2012/0219913.

Preferred examples of the basic compound 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.

The amine compound may be a primary, secondary or tertiary amine compound, and is preferably an amine compound in which at least one alkyl group is bonded to a nitrogen atom. More preferably, the amine compound is a tertiary amine compound. When the at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom, the amine compound may contain, in addition to the alkyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 12 carbon atoms May be bonded to the nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and is formed with an oxyalkylene group. The number of oxyalkylene groups in the molecule is 1 or more, preferably 3 to 9, more preferably 4 to 6. Among 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, Oxyethylene group.

The ammonium salt compound may be a primary, secondary, tertiary or quaternary ammonium salt compound, and is preferably an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom. When the at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom, the ammonium salt compound may contain a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably a 6 to 12 carbon atoms May be bonded to the nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain to form an oxyalkylene group. The number of oxyalkylene groups in the molecule is 1 or more, preferably 3 to 9, more preferably 4 to 6. Among 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, Oxyethylene group.

Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate. Among them, a halogen atom and a sulfonate are preferable.

In addition, the following compounds are also preferable as basic compounds.

In addition to the above-mentioned compounds, examples of the basic compound include the compounds described in paragraphs [0180] to [0225] of Japanese Patent Application Laid-Open No. 2011-22560, paragraphs [0218] to [0219] of Japanese Patent Application Publication No. 2012-137735, Compounds described in paragraphs [0416] to [0438] may also be used.

These basic compounds may be used singly or in combination of two or more kinds.

The composition of the present invention may or may not contain a basic compound. When contained, the content of the basic compound is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the composition.

The ratio of the photoacid generator (A) to the basic compound in the composition is preferably from 2.5 to 300 as the photoacid generator (A) / basic compound (molar ratio). That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and from the viewpoint of suppressing the resolution lowering due to the increase in the resist pattern due to the elapsed time after the post-exposure heating treatment, 300 or less is preferable. The photoacid generator (A) / basic compound (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

A low molecular weight compound having a nitrogen atom and having a group which is cleaved by the action of an acid (hereinafter also referred to as a compound (C)) is an acetal group, a carbonate group, a carbamate group, An ester group, a tertiary hydroxyl group and a hemimineral ether group are preferable, and a carbamate group and a hemimineral ether group are particularly preferable.

The molecular weight of the compound (C) is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.

As the compound (C), an amine derivative having a group which is eliminated on the nitrogen atom by the action of an acid is preferable.

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

In the general formula (d-1)

R _b each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group Preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). And R &lt; _{b &} gt _; may be connected to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group or aralkyl group represented by R _b is substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group or an oxo group, There may be. The same applies to the alkoxyalkyl group represented by R _b .

R _b is preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group. More preferably a linear or branched alkyl group or cycloalkyl group.

Examples of the ring formed by connecting two R _b's to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.

The specific structure of the group represented by the general formula (d-1) is not limited to the structure disclosed in the paragraph [0466] of the specification of United States Patent Application Publication No. 2012/0135348.

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

In the general formula (6), R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two R _a may be the same or different, and two R _a 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.

_B R is R and _b agree in the formula (d-1), preferred examples are the same.

1 represents an integer of 0 to 2, m represents an integer of 1 to 3, and 1 + m = 3 is satisfied.

The alkyl group as R _a in the formula (6), a cycloalkyl group, an aryl group, an aralkyl group R _b represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group may be optionally substituted are substituted with one group machangajiin described as being good group as .

Specific examples of the alkyl group, cycloalkyl group, aryl group and aralkyl group of R _a (these alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups may be substituted with the above groups) include groups similar to the specific examples described above for R _b have.

Specific examples of the preferable compound (C) include, but are not limited to, those disclosed in paragraph [0475] of U.S. Patent Application Publication No. 2012/0135348.

The compound represented by the general formula (6) can be synthesized in accordance with Japanese Patent Application Laid-Open Nos. 2007-298569 and 2009-199021.

In the present invention, the compound (C) may be used singly or in combination of two or more.

The content of the compound (C) in the composition of the present invention is not particularly limited, but is preferably 0.001 to 20% by mass, more preferably 0.001 to 10% by mass, more preferably 0.01 To 5% by mass.

A basic compound whose basicity is lowered or disappeared by irradiation with an actinic ray or radiation has a proton acceptor functional group and is decomposed by irradiation with an actinic ray or radiation to decrease the proton acceptor property, Acidic compound. Hereinafter also referred to as compound (PA).

A proton acceptor functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, and includes, for example, a functional group having a macrocyclic structure such as a cyclic polyether, a nitrogen having a non-covalent electron pair Means a functional group having an atom. The nitrogen atom having a non-covalent electron pair not contributing to the pi -conjugate is, for example, a nitrogen atom having a partial structure represented by the following general formula.

Preferable partial structures of the proton acceptor functional groups include, for example, crown ethers, azacrown ethers, primary to tertiary amines, pyridine, imidazole and pyrazine structures.

The compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is decreased, disappearance or changed from proton acceptor property to acidic. Herein, the change of the proton acceptor property from the degradation, disappearance, or change from the proton acceptor property to the acid is a change of the proton acceptor property due to the addition of the proton to the proton acceptor functional group. Specifically, the change of the proton acceptor property Means that the equilibrium constant in the chemical equilibrium is reduced when a fluorine adduct is formed from the compound (PA) and the proton.

The proton acceptor property can be confirmed by performing pH measurement.

In the present invention, the acid dissociation constant (pKa) of the compound generated by decomposition of the compound (PA) by irradiation with an actinic ray or radiation preferably satisfies a pKa <-1, more preferably -13 <pKa < -1, and more preferably -13 < pKa < -3.

In the present invention, the acid dissociation constant (pKa) represents an acid dissociation constant (pKa) in an aqueous solution and is, for example, described in Chemical Handbook (II) (revised edition 4, 1993, The Chemical Society of Japan, MARUZEN Co., Ltd.). ), And the lower this value is, the higher the acid strength is. Specifically, the acid dissociation constant (pKa) in an aqueous solution can be measured by measuring an acid dissociation constant at 25 캜 using an infinitely diluted aqueous solution. Data of the Hammett substituent constant and known document value The value based on the base can also be obtained by calculation. The values of pKa described in the present specification all represent 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 the compound represented by the following general formula (PA-1), for example, as the above-mentioned propane adduct produced by decomposition by irradiation of an actinic ray or radiation. The compound represented by the general formula (PA-1) is a compound which has an acidic group together with a proton acceptor functional group and thus has a proton acceptor property lowered, disappearance or acidity from proton acceptor property than that of the compound (PA).

In the general formula (PA-1)

Q represents -SO ₃ H, -CO ₂ H or -W ₁ NHW ₂ R _f . Wherein 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 -. Wherein 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 U.S. Patent Application Publication No. 2011/0269072.

Further, in the present invention, a compound (PA) other than a compound which generates a compound represented by the formula (PA-1) may be appropriately selected. For example, a compound having an ionic compound and a proton acceptor moiety in its cation moiety may be used. And more specifically, a compound represented by the following general formula (7).

In the formula, A represents a sulfur atom or an iodine atom.

m represents 1 or 2, and n represents 1 or 2. Provided that m + n = 3 when A is a sulfur atom and m + n = 2 when A is an iodine atom.

R represents an aryl group.

R _N represents an aryl group substituted by a proton acceptor functional group.

X ^- represents 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 are preferably a phenyl group.

Specific examples of the proton acceptor functional group having R _N are the same as the proton acceptor functional groups described in the above formula (PA-1).

Specific examples of the ionic compound having a proton acceptor moiety at the cation moiety are the compounds exemplified in paragraph [0291] of the specification of U.S. Patent Application Publication No. 2011/0269072.

Such a compound can be synthesized by referring to, for example, methods described in Japanese Patent Application Laid-Open Nos. 2007-230913 and 2009-122623.

The compound (PA) may be used singly or in combination of two or more.

The content of the compound (PA) is preferably 0.1 to 10 mass%, more preferably 1 to 8 mass%, based on the total solid content of the composition.

In the composition of the present invention, an onium salt which is relatively weak acid relative to the photoacid generator (A) can be used as an acid diffusion control agent.

When an onium salt which generates a relatively weakly acidic acid is mixed with the acid generated from the photoacid generator (A) and the acid generated from the photoacid generator (A), the photoacid generator (A ) Causes the onion salt with weak acid anion to release weak acid by salt exchange and generate an onium salt with strong acid anion. In this process, since the strong acid is exchanged into the weak acid having a lower catalytic activity, the acid is apparently lost and the acid diffusion can be controlled.

The onium salt which is relatively weakly acidic with respect to the photo acid generator (A) is preferably a compound represented by the following formulas (d1-1) to (d1-3).

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon adjacent to S is not substituted with a fluorine atom) R ⁵² is an organic group; Y ³ is a straight chain, branched chain or cyclic alkylene group or arylene group; Rf is a hydrocarbon group containing a fluorine atom; and M ⁺ is independently a sulfonium or iodonium cation.

M ⁺ expressed as sulfonium cation or the iodonium cation preferred examples mentioned above _{^{S + (R 201) (R}} 202) (R 203) sulfonium _{^{cation, I + (R 204) (}} R 205) is represented as shown as May be mentioned as iodonium cations.

A preferable example of the anion moiety of the compound represented by the general formula (d1-1) is a structure exemplified in paragraph [0198] of JP-A-2012-242799.

Preferable examples of the anion moiety of the compound represented by the general formula (d1-2) include the structures exemplified in the paragraph [0201] of the Japanese Patent Application Laid-Open Publication No. 2012-242799.

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 JP-A No. 2012-242799.

The onium salt which is relatively weakly acidic with respect to the acid generator may be a compound having a cation site and an anion site in the same molecule and the cation site and the anion site linked by a covalent bond.

The compound is preferably a compound represented by one of the following formulas (E-1) to (E-3).

R ₁ , R ₂ and R ₃ in the general formulas (E-1) to (E-3) represent substituents having 1 or more carbon atoms.

L ₁ represents a divalent linking group or a single bond connecting a cation site and an anion site.

-X ^- it is _{^{-COO -, -SO 3 -, -SO}} 2 -, -N - represents an anion portion selected from -R _4. R ₄ is a monovalent substituent having a carbonyl group: -C (═O) -, a sulfonyl group: -S (═O) ₂ -, or a sulfinyl group: -S (═O) - at a connecting site to an adjacent N atom .

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 N atom.

Examples of the substituent having at least 1 carbon atom 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, a cycloalkylaminocarbonyl group, Can be heard. Preferably an alkyl group, a cycloalkyl group, or an aryl group.

L ₁ as a divalent linking group may be a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, . More preferably, L ₁ is an alkylene group, an arylene group, an ether bond, an ester bond, or a combination of two or more thereof.

Preferred examples of the compound represented by the general formula (E-1) include the compounds described in paragraphs [0037] to [0039] of JP-A-2013-6827 and paragraphs [0027] to [0029] of JP-A- The exemplified compounds.

Preferable examples of the compound represented by formula (E-2) include the compounds exemplified in paragraphs [0012] to [0013] of Japanese Patent Application Laid-Open Publication No. 2012-189977.

Preferred examples of the compound represented by formula (E-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP-A-2012-252124.

The content of the onium salt which is relatively weakly acidic with respect to the photoacid generator is preferably 0.5 to 10.0% by mass, more preferably 0.5 to 8.0% by mass, further preferably 1.0 to 8.0% by mass based on the total solid content of the composition Do.

(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)") when applied to liquid immersion lithography. The hydrophobic resin (D) is preferably different from the resin (B).

As a result, the hydrophobic resin (D) is uniformalized in the surface layer of the film, and when the immersion medium is water, the static / dynamic contact angle of the surface of the resist film with respect to water can be improved and the immersion liquid followability can be improved.

The hydrophobic resin (D) is preferably designed to be distributed on the interface as described above. However, unlike the surfactant, it is not necessarily required to have a hydrophilic group in the molecule, and it may not contribute to uniformly mixing the polar / non-polar material.

The hydrophobic resin (D) preferably has at least one of "fluorine atom", "silicon atom" and "CH ₃ partial structure contained in the side chain portion of the resin" from the viewpoint of the unevenness toward the surface layer of the film, It is more preferable to have species or more.

When the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin or may be contained in the side chain .

When the hydrophobic resin (D) contains a fluorine atom, it is preferably 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.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a straight chain or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom and has a substituent other than a fluorine atom good.

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 in 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.

The alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom and the aryl group having a fluorine atom are preferably the groups represented by the following formulas (F2) to (F4), but the present invention is not limited thereto .

Among the general formulas (F2) to (F4)

Each of R ₅₇ to R ₆₈ independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight chain or branched). Provided that 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 an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom Represents 1 to 4 carbon atoms).

It is preferable that all of R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are 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 more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. 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 the specification of United States Patent Application Publication No. 2012/0251948.

Specific examples of the group represented by formula (F4), for example, _{-C (CF 3) 2 OH,} -C (C 2 F 5) 2 OH, -C (CF 3) (CH 3) OH, -CH (CF ₃₎ there may be mentioned, such as OH, -C (CF _{3) 2} OH is preferred.

The partial structure containing a fluorine atom may be bonded directly to the main chain or may be a group selected 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 Or may be bonded to the main chain through a group obtained by combining two or more of them.

The hydrophobic resin (D) may contain a silicon atom. As the partial structure having a silicon atom, a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or cyclic siloxane structure is preferable.

Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in paragraph [0519] of U.S. Patent Application Publication No. 2012/0251948.

In addition, as described above, it is also preferable that the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion.

Here, the CH ₃ partial structure (hereinafter, simply referred to as "side chain CH ₃ partial structure") of the side chain portion in the hydrophobic resin (D) includes a CH ₃ partial structure having an ethyl group or a propyl group.

On the other hand, the methyl group (for example, the? -Methyl group of the repeating unit having a methacrylic acid structure) directly bonded to the main chain of the hydrophobic resin (D) has the effect of contributing to surface localization of the hydrophobic resin (D) Is not included in the CH ₃ partial structure in the present invention.

More specifically, when the hydrophobic resin (D) contains 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 formula (M) When R ₁₁ to R ₁₄ are CH ₃ "itself", the CH ₃ is not included in the CH ₃ partial structure of the side chain portion in the present invention.

On the other hand, part CH ₃ structure present through any atom from the CC main chain is assumed to correspond to the CH ₃ a partial structure of the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed that the CH ₃ partial structure in the present invention has "one".

In the above general formula (M)

R ₁₁ to R ₁₄ each independently represent a side chain moiety.

Examples of R ₁₁ to R _{14 in the} side chain moiety include a hydrogen atom and a monovalent organic group.

Examples of the monovalent organic group for R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group and an arylaminocarbonyl group , 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. As such a repeating unit, a repeating unit represented by the following general formula (II) and a repeating unit represented by the following general formula And more preferably at least one kind of repeating unit (x) among the repeating units.

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

X _b1 in the general formula (II) represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₂ represents a stable organic group with respect to an acid having at least one CH ₃ partial structure. Here, the organic group stable with respect to an acid is more preferably an organic group having no "acid decomposable group" described in the resin (B).

The alkyl group of X _b1 is preferably a 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.

X _b1 is preferably a hydrogen atom or a methyl group.

R ₂ is an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group having at least one CH ₃ partial structure. The 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 at least one CH ₃ partial structure.

The stable organic group in the acid having at least one CH ₃ partial structure as R ₂ preferably has 2 to 10 and more preferably 2 to 8 CH ₃ partial structures.

Specific preferred examples of the repeating unit represented by formula (II) are listed below. Further, the present invention is not limited to this.

The repeating unit represented by the formula (II) is preferably a stable (non-acid-decomposable) repeating unit in the acid, and more preferably a repeating unit having no group capable of generating a polar group by the action of an acid.

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

X _b2 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₃ represents a stable organic group with respect to an acid having at least one CH ₃ partial structure, and n represents an integer of 1 to 5 .

The alkyl group of X _b2 preferably has 1 to 4 carbon atoms, and may be a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, but is preferably a hydrogen atom. X _b2 is preferably a hydrogen atom.

More specifically, R ₃ is preferably an organic group which does not have the "acid-decomposable group" described in the hydrophobic resin (B) because it is a stable organic group with respect to an acid.

R ₃ is an alkyl group having at least one CH ₃ partial structure.

The stable organic group in the acid having at least one CH ₃ partial structure as R ₃ preferably has 1 to 10 or less CH ₃ partial structures, more preferably 1 to 8, and more preferably 1 to 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.

Specific preferred examples of the repeating unit represented by the general formula (III) are listed below. Further, the present invention is not limited to this.

The repeating unit represented by the general formula (III) is preferably a stable (non-acid-decomposable) repeating unit in the acid, more specifically a repeating unit having no group capable of generating a polar group by the action of an acid.

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

The hydrophobic resin (D) contains at least one repeating unit (x) among the repeating units represented by the general formula (II) and the repeating units represented by the general formula (III) By mole or more, the surface free energy of the hydrophobic resin (D) increases. As a result, the hydrophobic resin (D) is unevenly distributed on the surface of the resist film, so that the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the follow-up property of the immersion liquid can be improved.

The hydrophobic resin (D) can also be used in the case of containing (i) a fluorine atom and / or a silicon atom, (ii) even when the side chain portion includes a CH ₃ partial structure, And at least one group selected from the group consisting of R &lt; 1 &gt;

(x) an acid group,

(y) lactone structure, an acid anhydride group or an acid imide group,

(z) a group decomposed 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, (Alkylcarbonyl) methylene group, a bis (alkylsulfonyl) methylene group, a bis (alkylsulfonyl) imide group, a tris (alkylcarbonyl) , Tris (alkylsulfonyl) methylene group, and the like.

Preferable acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

Examples of the repeating unit having an acid group (x) include a repeating unit in which an acid group is directly bonded to the main chain of the resin such as a repeating unit derived from acrylic acid or methacrylic acid, or a repeating unit in which an acid group is bonded to the main chain of the resin through a connecting group Or a polymerization initiator or chain transfer agent having an acid group may be introduced at the end of the polymer chain by polymerization. The repeating unit having an acid group (x) may have at least any one of a fluorine atom and a silicon atom.

The content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, and still more preferably from 5 to 20 mol%, based on the total repeating units in the hydrophobic resin (D) to be.

Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. Wherein 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 the group is bonded directly to the main chain of the resin such as a repeating unit derived from an acrylate ester and a methacrylate ester. Or this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin through a linking group. Alternatively, the repeating unit may be introduced at the end of the resin by using a polymerization initiator or a chain transfer agent having this group at the time of polymerization.

As the repeating unit having a group having a lactone structure, for example, the same repeating unit having a lactone structure as described in the paragraph of the acid-decomposable resin (B) may be mentioned.

The content of the repeating unit having a lactone structure, acid anhydride group or acid imide group in the hydrophobic resin (D) is preferably 1 to 100 mol%, more preferably 3 to 98 mol% , More preferably 5 to 95 mol%.

Examples of the repeating unit having a group (z) decomposed by the action of an acid in the hydrophobic resin (D) include the same repeating units having an acid-decomposable group as listed in the resin (B). The repeating unit having a group (z) decomposed by the action of an acid may have at least any one of a fluorine atom and a silicon atom. The content of the repeating unit having a group (z) decomposed by the action of an acid in the hydrophobic resin (D) is preferably from 1 to 80 mol%, more preferably from 10 to 80 mol%, based on all repeating units in the resin (D) To 80 mol%, and more preferably 20 to 60 mol%.

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

In the general formula (III)

R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom), 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.

The alkyl group represented by R _{c32 in} the general formula (III) is preferably a linear or branched alkyl group having from 3 to 20 carbon atoms.

The cycloalkyl group is preferably a cycloalkyl group having from 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 from 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 they may have a substituent.

R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.

The bivalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), 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%, more preferably 10 to 90 mol%, and more preferably 30 to 70 mol% based on the total repeating units in the hydrophobic resin (D) % Is more preferable.

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

Of the general formula (CII-AB)

R _c11 'and R _c12 ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Zc 'includes two bonded carbon atoms (C-C) and represents an atomic group for forming an alicyclic structure.

The content of the repeating unit represented by the general formula (CII-AB) is preferably from 1 to 100 mol%, more preferably from 10 to 90 mol%, still more preferably from 30 to 90 mol% based on the total repeating units in the hydrophobic resin (D) More preferably 70 mol%.

Specific examples of the repeating units represented by the general formulas (III) and (CII-AB) are set forth below, but the present invention is not limited thereto. Ra in the formula denotes a _{H, CH 3, CH 2 OH} , CF 3 or CN.

When the hydrophobic resin (D) has a fluorine atom, the fluorine atom content is preferably 5 to 80 mass%, more preferably 10 to 80 mass%, with respect to the weight average molecular weight of the hydrophobic resin (D). The repeating unit containing a fluorine atom is preferably from 10 to 100 mol%, more preferably from 30 to 100 mol%, of the total repeating units contained in the hydrophobic resin (D).

When the hydrophobic resin (D) has a silicon atom, the silicon atom content is preferably 2 to 50 mass%, more preferably 2 to 30 mass%, based on the weight average molecular weight of the hydrophobic resin (D). The repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, of the total repeating units contained in the hydrophobic resin (D).

On the other hand, in the case where the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion, the hydrophobic resin (D) is preferably a composition containing substantially no fluorine atom and silicon atom. The content of the repeating unit having an atom or a silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, further preferably 1 mol% or less, relative to all the repeating units in the hydrophobic resin (D) Does not contain 0 mol%, i.e., a fluorine atom and a silicon atom. It is also preferred that the hydrophobic resin (D) consists substantially only of repeating units composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom. More specifically, the repeating unit constituted only by atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is preferably 95 mol% or more, more preferably 97 mol% or more of all repeating units of the hydrophobic resin (D) , 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 preferably from 10 to 60 mol% based on the total repeating units of the hydrophobic resin (D) , More preferably from 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 even more preferably 2,000 to 15,000.

The hydrophobic resin (D) may be used singly 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, and even more preferably 0.1 to 7% by mass, based on the total solid content in the composition.

It is natural that the hydrophobic resin (D) has less impurities such as metals as in the case of the resin (B), and the residual monomer or oligomer component is preferably 0.01 to 5 mass%, more preferably 0.01 to 3 mass% 1% by mass is more preferable. Thereby, a composition which is free from foreign matters in the liquid and changes with time such as sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersion degree) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3, still more preferably in the range of the resolution, the resist shape, the side wall of the resist pattern, Is in the range of 1 to 2.

The hydrophobic resin (D) may be commercially available or can be synthesized according to the conventional method (for example, radical polymerization). Examples of the general synthesis method include a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent to effect polymerization, a dropwise polymerization method in which a solution of a monomer species and an initiator is added dropwise over 1 to 10 hours to a heating solvent And a dropwise polymerization method is preferable.

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

(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, alkyl alkoxypropionate, lactone (preferably having 4 to 10 carbon atoms) , A monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, an alkylene carbonate, an alkyl alkoxyacetate, and an alkyl pyruvate.

Among them, a chain or cyclic ketone solvent or a lactone solvent is preferable from the viewpoint of more excellent effects of the present invention. More preferably, it is a cyclic ketone solvent or a lactone solvent, and cyclohexanone or? -Butyrolactone is particularly preferable.

Specific examples of these solvents include those described in paragraphs [0441] to [0455] of U.S. Patent Application Publication No. 2008/0187860.

In the present invention, a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group in the structure may be used as the organic solvent.

As the solvent containing a hydroxyl group, an alkylene glycol monoalkyl ether, an alkyl lactate and the like are preferable, and a propylene glycol monomethyl ether (PGME, Ethoxy-2-propanol), ethyl lactate, and methyl-2-hydroxybutyrate are more preferable. Examples of the solvent not containing a hydroxyl group include alkylene glycol monoalkyl ether acetates, alkylalkoxypropionates, monoketone compounds which may contain a ring, cyclic lactones and alkyl acetates, and propylene glycol monomethyl ether acetate (PGMEA, ally 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone,? -Butyrolactone, cyclohexanone and butyl acetate are particularly preferable, and propylene glycol monomethyl ether Acetate, ethyl ethoxypropionate, 2-heptanone are most preferred.

The mixing ratio (mass) of the hydroxyl group-containing solvent to the hydroxyl group-containing solvent is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40. A mixed solvent containing 50 mass% or more of a solvent not containing a hydroxyl group is particularly preferable in view of coating uniformity.

The solvent preferably contains propylene glycol monomethyl ether acetate and is preferably a mixed solvent of two or more types containing propylene glycol monomethyl ether acetate alone or propylene glycol monomethyl ether acetate.

As the solvent, it is preferable to use one having a reduced content of peroxide, thereby improving the storage stability of the resist composition. The content of the peroxide in the solvent is preferably 2.0 mol% or less, more preferably 1.0 mol% or less, still more preferably 0.5 mmol% or less, and particularly preferably substantially no peroxide.

(Surfactants)

The composition may also contain or not contain a surfactant and may contain one or more of fluorine and / or silicon surfactants (fluorine surfactants, silicone surfactants, surfactants having both fluorine and silicon atoms) Is more preferable.

By containing a surfactant in the composition, it becomes possible to impart a resist pattern with good adhesiveness and low development defects with good sensitivity and resolution at the time of using an exposure light source of 250 nm or less, particularly 220 nm or less.

And surfactants described in paragraph [0276] of U.S. Patent Application Publication No. 2008/0248425 as fluorine- and / or silicone-based surfactants.

In the present invention, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph [0280] of U.S. Patent Application Publication No. 2008/0248425 may be used.

These surfactants may be used alone or in combination of several.

When the composition contains a surfactant, the amount of the surfactant to be used is preferably 0.0001 to 2 mass%, more preferably 0.0005 to 1 mass%, based on the total solid content of the composition.

On the other hand, when the addition amount of the surfactant is 10 ppm or less with respect to the total amount of the composition (excluding the solvent), the surface ubiquity of the hydrophobic resin is increased, whereby the surface of the resist film can be made more hydrophobic, The followability can be improved.

(Other)

The composition of the present invention may or may not contain a carboxylic acid onium salt. Such a carboxylic acid onium salt may be those described in paragraphs [0605] to [0606] of U.S. Patent Application Publication No. 2008/0187860.

These onium salts of carboxylic acid can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with oxidation in an appropriate solvent.

When the composition contains a carboxylic acid onium salt, the content thereof is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 7% by mass, based on the total solid content of the composition.

The composition may contain, if necessary, a compound which promotes solubility in an acid generator, dye, plasticizer, photosensitizer, light absorber, alkali-soluble resin, dissolution inhibitor and developer (for example, a phenol compound having a molecular weight of 1000 or less, Alicyclic or aliphatic compound), and the like.

Such a phenol compound having a molecular weight of 1000 or less can be obtained by a method known to those skilled in the art, for example, in Japanese Patent Application Laid-Open Nos. 4-122938, 2-28531, 4,916,210, and 219294 Can be easily synthesized.

Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, dioxycholic acid and lithocholic acid, adamanthanecarboxylic acid derivatives, adamantanedicarboxylic acid, cyclohexanecarboxylic acid, Butoxycarbonyl group, hexyloxycarbonyl group, hexyloxycarbonyl group, hexyloxycarbonyl group, hexyloxycarbonyl group and the like.

The composition of the present invention is preferably a resist film having a film thickness of 80 nm or less from the viewpoint of improvement of resolution. It is possible to set the solid content concentration in the composition to an appropriate range so as to have an appropriate viscosity to improve the coatability and the film formability.

The solid content concentration of the composition of the present invention is preferably from 1.0 to 10 mass%, more preferably from 2.0 to 5.7 mass%, and still more preferably from 2.0 to 5.3 mass%. By setting the solid concentration in the above range, the composition can be uniformly applied onto the substrate, or a resist pattern having excellent line-through roughness can be formed. The reason for this is not clear, but presumably by setting the solid concentration to 10 mass% or less, preferably 5.7 mass% or less, aggregation of the material, particularly the photoacid generator (A) in the resist solution is suppressed, It is believed that it could be formed.

The solids concentration is the weight percentage of the weight of the other resist components, excluding the solvent, relative 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 applying the solution on a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 탆 or less, more preferably 0.05 탆 or less, and even more preferably 0.03 탆 or less. In filter filtration, for example, the filtration may be carried out by performing cyclic filtration or connecting a plurality of kinds of filters in series or in parallel, as disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-62667. In addition, the composition may be filtered a plurality of times. The composition may be degassed before or after the filtration of the filter.

The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition in which properties are changed by irradiation with an actinic ray or radiation. More specifically, the present invention relates to a process for producing a semiconductor such as an IC, a process for producing a circuit substrate such as a liquid crystal or a thermal head, a process for producing an imprint mold structure, a photoproduction process for use in a lithographic printing plate, To a radiation or radiation-sensitive resin composition.

&Lt; Pattern formation method >

Next, a pattern forming method according to the present invention will be described.

The pattern forming method according to the present invention has at least the following steps.

(A) a film forming process for forming a film (hereinafter also referred to as a resist film) by the above composition

(B) Exposure process for irradiating the film with an actinic ray or radiation

(C) a developing step of developing the film irradiated with the actinic ray or radiation using a developer

The exposure in the step (B) may be immersion exposure.

The pattern forming method of the present invention preferably includes (b) a post-exposure step and (d) a heating step.

The pattern forming method of the present invention may include (b) a plurality of exposure steps.

The pattern forming method of the present invention may include (d) a heating step plural times.

The resist film of the present invention is formed of the composition of the present invention, and more specifically, it is preferably a film formed by applying the composition to a substrate. In the pattern forming method of the present invention, the step of forming the film by the composition on the substrate, the step of exposing the film, and the developing step can be carried out by a generally known method.

The substrate on which the film is to be formed in the present invention is not particularly limited, and examples thereof include inorganic substrates such as silicon, SiN, SiO ₂ and SiN, and coating inorganic substrates such as SOG; semiconductor manufacturing processes such as IC; A substrate commonly used in a manufacturing process of a circuit board, or a lithography process of other photofabrication may be used. In addition, an antireflection film may be formed between the resist film and the substrate, if necessary. As the antireflection film, known organic or inorganic antireflection films can be suitably used.

It is also preferable to include a pre-heating step (PB) before the exposure process after the film formation.

It is also preferable to include a post exposure bake (PEB) process after the exposure process or before the development process.

The heating temperature is preferably 70 to 130 ° C in both PB and PEB, and more preferably 80 to 120 ° C.

The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and most preferably 30 to 90 seconds.

The heating can be performed by a means provided in a conventional exposure and developing machine, or by using a hot plate or the like.

The baking improves the sensitivity and pattern profile by promoting the reaction of the exposed portion.

There is no limitation on the wavelength of the light source used in the exposure apparatus of the present invention, but examples thereof include infrared light, visible light, ultraviolet light, ultraviolet light, ultraviolet light, X-rays and electron beams. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray , EUV (13 nm), and electron beam. KrF excimer laser, ArF excimer laser, EUV or electron beam are preferable, and ArF excimer laser is more preferable.

In the exposure step of the present invention, a liquid immersion exposure method can be applied. The liquid immersion exposure method can be combined with a super resolution technique such as a phase shift method or a modified illumination method.

In the case of liquid immersion lithography, the surface of the film is cleaned with a chemical liquid in an aqueous liquid before (1) a step of forming a film on a substrate and then exposing it, and / or (2) May be carried out.

The liquid immersion liquid is preferably a liquid as transparent as possible with respect to the exposure wavelength and as small as possible with a temperature coefficient of refractive index so as to minimize deformation of the optical image projected onto the film. It is preferable to use water in view of easiness of acquisition and easiness of handling in addition to the above-described viewpoint.

When water is used, an additive (liquid) which decreases the surface tension of water and increases the surface activity may be added in a small proportion. It is preferable that the additive does not dissolve the resist film on the wafer and neglects the influence of the lower surface of the lens element on the optical coating.

As such an additive, for example, an aliphatic alcohol having almost the same refractive index as water is preferable, and specific examples thereof include methyl alcohol, ethyl alcohol and isopropyl alcohol. An alcohol having almost the same refractive index as water can be added to obtain an advantage that the change in the refractive index of the liquid as a whole can be made very small even if the content of alcohol in the water evaporates to change the concentration.

On the other hand, when an opaque material or refractive index largely different from water is mixed with 193 nm light, distilled water is preferably used as water to be used because it causes optical image to be projected on the resist film. Alternatively, pure water obtained by filtration 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, and the TOC (organic substance concentration) is preferably 20 ppb or less, and it is preferable that the water is subjected to degassing treatment.

In addition, it is possible to improve the lithography performance by improving the refractive index of the immersion liquid. From this point of view, 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 by using the composition of the present invention is preferably 70 deg. Or more at a temperature of 23 +/- 3 deg. C and a humidity of 45 +/- 5%, and is suitable for exposure through an immersion medium More preferably 75 DEG or more, and further preferably 75 DEG to 85 DEG.

If the receding contact angle is too small, it can not be suitably used for exposure through the immersion medium, and the effect of reduction of the residual water (watermark) defect can not be sufficiently exhibited. In order to realize a desirable receding contact angle, it is preferable to include the hydrophobic resin (D) in the composition. Alternatively, a receding contact angle may be improved by forming a coating layer (so-called "top coat") of a hydrophobic resin composition on the resist film. The resin composition for forming a top coat preferably contains the above-mentioned hydrophobic resin (D). The resin composition for forming a topcoat may contain additives such as the above-described photoacid generator and a basic compound. By adding a basic compound to the resin composition for top coat formation, the exposure latitude improves.

In the liquid immersion exposure process, since the immersion liquid needs to move on the wafer in accordance with the movement of the exposure head scanning the wafer at high speed to form the exposure pattern, the contact angle of the immersion liquid with respect to the resist film in the dynamic state is important And the capability of following the high-speed scanning of the exposure head without the droplet remaining is required for the resist.

As the 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 developing solution, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent or an ether solvent and a hydrocarbon solvent may be used.

Examples of the ketone-based solvent include aliphatic ketones such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylamyl ketone) But are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetonyl alcohol, acetylcarbinol, Acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, and the like.

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 Ethoxypropionate, 3-methoxybutylacetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl formate, , Ethyl lactate, butyl lactate, propyl lactate, isoamyl acetate, butyl butanoate, and methyl-2-hydroxybutylate.

Examples of the alcoholic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, Alcohols such as alcohol, 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, and methoxymethyl butanol; and the like.

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

Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, Diazolidinone 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-mentioned solvents may be mixed, or they may be mixed with other solvents or water. However, in order to sufficiently exhibit the effect of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, more preferably substantially water-free.

That is, the amount of the organic solvent to be used for the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less based on 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 a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent.

The vapor pressure of the organic developer at 20 캜 is preferably 5. Or less, more preferably 3 ㎪ or less, and particularly preferably 2 ㎪ or less. By reducing the vapor pressure of the organic developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, so that the temperature uniformity within the wafer surface is improved, and as a result, the dimensional uniformity within the wafer surface is improved.

If necessary, a suitable amount of a surfactant may be added to the organic developing solution.

The surfactant is not particularly limited and, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. As such fluorine- and / or silicon-based surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950 Japanese Patent Application Laid-Open Nos. 63-34540, 7-230165, 8-62834, 9-54432, 9-5988 Surfactants described in U.S. Patent Nos. 5,405,720, 5,360,692, 5529881, 5296330, 5436098, 5576143, 5294511, and 5824451, And is preferably a non-ionic surfactant. The nonionic surfactant is not particularly limited, but a fluorinated surfactant or a silicone surfactant is more preferably used.

The amount of the surfactant to be used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on 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 in the basic compound that the above-mentioned composition may contain.

Examples of the developing method include a method (dipping method) in which the substrate is immersed in a tank filled with a developer for a predetermined time (dipping method), a method (puddle method) in which the developing solution is paused by surface tension on the substrate surface for a predetermined time, A method of spraying a developer (spray method), a method of continuously discharging a developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method), and the like can be applied.

When the various developing methods include a step of discharging the developing solution from the developing nozzles of the developing apparatus toward the resist film, the discharge pressure (flow rate per unit area of the discharged developing solution) of the developing solution to be discharged is preferably 2 ml / sec / More preferably not more than 1.5 ml / sec / mm 2, further preferably not more than 1 ml / sec / mm 2. Although the lower limit of the flow velocity is not particularly specified, it is preferably 0.2 ml / sec / mm 2 or more in view of throughput.

By setting the discharge pressure of the developer to be discharged in the above range, it is possible to remarkably reduce the defects of the pattern derived from the resist residue after development.

Though the details of this mechanism are not certain, it is presumably because the pressure applied to the resist film by the developer is reduced by prescribing the discharge pressure within the above range, thereby suppressing inadvertent cutting or collapse of the resist film and the resist pattern.

The discharge pressure (ml / sec / mm 2) of the developer is a value at the exit of the developing nozzle in the developing apparatus.

Examples of a method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure by a pump or the like, a method of changing the discharge pressure by adjusting the pressure by feeding from a pressurizing tank, and the like.

Further, a step of stopping development while replacing with a solvent after the step of developing using a developing solution containing an organic solvent may be performed.

It is preferable to include a step of rinsing with a rinsing liquid after the step of developing using a developing solution containing an organic solvent.

As the rinse solution used in the rinsing step after the developing process using the organic solvent-containing developer, there is no particular limitation as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. As the rinsing liquid, it is preferable to use a rinsing liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent and an ether-based solvent.

Specific examples of the hydrocarbon-based solvent, the ketone-based solvent, the ester-based solvent, the alcohol-based solvent, the amide-based solvent and the ether-based solvent include the same ones as described in the developer containing an organic solvent.

After the step of developing using a developing solution containing an organic solvent, a rinsing liquid containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent and an amide solvent is preferably used More preferably, a step of washing using a rinsing liquid containing an alcoholic solvent or an ester-based solvent, and particularly preferably a step of rinsing with a rinsing liquid containing a monohydric alcohol , And most preferably, a step of washing with a rinsing liquid containing at least 5 monohydric alcohols.

Examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples thereof include 1-butanol, 2-butanol, 3-methyl- Butanol, 1-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. Particularly preferred monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and the like.

A plurality of components may be mixed, or they may be mixed with an organic solvent other than the above.

The water content in the rinsing liquid is preferably 10 mass% or less, more preferably 5 mass% or less, particularly preferably 3 mass% or less. By setting the water content to 10 mass% or less, good developing characteristics can be obtained.

The vapor pressure of the rinsing liquid to be used after the developing process using the organic solvent-containing developer is preferably from 0.05 to 5, more preferably from 0.1 to 5, more preferably from 0.1 to 2, , And most preferably 3% or less. By adjusting the vapor pressure of the rinse liquid to 0.05-5 GPa or less, the temperature uniformity within the wafer surface is improved and the swelling due to infiltration of the rinsing liquid is suppressed, thereby improving the dimensional uniformity within the wafer surface.

An appropriate amount of surfactant may be added to the rinse solution.

In the rinsing process, the wafer having undergone development using a developer containing an organic solvent is subjected to a cleaning treatment using a rinsing liquid containing the organic solvent. The method of the cleaning treatment is not particularly limited. For example, a method of continuously discharging the rinsing liquid onto the substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in the tank filled with the rinsing liquid for a predetermined time A method of spraying a rinsing liquid onto the substrate surface (spraying method), and the like can be applied. Among them, a cleaning treatment is carried out by a rotation coating method, and after cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm, It is preferable to remove it from the substrate. It is also preferable to include a post-baking step after the rinsing step. By baking, the developing solution and the rinsing liquid remaining in the patterns and in the pattern are removed. The heating step after the rinsing step is usually carried out at 40 to 160 ° C, preferably 70 to 95 ° C, for 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The pattern forming method of the present invention can be used in combination of both a step of performing development using an alkali developing solution (alkali development step) and a step of developing using an organic solvent (development step of organic solvent). As a result, a finer pattern can be formed.

In the present invention, the portions with weaker exposure intensity are removed by the organic solvent development process, but further portions with stronger exposure intensity are removed by further performing the alkali development process. As described above, since the area of the intermediate exposure intensity can be left as a pattern without dissolving only the area of the intermediate exposure intensity by the multiple development process in which development is performed plural times, it is possible to form a finer pattern than usual (Japanese Patent Laid-Open Publication No. 2008-292975 The same mechanism as that of FIG.

Although the alkali developing step can be performed both before and after the organic solvent development, it is more preferable to carry out the alkali developing step before the organic solvent developing step.

The present invention also relates to a method of manufacturing an electronic device including the method of forming a negative pattern of the present invention and an electronic device manufactured by the method.

The electronic device of the present invention is suitably mounted in an electric / electronic device (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

(Example)

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

&Lt; Preparation of composition (resist composition) >

The components shown in the following Table 3 were dissolved in a solvent shown in the table in a solid content of 3.5% by mass and each was filtered through a polyethylene filter having a pore size of 0.03 탆 to prepare a sensitizing actinic ray or radiation-sensitive resin composition (resist composition) did.

The various components used in Table 3 are summarized below.

Various compounds such as the following resins A-1 to A-5 and PAG-1 to PAG-5 are known documents (for example, Japanese Patent Application Laid-Open Publication No. 2011-252148, Japanese Patent Application Publication No. 2009-258586, -256879, etc.).

The composition ratios in the above table represent molar ratios of the repeating units contained in the above-mentioned Resins A-1 to A-5, and the composition ratios of the repeating units in the above-mentioned formula are shown in order from the left.

"F" in the above formula represents the content of fluorine atoms in the anion [(total molecular weight of fluorine atoms / total molecular weight of anions) x 100].

The composition ratios in the above table represent molar ratios of the repeating units contained in the above-mentioned resins HR-1 to HR-3, and the composition ratios of the repeating units in the above formula are shown in order from the left.

[solvent]

SL-1: Propylene glycol monomethyl ether acetate (PGMEA)

SL-2: Cyclohexanone

SL-3:? -Butyrolactone

[Surfactants]

W-1: PF656 (manufactured by OMNOVA Solutions Inc.)

<Evaluation>

(Pattern formation)

An organic antireflection film ARC29SR (NISSAN CHEMICAL INDUSTRIES, LTD.) Was applied on a silicon wafer and baked at 205 DEG C for 60 seconds to form an antireflection film having a film thickness of 95 nm. Sensitive active or radiation-sensitive resin compositions shown in Table 3 were coated on the resist film and baked (PB) for 60 seconds at 100 ° C to form a resist film having a thickness of 100 nm.

Using the ArF excimer laser immersion scanner (manufactured by ASML Holding NV; XT1700i, NA 1.20, C-Quad, OUTER SIGMA 0.900, INNER SIGMA 0.812, XY deflection), the obtained wafer was used to form a hole portion 45 nm, (Here, a portion corresponding to the hole is shielded for negative image formation). Ultrapure water was used as the immersion liquid. And then heated (PEB: Post Exposure Bake) at 105 DEG C for 60 seconds. Then, it was purged with an organic solvent-based developer (butyl acetate) for 30 seconds, developed, and rinsed with a rinsing liquid (4-methyl-2-pentanol) for 30 seconds. Subsequently, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to obtain a contact hole pattern having a hole diameter of 45 nm. In Example 14, 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 4-methyl-2-pentanol solvent were used to form a resist film A top coat layer having a thickness of 100 nm was formed, followed by exposure and development.

(Evaluation of Development Defect)

The number of developed defects was measured by a defect inspection apparatus KLA2360 (manufactured by KLA-Tencor Corporation) for a silicon wafer on which a contact hole pattern was formed by the above-described method to calculate the number of development defects per unit area [cm 2]. The smaller the value, the better. The results are summarized in Table 3.

(Exposure latitude (EL))

The optimum exposure amount at the time of resolving a contact hole pattern having a hole portion of 45 nm was evaluated as the sensitivity (E _opt ) (mJ / cm 2) by observing the hole size with a scanning electron microscope (SEM, Hitachi, Ltd. S- Cm &lt; 2 &gt;). Based on the obtained optimum exposure amount (E _opt ), the exposure amount when the hole size became ± 10% of the target value of 45 nm (that is, 40.5 nm and 49.5 nm) was obtained. Then, the exposure latitude EL (%) defined by the following equation was calculated. The larger the value of EL is, the smaller the change in performance due to the change in the exposure amount is. The results are summarized in Table 3.

[(%)] = ([(Exposure dose at which the hole portion becomes 40.5 nm) - (exposure amount at which the hole portion becomes 49.5 nm)] / E _opt ) x 100

(Pattern shape evaluation)

The sectional shape of the contact hole pattern obtained by the above method was observed using a scanning electron microscope to measure the hole diameter Lb at the bottom of the resist pattern and the hole diameter La at the top of the resist pattern did. The closer La / Lb of La to Lb is, the closer to 1, the better the pattern shape. The evaluation was carried out in the following five steps by the absolute value of the difference between La and Lb (La / Lb) and 1: 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 with good exposure latitude, development characteristics, and pattern profile was formed.

Further, as can be seen from the comparison of Examples 1 to 4, it was confirmed that the resin (B) had the above characteristics when the resin (B) had a repeating unit represented by the general formula (VIII) (Example 4).

As can be seen from the comparison between Example 1 and Examples 5 to 6, when the cation in the photo acid generator is a cation represented by the general formulas (C-2) to (C-3) .

In addition, as can be seen from the comparison between Example 1 and Example 7, the compound represented by the general formula (A-1) and the compound can be used in combination with a compound generating an acid by irradiation with another actinic ray or radiation (Example 7), it was confirmed that the above characteristics were better.

Further, as can be seen from the comparison between Example 1 and Example 10, it was confirmed that when the solvent contains a lactone type solvent (Example 1), the above characteristics are more excellent.

As can be seen from the comparison between Example 1 and Example 11, it was confirmed that the above characteristics were better when the ketone solvent was included in the solvent (Example 1).

Further, as can be seen from the comparison between Example 1 and Examples 12 to 13, the onium salt which is relatively weak acid relative to the photoacid generator (A) or the onium salt which is the basic compound (d-1) When the basic compound having a protecting group constituting the mating group was used (Example 12 and Example 13), it was confirmed that the above characteristics were better.

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

Claims (18)

(A) a step of forming a film by a sensitizing actinic ray or radiation-sensitive resin composition containing (A) and (B)
(A) a compound which generates an acid by irradiation with an actinic ray or radiation represented by the general formula (A-1)
(B) a resin having an increased polarity due to the action of an acid having a repeating unit represented by the general formula (nI) and having reduced solubility in a developer containing an organic solvent
(B) irradiating the film with an actinic ray or radiation, and
(C) a step of developing the film irradiated with the actinic ray or radiation using a developer containing an organic solvent.

[In the 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 them represents an alkyl group substituted by a fluorine atom or at least one fluorine atom. p represents an integer of 1 to 3; R ¹ and R ² each independently represent a hydrogen atom or an organic group. q represents an integer of 1 to 8; L ¹ represents a single bond, -O-, -COO- or -OCO-. L ² represents a single bond or a divalent linking group. Y represents a group having a cyclic structure having 3 to 18 carbon atoms which may have a substituent. Z ¹⁺ represents a cation. The content of fluorine atoms in the anion in the general formula (A-1) is 0 to 20% by mass)

Wherein R ₁₃ 'to R ₁₆ ' each independently represent 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 group having an acid-decomposable group. X ₁ and X ₂ each independently represent a methylene group, an ethylene group, an oxygen atom or a sulfur atom. n represents an integer of 0 to 2] The method according to claim 1,
Wherein the compound represented by the general formula (A-1) is a compound represented by the following general formula (A-2).

[In the general formula (A-2), R ¹ and R ² each independently represent a hydrogen atom or an organic group which is not substituted with fluorine. q represents an integer of 1 to 8; L ² represents a single bond or a divalent linking group. Y represents a group having a cyclic structure having 3 to 18 carbon atoms which may have a substituent. The content of the fluorine atom in the anion in the general formula (A-2) is 0 to 20% by mass or less. Z ¹ represents a cation] 3. The method according to claim 1 or 2,
And Y is a polycyclic aliphatic group. 3. The method according to claim 1 or 2,
In the formula _{(nⅠ), R 13 '~} R 16' wherein at least one resulting pattern forming method characterized in that it has an acid-decomposable group of. 5. The method of claim 4,
The group having an acid-decomposable group is a group represented by * ¹ -L ³ -AD (wherein L ³ represents an alkylene group, AD represents an acid-decomposable group, and * ¹ represents a bonding position with the resin) / RTI &gt; 3. The method according to claim 1 or 2,
Wherein the resin (B) has a repeating unit represented by the following general formula (VIII).

[In the 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) 3. The method according to claim 1 or 2,
The above actinic ray-sensitive or radiation-sensitive resin composition further comprises a hydrophobic resin, and the content of the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive resin composition is 0.01 to 10% by mass based on the solid content . 8. The method of claim 7,
Wherein 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. 8. The method of claim 7,
Wherein the hydrophobic resin has a repeating unit represented by the general formula (nI).

Wherein R ₁₃ 'to R ₁₆ ' each independently represent 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 group having an acid-decomposable group. X ₁ and X ₂ each independently represent a methylene group, an ethylene group, an oxygen atom or a sulfur atom. n represents an integer of 0 to 2] 3. The method according to claim 1 or 2,
Wherein the actinic radiation sensitive or radiation-sensitive resin composition further comprises a chain-like or cyclic ketone-based solvent. 3. The method according to claim 1 or 2,
Wherein the actinic radiation sensitive or radiation-sensitive resin composition further comprises a lactone solvent. 3. The method according to claim 1 or 2,
^Wherein Z &lt; ^{1 +} &gt; is any one of the cations represented by the general formulas (C-1) to (C-3).

[In the formula (C-1), R ³ to R ⁹ each independently represent a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom or an organic group. At least one of R ³ to R ⁹ represents a hydroxyl group, a carboxyl group, a halogen atom or an organic group. R ¹⁰ and R ¹¹ each independently represent 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. 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]

[In the general formula (C-2), R ¹² and R ¹³ each independently represent 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, a cycloalkyl 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. r represents an integer of 0 to 2; m15 represents an integer of 0 to 8; And R &lt; ¹² &gt; and R &lt; ¹³ &gt; may be bonded to each other to form a ring]

[In the 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 m16 to m18 represents an integer of 1 or more] 3. The method according to claim 1 or 2,
The above actinic ray-sensitive or radiation-sensitive resin composition is produced by irradiation of an actinic ray or radiation different from a compound generating an acid by irradiation of an actinic ray or radiation represented by the above-mentioned general formula (A-1) &Lt; / RTI &gt; further comprising a compound capable of forming a pattern. The actinic ray-sensitive or radiation-sensitive resin composition for use in the pattern forming method according to claim 1,
A photothermographic material comprising a hydrophobic resin and a hydrophobic resin. The actinic ray-sensitive or radiation-sensitive resin composition for use in the pattern forming method according to claim 1,
Wherein the solvent further comprises a ketone-based solvent,
^Wherein the Z ¹⁺ is any one of cations represented by the general formulas (C-1) to (C-3).

[In the formula (C-1), R ³ to R ⁹ each independently represent a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom or an organic group. At least one of R ³ to R ⁹ represents a hydroxyl group, a carboxyl group, a halogen atom or an organic group. R ¹⁰ and R ¹¹ each independently represent 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. 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]

[In the formula (C-2), R ¹² and R ¹³ each independently represent 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, a cycloalkyl 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. r represents an integer of 0 to 2; m15 represents an integer of 0 to 8; And R &lt; ¹² &gt; and R &lt; ¹³ &gt; may be bonded to each other to form a ring]

[In the 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 m16 to m18 represents an integer of 1 or more] The actinic ray-sensitive or radiation-sensitive resin composition for use in the pattern forming method according to claim 1,
Further comprising a lactone-based solvent,
^Wherein the Z ¹⁺ is any one of cations represented by the general formulas (C-1) to (C-3).

[In the formula (C-1), R ³ to R ⁹ each independently represent a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom or an organic group. At least one of R ³ to R ⁹ represents a hydroxyl group, a carboxyl group, a halogen atom or an organic group. R ¹⁰ and R ¹¹ each independently represent 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. 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]

[In the formula (C-2), R ¹² and R ¹³ each independently represent 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, a cycloalkyl 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. r represents an integer of 0 to 2; m15 represents an integer of 0 to 8; And R &lt; ¹² &gt; and R &lt; ¹³ &gt; may be bonded to each other to form a ring]

[In the 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] The actinic ray-sensitive or radiation-sensitive resin composition for use in the pattern forming method according to claim 1,
A compound capable of generating an acid upon irradiation with an actinic ray or radiation different from a compound generating an acid by irradiation with an actinic ray or radiation represented by the general formula (A-1) Or radiation sensitive resin composition. A method of manufacturing an electronic device, comprising the pattern forming method according to any one of claims 1 to 5.