TW201443570A - Pattern formation method, actinic ray-sensitive or radiation-sensitive resin composition used in same, electronic device using same, and production method thereof - Google Patents

Abstract

An object of the present invention is to provide a pattern formation method capable of forming a pattern having good exposure latitude, good development characteristics, and a good shape of pattern profile. The pattern formation method of the present invention comprises: (i) a step of using an actinic ray-sensitive or radiation-sensitive resin composition to form a film, the actinic ray-sensitive or radiation-sensitive resin composition containing a compound that is represented by formula (A-1) and resin that comprises a repeating unit that is represented by formula (nI) and that exhibits increased polarity and decreased solubility with respect to a liquid developer containing an organic solvent as a result of the action of an acid; (ii) a step of subjecting the film to irradiation of actinic rays or radiation; and (iii) a step of subjecting the film that has been irradiated with actinic rays or radiation to development by using a liquid developer that contains an organic solvent.

Description

Pattern forming method, sensitized ray-sensitive or radiation-sensitive resin composition used therewith, electronic device using the same, and method of manufacturing the same

The present invention relates to a pattern forming method, a sensitizing ray-sensitive or radiation-sensitive resin composition used therefor, a method of manufacturing an electronic device using the same, and an electronic device. More specifically, the present invention relates to the fabrication of circuit substrates suitable for semiconductor manufacturing steps such as ICs, liquid crystals, thermal heads, and the like, and other photolithography lithography steps. Method; a sensitizing ray-sensitive or radiation-sensitive resin composition used in the pattern forming method; and a method of manufacturing an electronic device using the same, and an electronic device. In particular, the present invention relates to a pattern forming method for exposure in an ArF exposure apparatus and an ArF liquid immersion type projection exposure apparatus using a far ultraviolet light having a wavelength of 300 nm or less as a light source, and a sensitizing ray property used in the pattern forming method. Or a radiation sensitive resin composition, a method of manufacturing an electronic device, and an electronic device.

Conventionally, in the manufacturing process of a semiconductor device such as an IC or an LSI, fine processing by lithography using a photoresist composition has been performed.

In recent years, a pattern forming method using a developing solution (organic developing solution) containing an organic solvent has been continuously developed (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-123469

On the other hand, there has recently been a general demand for high performance of various electronic devices, and accordingly, further improvement of the characteristics of the photoresist pattern used for microfabrication is required. In particular, in the case where a finer contact hole pattern is to be formed, problems such as insufficient exposure latitude (EL: Exposure Latitude), development defects, and pattern profile deterioration are likely to occur, and improvement in such photoresist performance is being sought.

The inventors of the present invention evaluated the results of the various characteristics described above using the pattern forming method described in Patent Document 1, and found that although the conventionally required level was satisfied, the level of recent requirements was not satisfied, and further improvement was necessary.

SUMMARY OF THE INVENTION An object of the present invention is to provide a pattern forming method in which a pattern having an exposure latitude, a developing property, and a pattern contour having a good shape is formed in view of the above circumstances.

Further, an object of the present invention is to provide a sensitized ray-sensitive or radiation-sensitive resin composition used therefor, an electronic device using the same, and a method for producing the same.

As a result of intensive studies on the problems of the prior art, the present inventors have found that by using a sensitized ray-sensitive or radiation-sensitive resin composition containing a predetermined resin and a predetermined photoacid generator, The developing treatment of the solvent developer can solve the above lessons question.

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

(1) A pattern forming method comprising: (i) a step of forming a film by a photosensitive ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B), wherein (A) is described later. a compound which generates an acid by irradiation with an actinic ray or a radiation represented by the formula (A-1), and (B) has a repeating unit represented by the following formula (nI), and the polarity is increased by the action of an acid and is contained. a resin having reduced solubility of a developing solvent of the organic solvent; (ii) a step of irradiating the film with actinic rays or radiation; and (iii) developing a film irradiated with actinic rays or radiation using a developing solution containing an organic solvent A step of.

(2) The method of forming a pattern according to the above (1), wherein the compound represented by the formula (A-1) is a compound represented by the following formula (A-2).

(3) The pattern forming method according to (1) or (2), wherein the Y-based 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 ' is a group having an acid-decomposable group.

(5) The pattern forming method according to (4), wherein the group represented by the group * ^{1 -} L ³ -AD having an acid-decomposable group; and L ³ represents an alkylene group; and 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 formula (VIII).

The method of forming a pattern according to any one of (1) to (6), wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains a hydrophobic resin, and is composed of a sensitized ray-sensitive or radiation-sensitive resin. The content of the hydrophobic resin in the product is 0.01 to 10% by mass based on the solid content.

(8) The method of forming a pattern according to the above aspect, wherein the hydrophobic resin has one or more selected from the group consisting of a fluorine atom, a ruthenium atom, and a CH ₃ partial structure contained in a 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 formula (nI).

(10) The pattern forming method according to any one of (1) to (9), wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains a chain or cyclic ketone solvent.

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

The pattern forming method according to any one of (1) to (11), wherein Z ¹⁺ is any one of cations represented by the following formulas (C-1) to (C-3).

The pattern forming method according to any one of (1) to (12), wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains a formula represented by the following formula (A-1) A compound which generates an acid by irradiation of actinic rays or radiation is different from a compound which generates an acid by irradiation with actinic rays or radiation.

(14) A sensitizing ray-sensitive or radiation-sensitive resin composition, which is used in the patterning method described in (1) Or a radiation sensitive resin composition further comprising a hydrophobic resin.

(15) A sensitizing ray-sensitive or radiation-sensitive resin composition, which is a sensitizing ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to (1), further comprising a chain or a ring The ketone solvent, wherein Z ¹⁺ is any one of the cations represented by the following formulas (C-1) to (C-3).

(16) A sensitizing ray-sensitive or radiation-sensitive resin composition, which is a sensitizing ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to (1), further containing a lactone-based solvent, Among them, Z ¹⁺ is any one of the cations represented by the following formulas (C-1) to (C-3).

(17) A sensitizing ray-sensitive or radiation-sensitive resin composition, which is a sensitizing ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to (1), which further contains a formula (hereinafter) A-1) A compound which generates an acid by irradiation with actinic rays or radiation, which is different from a compound which generates an acid by irradiation with actinic rays or radiation.

(18) A method of producing an electronic device, comprising the pattern forming method according to any one of (1) to (13).

(19) An electronic device manufactured by the method of manufacturing an electronic device according to (18).

According to the present invention, it is possible to provide a pattern forming method capable of forming a pattern having an exposure latitude, a developing property, and a pattern outline having a good shape. Further, according to the present invention, a sensitized ray-sensitive or radiation-sensitive resin composition used therefor, an electronic device using the same, and a method for producing the same can be provided.

[Formation of the Invention]

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

Regarding the writing method of the group (atomic group) in the present specification, it is not described that the substituted or unsubstituted writing method includes a group having no substituent (atomic group) and a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "actinic ray" or "radiation" means, for example, a ray spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X ray, an electron beam (EB), or the like. Further, the light system of the present invention means actinic rays or radiation.

The "exposure" in this specification refers to exposure by far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers, and uses electron beams, ion beams, etc., unless otherwise specified. The depiction by the particle beam is also included in the exposure.

In the present specification, the "(meth)acrylic monomer" means at least one of the monomers 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”.

In the present specification, the term "organic group" means a functional group containing at least one or more carbon atoms (for example, an alkyl group, a cycloalkyl group, an aryl group, or a group such as a combination thereof), and also contains a hetero group. An atom (for example, an oxygen atom).

The feature of the present invention is a characteristic point which is developed with an organic solvent using a resin containing a repeating unit having a norbornane skeleton in the main chain and a composition of a predetermined photoacid generator. More specifically, first, by containing a norbornane skeleton in the resin, the resin becomes rigid, and the diffusibility of the photoacid generator in the film is suppressed, and as a result, the desired effect is obtained. In addition, when the content of the fluorine atom in the photo-acid generator is less than or equal to a predetermined value, the photo-acid generator is uniformly dispersed in the photoresist film because the driving force of the photo-acid generator on the surface of the photoresist film is small. The pattern shape or EL is a good one. In addition, when the resin containing the repeating unit having a norbornane skeleton in the main chain and the photoacid generator are combined, the pattern at the time of formation of the contact hole pattern is obtained by multiplying the effect of reducing the diffusibility of the acid generator. The shape or EL will be significantly better. In addition, in the case where the above-described characteristics are more excellent, the photosensitive ray-sensitive or radiation-sensitive resin composition may contain a hydrophobized resin to be described later.

The pattern forming method of the present invention has the following steps (i) to (iii).

(i) a step of forming a film by a photosensitive ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B), wherein (A) is represented by the formula (A-1) by actinic a compound that produces an acid by irradiation of radiation or radiation, (B) a resin having a repeating unit represented by the formula (nI) which increases in polarity by an action of an acid and which has reduced solubility in an organic solvent-containing developing solution; (ii) irradiation of an actinic ray or radiation to the film (iii) a step of developing a film irradiated with actinic rays or radiation using a developing solution containing an organic solvent, and hereinafter, first, detailing the sensitizing ray-sensitive or radiation-sensitive resin used in the step (i) The components contained in the composition (hereinafter, simply referred to as "composition") will be described in detail.

<Compound represented by the general formula (A-1) which generates an acid by irradiation with actinic rays or radiation>

The composition contains a compound represented by the formula (A-1) which generates an acid by irradiation with actinic rays or radiation (hereinafter, also referred to as "photoacid generator (A)", "general (A- 1) The compound indicated)).

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

In the 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 a fluorine atom or is substituted with at least one fluorine atom. Alkyl.

The organic group represented by Q ¹ and Q ² is preferably CF ₃ or the like.

Among them, at least one of the exposure latitude, the development characteristics, and the pattern outline is an excellent point (hereinafter, also referred to as "the effect of the present invention is more excellent"), and Q ¹ and Q ² are each An alkyl group independently substituted with a fluorine atom or substituted with at least one fluorine atom is preferred, a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is more preferred, and a fluorine atom or CF ₃ is more preferably both. It is especially good for those with fluorine atoms.

Further, the carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 4. Further, an alkyl group having at least one fluorine atom is preferably a perfluoroalkyl group. Examples of the above alkyl group include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , 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, in the point where the effect of the present invention is excellent, a single bond, or a * ¹ -COO-* ² group (bonded with * ¹ and (CQ ¹ Q ² ) _p , with * ² and (CR ¹ R ² ) _q Bonding) is preferred.

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

The organic group represented by R ¹ and R ² may, for example, be an alkyl group or a cycloalkyl group.

Among them, in the point that the effect of the present invention is excellent, each of R ¹ and R ² is preferably a hydrogen atom or an alkyl group, and both of them are preferably a hydrogen atom system.

Further, the alkyl group may have a substituent (preferably a fluorine atom), and those having a carbon number of 1 to 4 are preferred. More preferably, it is 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, for example, the groups exemplified for the alkyl groups of Q ¹ and Q ² described above.

L ² represents a single bond or a divalent linking group. Examples of the two-valent linking group include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, An alkyl group (preferably having a carbon number of 1 to 6), a cycloalkyl group (preferably having a carbon number of 3 to 10), an alkenyl group (preferably having a carbon number of 2 to 6), or a combination thereof Two-valent linkage base, etc. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene-, - CONH-alkylene- or -NHCO-alkylene-preferably, -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene- For better. In particular, the L ² system * ¹ -OCO-* ² group (bonded with * ¹ to (CR ¹ R ² ) _{q and} bonded with * ² and Y) is more preferred.

Y represents a cyclic structure having a carbon number of 3 to 18 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.

Further, in the case where the effect of the present invention is more excellent, the carbon number is preferably from 6 to 15, and more preferably from 10 to 12.

The cyclic aliphatic group (alicyclic hydrocarbon group) of Y may have a single ring structure or a polycyclic structure. In the case of a cyclic aliphatic group having a monocyclic structure, a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group is preferred. Examples of the cyclic aliphatic group (polycyclic aliphatic group) having a polycyclic structure include a thiol group, a tricyclic fluorenyl group, a tetracyclic fluorenyl group, a tetracyclododecyl group, and an adamantyl group. Polycyclic cycloalkyl.

In particular, the Y-based polycyclic aliphatic group is more preferable because the effect of the present invention is more excellent, and adamantyl group is more preferable.

p represents an integer from 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 from 2 to 8. Among them, the effect of the present invention is more excellent, 2 to 4 is preferable, 2 or 3 is more preferable, and 2 is particularly preferable.

The anion (sulfonic acid anion) in the formula (A-1) has a fluorine atom content of 0 to 20% by mass. In particular, the effect of the present invention is more excellent, and the content of the fluorine atom is preferably from 1 to 18% by mass, more preferably from 3 to 15% by mass.

When the content of the fluorine atom is outside the above range, the effect of the present invention is poor.

Further, the above anion (sulfonic acid anion) is intended to be a moiety other than Z ¹⁺ (anionic moiety) in the formula (A-1).

Further, the content of the fluorine atom is intended to be a ratio of the total molecular weight of the fluorine atom in the anion to the total molecular weight of the anion (total molecular weight of the fluorine atom / total molecular weight of the anion). For example, when the molecular weight of the entire anion is 380 and the fluorine is contained in the anion, the content of the fluorine atom is 10% by mass [(19 × 2/380) × 100].

Z ¹⁺ represents a cation.

The cation is, for example, a phosphonium cation, a phosphonium cation, an iodonium cation, an ammonium cation, a benzothiazolium cation, a phosphonium cation, or the like. Among these, a phosphonium cation and an iodonium cation are preferred, and an aryl phosphonium cation is more preferred.

Among them, the cation represented by the following general formulae (C-1) to (C-3) is preferable because the effect of the present invention is more excellent. Hereinafter, the general formulae (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. Further, at least one of R ³ to R ⁹ represents a hydroxyl group, a carboxyl group, a halogen atom or an organic group.

Wherein 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, or a cycloalkylcarbonyloxy group. A halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group is preferred.

Further, R ⁸ and R ⁹ each 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-sided oxyalkyl group, a 2-sided oxycycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxy group. Alkylcarbonylcycloalkyl.

Further, any two of R ³ to R ⁷ may be bonded to each other to form a ring. Further, R ⁸ and R ⁹ or R ¹⁰ and R ¹¹ may be bonded to each other to form a ring. Further, the ring structure may contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or a guanamine bond.

The ring structure may, for example, be an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a polycyclic fused ring in which two or more such rings are combined. As far as the ring structure is concerned, a 3 to 10 member ring is exemplified, a 4 to 8 member ring is preferred, and a 5 or 6 member ring is more preferred.

R ³ to R ¹¹ may further have a substituent, and as such a substituent, 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 aryl group or an alkane may be mentioned. Oxyl, aryloxy, fluorenyl, arylcarbonyl, alkoxyalkyl, aryloxyalkyl, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonyloxy, aryloxycarbonyloxy, etc. .

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

In the 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 as the atom constituting the ring, a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom may be contained. These groups may have a substituent.

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 group, or an alkylene oxide chain. It is better.

Further, R ¹⁵ represents a hydroxyl group, a carboxyl group, a halogen atom or an organic group. Wherein R ¹⁵ represents 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 group having a cycloalkyl group; It is better. Further, R ¹⁵ is a plural number, and may be the same or different.

The alkyl group of R ¹² to R ¹⁵ is linear or branched, and those having 1 to 10 carbon atoms are preferred.

The cycloalkyl group of R ¹² to R ¹⁵ may, for example, be a monocyclic or polycyclic cycloalkyl group.

The alkoxy group of R ¹⁴ to R ¹⁵ is linear or branched, and those having 1 to 10 carbon atoms are preferred.

The alkoxycarbonyl group of R ¹⁴ to R ¹⁵ is linear or branched, and those having 2 to 11 carbon atoms are preferred.

The group having a cycloalkyl group of R ¹⁵ may, for example, be a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

The alkyl group of the alkylcarbonyl group of R ¹⁵ may, for example, be the same as the above-mentioned alkyl group.

The alkylsulfonyl group and the cycloalkylsulfonyl group of R ¹⁵ are preferably linear, branched or cyclic, and those having 1 to 10 carbon atoms are preferred.

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 alkoxy group. Alkyloxy group and the like.

R ¹² and R ¹³ may be bonded to each other to form a ring, and in terms of the ring structure formed, a ring of 5 or 6 members formed by R ¹² and R ¹³ together with a sulfur atom may be mentioned, and a ring of 5 members is particularly preferable ( That is, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. The ring structure may have a substituent, and 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 the like. Alkoxycarbonyloxy group and the like. There may be a plurality of substituents to the ring structure, and they may be bonded to each other to form a ring.

And R ¹³ to R ^12, the Department of methyl, ethyl, naphthyl group, and R ¹² and R ¹³ are bonded to each other to form together with the sulfur atoms of the divalent group tetrahydrothiophene ring structure is preferred and the like, R ¹² And a divalent group in which R ^{13 is} bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom is particularly preferable.

r represents an integer from 0 to 2. Among them, 0 or 1 is preferred, and 1 is more preferred.

M15 represents an integer from 0 to 8. Among them, 0~2 is preferred.

Hereinafter, the cation represented by the formula (C-2) will be exemplified.

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

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.

Among them, R ¹⁶ to R ¹⁸ are preferably a methyl group, a tertiary butyl group, a methoxy group, a fluorine atom or a chlorine atom.

Further, any two of R ¹⁶ to R ¹⁸ may be bonded to each other to form a ring. Further, the ring structure may contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or a guanamine bond.

M16~m18 each independently represent an integer from 0 to 5. Among them, 1 to 3 is preferred, and 1 is more preferred.

Further, at least one of m16 to m18 represents an integer of 1 or more.

Hereinafter, the cation represented by the formula (C-3) will be exemplified.

In the preferred embodiment of the compound represented by the above formula (A-1), the compound represented by the following formula (A-2) (photoacid generation) is more preferable as the effect of the present invention. Agent).

Further, the definitions and preferred aspects of the respective groups in the above formula (A-2) are as described above.

The photoacid generator (A) can be synthesized by a known method, and can be synthesized, for example, according to the method described in JP-A-2007-161707.

The photoacid generator (A) can be used alone or in combination of two or more.

The content of the photoacid generator (A) in the composition is not particularly limited, but the effect of the present invention is more excellent, and 12 to 30% by mass is preferable with respect to the total solid content in the composition, 12~ 20% by mass is more preferred.

Moreover, the total solid content is intended to mean the total mass of the components constituting the photoresist film to be described later, and the other components of the solvent are removed.

<Resin having a repeating unit represented by the general formula (nI) which increases in polarity by an action of an acid and which has reduced solubility in an organic solvent-containing developing solution>

The composition contains a resin having an increase in polarity due to an action of an acid by a repeating unit represented by the formula (nI) and having reduced solubility in an organic solvent-containing developing solution (hereinafter also referred to as "acid-decomposable resin"). Or "resin (B)").

The resin (B) is a main chain or a side chain of the resin, or both of a main chain and a side chain, and has a group which decomposes by an action of an acid to generate a polar group (hereinafter, Also known as "acid-decomposable group" is preferred.

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

In the formula (nI), R ₁₃ '~R ₁₆ ' each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or an alkyl group. a carbonyl group, a group having a lactone structure, or a group having an acid-decomposable group.

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

n represents an integer from 0 to 2. Preferably, it represents 0~1.

The acid-decomposable group in the group having an acid-decomposable group of R ₁₃ ' to R ₁₆ ', as described above, is decomposed by the action of an acid to form a group of a polar group, and the polar group is decomposed by the action of an acid. The structure of the detached base protection is preferred.

The polar group is not particularly limited as long as it is insoluble or insoluble in the developer containing the organic solvent, but a phenolic hydroxyl group, a carboxyl group, or a fluorinated alcohol group (preferably hexafluoroisopropanol) , sulfonate, sulfonylamino, sulfonyl sulfoximine, (alkylsulfonyl) (alkylcarbonyl) methylene, (alkylsulfonyl) (alkylcarbonyl) fluorene Amino, bis(alkylcarbonyl) methylene , bis(alkylcarbonyl) fluorenylene, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl) fluorenylene, stilbene (alkylcarbonyl)methylene, ginseng An acidic group such as an alkylsulfonyl group methylene group (a group which is dissociated in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide used as a developing solution for photoresist), or an alcoholic hydroxyl group.

Further, the alcoholic hydroxyl group means a hydroxyl group bonded to a hydrocarbon group, and is a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and a fat which is substituted by an electron attracting group such as a fluorine atom as a hydroxyl group. A steroid (for example, a fluorinated alcohol group (hexafluoroisopropanol group, etc.)) is excluded. In the case of an alcoholic hydroxyl group, a hydroxyl group having a pKa of 12 or more and 20 or less is preferred.

The preferred polar group may, for example, be a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) or a sulfonic acid group.

The preferred group as the acid-decomposable group is a group in which the hydrogen atom of the group is substituted with a group derived from an acid.

Examples of the acid-desorbed group include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )( R ₀₂ ) (OR ₃₉ ) and so on.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl 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 arylalkyl 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, an ethyl group, a propyl group, an n-butyl group, and a secondary butyl group. Hexyl, octyl, etc.

The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be a monocyclic type or a polycyclic type. In the case of the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferred, and in the case of a polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferred. Further, at least one of the carbon atoms in the cycloalkyl group may be substituted with 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 anthracenyl group.

The aralkyl group having 7 to 12 carbon atoms of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferred.

The alkenyl group having 2 to 8 carbon atoms of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferred.

In the case of a ring formed by bonding R ₃₆ and R ₃₇ , a cycloalkyl group (monocyclic or polycyclic) is preferred. In the case of a cycloalkyl group, a cycloalkyl group which is a monocyclic group such as a cyclopentyl group or a cyclohexyl group; a cycloalkyl group having a sulfhydryl group, a tetracyclononyl group, a tetracyclododecyl group, an adamantyl group or the like is Preferably. A cycloalkyl group having a monocyclic number of 5 to 6 carbon atoms is more preferable, and a cycloalkyl group having a carbon number of 5 is particularly preferred.

The acid-decomposable group is preferably a cumene ester group, an enol ester group, an acetal ester group or a third-stage alkyl ester group, and more preferably -C(=O)-OR. The alkyl ester group of the third stage represented by ₀ .

In the formula, examples of R ₀ include a tertiary alkyl group such as t-butyl group and t-pentyl group, an isodecyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, and a 1-iso group. Alkoxymethyl group such as butoxyethyl, 1-cyclohexyloxyethyl or the like, 1-methoxymethyl group, 1-methoxymethyl group, 1-ethoxymethyl group, etc., 3-side Oxyalkyl, tetrahydropyranyl, tetrahydrofuranyl, trialkyldecylalkyl, 3-oxocyclohexyl ester, 2-methyl-2-adamantyl, mevalonate Base.

The group having an acid-decomposable group is preferably a group represented by * ¹ -L ³ -AD in order to further prevent the occurrence of acid diffusion.

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

Further, the alkylene group represented by L ³ may also contain a hetero atom. That is, it may be an alkylene group containing a hetero atom. The kind of the hetero atom which may be 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 ruthenium atom. For example, -Y ₁ H, -Y ₁ -, -N(R _a )-, -C(=Y ₂ )-, -CON(R _b )-, -C(=Y ₃ )Y ₄ -, -SO _t -, -SO ₂ N(R _c )-, a halogen atom, or a combination of two or more kinds of such 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 ruthenium atom. Among them, an oxygen atom or a sulfur atom is preferred from the viewpoint of easier handling.

The above R _a , R _b and R _c are each independently a hydrocarbon group selected from a hydrogen atom or a carbon number of 1 to 20. T represents an integer from 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.

It is preferable that at least one of R ₁₃ '~R ₁₆ ' is a group having an acid-decomposable group from the point where the dissolution contrast is improved.

Examples of the halogen atom in R ₁₃ '~R ₁₆ ' include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

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

In the formula (F1), R ₅₀ to R ₅₅ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R ₅₀ to R ₅₅ represents an alkyl group in which a fluorine atom or 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, a decyl group or an alkoxycarbonyl group), preferably a hydrogen atom.

It is preferred that all of R ₅₀ to R ₅₅ are fluorine atoms.

The content of the repeating unit represented by the formula (nI) is not particularly limited, but the effect of the present invention is more excellent, and 5 to 50 mol% is preferable with respect to the total repeating unit in the resin (B). 10 to 40 mol% is better, and 15 to 35 mol% is better.

The following specific examples are given to the repeating unit represented by the above formula (nI), but the present invention is not limited to these compounds. Among them, the repeating unit represented by (II-f-16) to (II-f-19) is preferred.

It is preferable that the resin (B) has a repeating unit represented by the following formula (VIII) from the viewpoint of substrate adhesion.

In the above 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 formula (VIII) is not particularly limited, but the effect of the present invention is more excellent, and it is preferably 5 to 60 mol% based on all the repeating units in the resin (B). 15~55 mol% is better, 30~50 mol% is better.

The resin (B) is preferably a repeating unit represented by the above formula (nI) and a repeating unit represented by the formula (VIII). Accordingly, the adhesion of the photoresist film to the substrate is improved.

The following specific examples of the repeating unit represented by the above formula (VIII) include the following specific examples, but the present invention is not limited thereto.

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

In the formula (AI), Xa ₁ represents a hydrogen atom and 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) or a cycloalkyl group (monocyclic or polycyclic). Two of Rx ₁ to Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

The alkyl group which may have a substituent represented by Xa ₁ may, for example, be a group represented by a methyl group or -CH ₂ -R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and a mercapto group having 5 or less carbon atoms, preferably an alkyl group having 3 or less carbon atoms. Good for methyl. In one aspect, Xa _{1 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The divalent linking group of T may, for example, be an alkyl group, a -COO-Rt- group or a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkyl group.

A T-based single bond or a -COO-Rt- group is preferred. The Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group or a -(CH ₂ ) ₃ - group.

In the case of the alkyl group of Rx ₁ to Rx ₃ , the carbon number of the methyl group, the ethyl group, the n-propyl group, the isopropyl group, the n-butyl group, the isobutyl group, the t-butyl group, etc. is 1 to 4 good.

In the case of a cycloalkyl group of Rx ₁ to Rx ₃ , a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a polycyclic ring such as a thiol group, a tetracyclononyl group, a tetracyclododecyl group or an adamantyl group; The cycloalkyl group is preferred.

The cycloalkyl group formed by bonding two Rx ₁ to Rx ₃ is a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a thiol group, a tetracyclic fluorenyl group, and a tetracyclic decyl group; A polycyclic cycloalkyl group such as an adamantyl group is preferred. A cycloalkyl group having a carbon number of 5 to 6 is particularly preferred.

The cycloalkyl group formed by bonding two Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring may have a hetero atom such as an oxygen atom or a substituent having a hetero atom such as a carbonyl group.

The repeating unit represented by the formula (AI), for example, wherein Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to each other to form the above cycloalkyl group is preferred.

Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, and an alkoxycarbonyl group. (carbon number 2 to 6), etc., and a carbon number of 8 or less is preferable.

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

Specific examples of the resin (B), which are disclosed in [0265] of the specification of the U.S. Patent Application Publication No. 2012/0135348, are not limited to the examples.

The resin (B) has a repeating unit represented by the formula (AI), and for example, a repeating unit represented by the formula (I) and a resin having at least one of the repeating units represented by the formula (II) are Better.

In the formulae (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 a carbon atom bonded to R ₂ .

R ₁ and R _{3 are} preferably represented by a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. R _11. 1 monovalent organic group and R preferred embodiment of the same system and the general formula (AI) of particular those described in Example _11.

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

The cycloalkyl group in R ₂ may be a single ring or a polycyclic ring, and may have a substituent.

R ₂ is preferably an alkyl group, more preferably a carbon number of 1 to 10, still more preferably an alkyl group having 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. In the case where R is an alicyclic structure formed together with the carbon atom, a monocyclic alicyclic structure is preferred, and the carbon number thereof is preferably from 3 to 7, more preferably from 5 or 6.

R _{3 is} preferably a hydrogen atom or a methyl group, more preferably a methyl group.

The alkyl group in R ₄ , R ₅ and R ₆ may be linear or branched, and may have a substituent. In the case of an alkyl group, a carbon number of 1 to 4 such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a t-butyl group is preferred.

The cycloalkyl group in R ₄ , R ₅ and R ₆ may be a single ring or a polycyclic ring and may have a substituent. In the case of a cycloalkyl group, a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a cycloalkyl group having a polycyclic group such as a thiol group, a tetracyclononyl group, a tetracyclododecyl group or an adamantyl group; good.

Examples of the substituent which each of the above-mentioned groups may have are the same as those of the above-mentioned substituents which each group of the formula (AI) may have.

The resin (B) is more preferably a resin containing a repeating unit represented by the formula (I) represented by the formula (AI) and a repeating unit represented by the formula (II).

The repeating unit system having an acid-decomposable group contained in the resin (B) may be used alone or in combination of two or more. In the case of the combination, the specific examples disclosed in the paragraph [0287] of the specification of the US Patent Application Publication No. 2012/0135348 can be used, but are not limited thereto.

The resin (B) is preferably a repeating unit having a lactone structure or a sultone (cyclic sulfonate) structure.

The lactone group or the sultone group may be used as long as it has a lactone structure or a sultone structure, but is preferably a 5- to 7-membered ring lactone structure or a sultone structure. The 7-membered ring lactone structure or the sultone structure is formed in the form of a bicyclic structure or a spiro structure, and is preferred to those of other ring structures. The formula (LC1-1) to (LC1-17) and the following formulas (SL1-1) and (SL1-2) disclosed in the paragraph [0318] having the specification of the US Patent Application Publication No. 2012/0135348 Having any of them The repeating unit of the ester structure or the sultone structure is more preferred. Also, the lactone structure or the sultone structure may be directly bonded to the main chain. More preferably, the lactone structure or the sultone structure is (LC1-1), (LC1-4), (LC1-5), (LC1-8), (LC1-4). When a specific lactone structure or a sultone structure is used, LWR and development defects become good.

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

The resin (B) is preferably a repeating unit having a hydroxyl group or a cyano group other than the general formula (AI). According to this, the substrate adhesion, developer pro And sex will improve. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group, and a group having no acid-decomposable base is preferred. As the alicyclic hydrocarbon structure in the hydroxy or cyano substituted alicyclic hydrocarbon structure, adamantyl, diamantyl, norbornyl group is preferred. In the case of the alicyclic hydrocarbon structure preferably substituted by a hydroxyl group or a cyano group, a partial structure represented by the following formulas (VIIa) to (VIId) is preferred.

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

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

In the formula (AIIa) to (AIId), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c to R ₄ c are synonymous with R ₂ c to R ₄ c in the formulae (VIIa) to (VIIc).

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

Specific examples of the repeating unit having a hydroxyl group or a cyano group include the repeating unit disclosed in the paragraph [0340] of the specification of the U.S. Patent Application Publication No. 2012/0135348, but the present invention is not limited to the examples.

The resin (B) is a resolving power, a heat resistance, a sensitivity, etc., which are required to adjust dry etching resistance, standard developer suitability, substrate adhesion, photoresist profile, and even photoresist, in addition to the above-mentioned repeating structural unit. For the purpose, there can be a wide variety of repeating structural units.

The repeating structural unit of the following monomer is exemplified as the repeating structural unit of the following monomer, but is not limited to these examples.

Accordingly, the properties required for the resin (B) used in the composition of the present invention are, in particular, (1) solubility in a coating solvent, (2) film forming property (glass transfer point), and (3) alkali development. The fine adjustment of (4) film thinning (hydrophobicity, alkali-soluble base selection), (5) adhesion of the unexposed portion to the substrate, and (6) dry etching resistance are possible.

Examples of such a monomer include, for example, one selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl groups. A compound having an addition polymerizable unsaturated bond such as an ester.

In addition, if it is equivalent to the above various repeating structural units The addition polymerizable unsaturated compound which can be copolymerized with a monomer can also be copolymerized.

In the resin (B), the molar ratio of each repeating structural unit is appropriately set to adjust the dry etching resistance of the photoresist or the standard developer suitability, substrate adhesion, photoresist profile, and even photoresist. Performance resolution, heat resistance, sensitivity, etc.

When the composition of the present invention is used for ArF exposure, it is preferred that the resin (B) used in the composition of the present invention has substantially no aromatic group from the viewpoint of transparency to ArF light. More specifically, in all the repetitions of the resin (B), the repeating unit having an aromatic group is preferably 5 mol% or less of the total, and more preferably 3 mol% or less, and more preferably 0 mol. %, that is, a repeating unit having no aromatic group is more preferable. Further, the resin (B) is preferably a monocyclic or polycyclic alicyclic hydrocarbon structure.

Moreover, it is preferable that the resin (B) does not contain a fluorine atom or a ruthenium atom from the viewpoint of compatibility with a hydrophobic resin to be described later.

The resin (B) in the present invention can be synthesized according to a usual method (e.g., radical polymerization). Specifically, the synthesis method disclosed in paragraphs [0126] to [0128] of the specification of the US Patent Application Publication No. 2012/0164573 can be utilized.

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, still more preferably from 3,000 to 15,000, and particularly preferably from 3,000 to 11,000, in terms of polystyrene, according to the GPC method. By setting the weight average molecular weight to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance or dry etching resistance, and it is possible to prevent deterioration of developability, increase in viscosity, and deterioration in film formability.

The degree of dispersion (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 more excellent the resolution and the photoresist shape, and the side walls of the photoresist pattern are smooth and excellent in roughness.

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

<Other ingredients>

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

Hereinafter, any component will be described in detail.

(Compound (B2) which generates an acid by irradiation with actinic rays or radiation)

The composition of the present invention may contain a compound (B2) which generates an acid by irradiation with actinic rays or radiation, which is different from the compound represented by the above formula (A-1) (hereinafter, also referred to as "photoacid" Producer" or "compound (B2)").

In the case of the compound (B2), a compound which generates an organic acid by irradiation with actinic rays or radiation is preferred.

The compound (B2) may be in the form of a low molecular compound or may be in a form of being incorporated into a part of the polymer. Further, the form of the low molecular compound and the form of 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 still more preferably 1,000 or less.

When the compound (B2) is in a form of being incorporated into a part of the polymer, it may be incorporated into one of the aforementioned acid-decomposable resins, or may be a resin which is different from the acid-decomposable resin.

In the present invention, the compound (B2) is preferably a form of a low molecular compound.

In the case of the compound (B2), a photo-cationic polymerization photoinitiator, a photoradical polymerization photoinitiator, a dye-based photochromic agent, a photochromic agent, or a micro-resist can be appropriately selected. A known compound and a mixture thereof which generate an acid by irradiation with actinic rays or radiation are used.

For example, a diazonium salt, a phosphonium salt, a phosphonium salt, an iodonium salt, a sulfonium sulfonium imide, a sulfonium sulfonate, a diazodiazine, a diterpene, and an o-nitrobenzenesulfonate can be mentioned.

The preferred compound in the compound (B2) may, for example, be a compound represented by the following formula (ZI), (ZII) or (ZIII).

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

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

Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group. Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkyl group (for example, a butyl group and a pentyl group).

Z ^- represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ^- may, for example, be a sulfonic acid anion, a carboxylic acid anion, a sulfonyl quinone imine anion, a bis(alkylsulfonyl) quinone imine anion, or a decyl group. Sulfhydryl) methyl anion and the like.

The non-nucleophilic anion refers to an anion having a significantly low ability to cause a nucleophilic reaction, and can inhibit an anion which decomposes over time due to an intramolecular nucleophilic reaction. Accordingly, the temporal stability of the sensitized ray-sensitive or radiation-sensitive resin composition is enhanced.

Examples of the sulfonic acid anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphorsulfonate anion, and the like.

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

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be 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, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, the cycloalkyl group, and the 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 phosphorus fluoride (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), cesium fluoride, and the like (for example, SbF ₆ ^- ).

On Z ^- of the non-nucleophilic anion, the α position by at least a fluorine atom-substituted aliphatic sulfonic acid anion, a fluorine atom or an aromatic sulfonic acid anion substituted with a fluorine atom, an alkyl group by fluorine An atom-substituted bis(alkylsulfonyl) quinone imine anion, and an alkyl (alkylsulfonyl)methyl anion having an alkyl group substituted by a fluorine atom is preferred. In the case of a non-nucleophilic anion, a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, and more preferably a nonafluorobutanesulfonate anion or perfluorooctane An alkanesulfonate anion, an anion of pentafluorobenzenesulfonate, an anion of 3,5-bis(trifluoromethyl)benzenesulfonate.

Among the compounds (B2), a compound exemplified in paragraph [0143] of US2012/0207978A1 can be cited as a particularly preferred example.

The compound (B2) can be synthesized by a known method, and can be synthesized, for example, according to the method described in JP-A-2007-161707.

In the case of using two or more kinds of the compound (B2), the total content of the compound (B2) is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass based on the total solid content of the composition. %, more 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 controlling agent. The acid diffusion controlling agent functions as a quenching agent that absorbs an acid generated by a photoacid generator or the like. In the case of the acid diffusion controlling agent, a basic compound, a low molecular compound having a nitrogen atom and having a leaving group by an action of an acid, a basic compound which is alkalinized or disappeared by irradiation with actinic rays or radiation, The photoacid generator becomes a relatively weak acid sulfonium salt.

In the case of a basic compound, it is preferred to have the following formula A compound of the structure shown in (A) to (E).

In the general formulae (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different from each other to represent a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), or a cycloalkyl group. It is a carbon number of 3 to 20) or an aryl group (carbon number of 6 to 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 from each other to represent an alkyl group having 1 to 20 carbon atoms.

In the above alkyl group, the alkyl group having a substituent is an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. good.

The alkyl group in the general formulae (A) and (E) is preferably unsubstituted.

As preferred compounds, hydrazine, aminopyrrolidine, pyrazole, pyrazoline, and piperidin are mentioned. Amino group Porphyrin, aminoalkyl a porphyrin, a piperidine or the like; as a more preferable compound, a compound having an imidazole structure, a dioxonium bicyclic structure, a hydrazine hydroxide structure, a hydrazine 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/or an ether bond, and the like.

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

The preferred basic compound may further be an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group or an ammonium salt compound having a sulfonate group.

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferred. The amine compound is preferably a tertiary amine compound. The amine compound is bonded to a nitrogen atom with at least one alkyl group (preferably having a carbon number of 1 to 20), and a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (except for an alkyl group). Good carbon number 6~12) can also be bonded to nitrogen atoms. The amine compound is preferably an oxygen atom in the alkyl chain, and an alkoxyalkyl group is preferred. The number of oxygen alkyl groups is one or more, preferably from 3 to 9, more preferably from 4 to 6, in the molecule. Among the oxygen alkyl groups, an oxygen-extended ethyl group (-CH ₂ CH ₂ O-) or an oxygen-extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred. More preferably, it is an oxygen-extended ethyl group.

As the ammonium salt compound, an ammonium salt compound of a primary, secondary, tertiary or tertiary grade can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferred. The ammonium salt compound is preferably a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group, as long as at least one alkyl group (preferably having a carbon number of 1 to 20) is bonded to a nitrogen atom. It can also be bonded to a nitrogen atom for a carbon number of 6 to 12). The ammonium salt compound is preferably one having an oxygen atom in the alkyl chain and an alkoxyalkyl group. The number of the oxygen-extended alkyl groups is one or more, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an oxygen-extended ethyl group (-CH ₂ CH ₂ O-) or an oxygen-extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred. More preferably, it is an oxygen-extended ethyl group.

As the anion of the ammonium salt compound, a halogen atom can be cited A sulfonate, a borate, a phosphate or the like, among which a halogen atom or a sulfonate is preferred.

Further, the following compounds are also preferred as the basic compound.

In the case of the basic compound, in addition to the above-mentioned compounds, paragraphs [0180] to [0225] of JP-A-2011-22560, and paragraphs [0218] to [0219 of JP-A-2012-137735 may be used. The compound described in paragraphs [0416] to [0438] of the International Publication No. WO2011/158687A1.

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

The composition of the present invention may contain a basic compound. However, 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 use of the photoacid generator (A) to the composition of the basic compound is preferably a photoacid generator (A) / a basic compound (mole ratio) = 2.5 to 300. In other words, from the point of sensitivity and resolution, the molar ratio of 2.5 or more is preferable, and from the viewpoint of suppressing the decrease in the resolution of the photoresist pattern after the exposure to the heat treatment, 300 or less is preferable. good. The photoacid generator (A)/basic compound (mole ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

A low molecular compound having a nitrogen atom and having a leaving group by an action of an acid (hereinafter, also referred to as a compound (C)) is a group which is liberated by an action of an acid, and an acetal group, a carbonate group, an amine A carbamate group, a tertiary ester group, a tertiary hydroxyl group, and a half amine acetal group are preferred, and a urethane group and a half amine acetal group are particularly preferred.

The molecular weight of the compound (C) is preferably from 100 to 1,000, more preferably from 100 to 700, and particularly preferably from 100 to 500.

In the case of the compound (C), an amine derivative having a group which is liberated by an acid action on a nitrogen atom is preferred.

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

In the formula (d-1), Rb each independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 10), a cycloalkyl group (preferably having a carbon number of 3 to 30), and an aryl group. The carbon number is 3 to 30), the aralkyl group (preferably, the carbon number is 1 to 10), or the alkoxyalkyl group (preferably, the carbon number is 1 to 10). The Rb groups may be bonded to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group or aralkyl group represented by Rb may be a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group or a piperidinyl group. A functional group such as a phenyl group or a pendant oxy group, an alkoxy group or a halogen atom is substituted. The alkoxyalkyl group represented by Rb is also the same.

Rb is preferably a linear or branched alkyl group, a cycloalkyl group, Aryl. More preferably, it is a linear or branched alkyl group or a cycloalkyl group.

Examples of the ring formed by linking two Rbs 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 formula (d-1) is as disclosed in the paragraph [0466] of the specification of the US Patent Application Publication No. 2012/0135348, but is not limited thereto.

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

In the formula (6), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When 1 is 2, the two Ra groups may be the same or different, and the two Ra groups may be bonded to each other to form a hetero 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.

The Rb is synonymous with Rb in the formula (d-1), and the preferred examples are also the same.

l represents an integer from 0 to 2, and m represents an integer from 1 to 3, which satisfies l+m=3.

In the formula (6), the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkyl group as the Rb, the cycloalkyl group, the aryl group, and the aralkyl group are the groups of the group which may be substituted. Replaced by the same base.

Specific examples of the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group of Ra (the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group may be substituted by the above group) may be mentioned. The same base as the above specific example of Rb.

Preferred compounds (C) are specifically listed in the United States. The compound disclosed in paragraph [0475] of the specification of the publication No. 2012/0135348 is disclosed, but is not limited thereto.

The compound represented by the formula (6) can be synthesized based on, for example, JP-A-2007-298569, JP-A-2009-199021, and the like.

In the present invention, the compound (C) may be used alone 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, even more preferably based on the total solid content of the composition. It is 0.01 to 5% by mass.

A compound which is reduced or disappeared alkaline by irradiation with actinic rays or radiation has a proton acceptor functional group, and is decomposed by irradiation with actinic rays or radiation, and proton acceptor is reduced, disappeared, or protonated. A compound that is reactively converted to an acid. Also written below is the compound (PA).

The proton acceptor functional group means a group which can electrostatically interact with a proton or a functional group having an electron, for example, a functional group having a polycyclic structure such as a cyclic polyether, or a lone electron having no π conjugate The functional group of the nitrogen atom. The nitrogen atom having a lone pair of electrons not participating in the π-conjugation means, for example, a nitrogen atom having a partial structure represented by the following formula.

With regard to a preferred partial structure of the proton acceptor functional group, for example, a crown ether, an azacrown ether, a mono- to tertiary amine, a pyridine, an imidazole, and a pyridyl group are mentioned. Structure, etc.

The compound (PA) is a compound which decomposes by irradiation with actinic rays or radiation to reduce or eliminate proton acceptability, or convert from proton acceptor to acid. Herein, the decrease or disappearance of proton acceptor or the change from proton acceptor to acid refers to a change in proton acceptor caused by the addition of a proton to a proton acceptor functional group, specifically, When a compound (PA) having a proton-receptive functional group and a proton-forming proton-added body have an equilibrium constant in chemical equilibrium, the equilibrium constant is reduced.

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

In the present invention, the acid dissociation constant pKa of the compound which is decomposed by the compound (PA) by irradiation with actinic rays or radiation is preferably a pKa < -1, more preferably -13 < pKa < -1. More preferably, it is -13 < pKa < -3.

In the present invention, the acid dissociation constant pKa is an acid dissociation constant pKa in an aqueous solution, and is, for example, a chemical note (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). Low means that the acid strength is greater. The acid dissociation constant pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C using an infinitely diluted aqueous solution, and can also be determined by Hammett using the following software package 1 The value of the substituent constant and the database of well-known literature values. The pKa values described in the present specification all indicate values obtained by calculation using the package software.

Package Software 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

The compound (PA) is, for example, a proton-added product obtained by decomposition of a compound represented by the following formula (PA-1) as a result of irradiation with actinic rays or radiation. The compound represented by the formula (PA-1) has a proton acceptor functional group and an acidic group at the same time, and the proton acceptor is reduced, disappeared, or converted by proton acceptor as compared with the compound (PA). An acidic compound.

QA-(X) _n -BR (PA-1)

In the 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 the paragraph [0280] of the specification of the US Patent Application Publication No. 2011/0269072.

Further, in the present invention, a compound (PA) other than the compound which produces the compound represented by the formula (PA-1) can be appropriately selected. For example, it can be used as an ionic compound, and the cation portion has a proton acceptor site. Compound. More specifically, a compound represented by the following formula (7) and the like can be given.

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

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

R represents an aryl group.

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

X ^- represents a counter anion.

Specific examples of X ^- may be the same as those of the photoacid generator.

Specific examples of the aryl group of R and R _N include a phenyl group.

Specific examples of the proton acceptor functional group possessed by R _N are the same as those described for the above formula (PA-1).

In the following, specific examples of the ionic compound having a proton acceptor moiety in the cation moiety include the compounds exemplified in paragraph [0291] of the specification of the US Patent Application Publication No. 2011/0269072.

In addition, the compound can be synthesized by a method described in, for example, JP-A-2007-230913 and JP-A-2009-122623.

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

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

As the composition of the present invention, an onium salt which is a relatively weak acid with respect to the photoacid generator (A) can be used as an acid diffusion controlling agent.

A mixed photoacid generator (A) and a ruthenium salt which generates an acid which is a relatively weak acid with respect to an acid produced by the photoacid generator (A), and is irradiated by actinic radiation or radiation. When the acid generated by the photoacid generator (A) collides with the unreacted phosphonium salt having a weak acid anion, a weak acid is released via salt exchange to produce a phosphonium salt having a strong acid anion. In this process, since the strong acid is exchanged for a weak acid having a lower catalytic activity, in appearance, the acid is deactivated and the acid diffusion can be controlled.

The phosphonium salt which is relatively weakly acidic with respect to the photoacid 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 (except that a carbon group adjacent to S is not substituted with a fluorine atom), and R ⁵² is an organic group. Y ³ is a linear, branched or cyclic alkyl or aryl group, and Rf is a fluorine atom-containing hydrocarbon group, and the M ⁺ systems are each independently a hydrazine or an iodonium cation.

Preferred examples of the phosphonium cation or the iodonium cation represented by M ⁺ include the phosphonium cation represented by the above S ⁺ (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ), and I ⁺ (R ₂₀₄ ) (R) ₂₀₅ ) The iodonium cation represented.

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

A preferred example of the anion portion of the compound represented by the formula (d1-2) is a structure exemplified in paragraph [0201] of JP-A-2012-242799.

Preferred examples of the anion portion of the compound represented by the formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP-A-2012-242799.

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

The compound represented by any one of the following formulae (E-1) to (E-3) is preferred for the above compound.

In the general formulae (E-1) to (E-3), R ₁ , R ₂ and R ₃ represent a substituent having 1 or more carbon atoms.

L ₁ represents a divalent linking group or a single bond linking a cationic moiety to an anionic moiety.

-X ^- represents an anion moiety selected from the group consisting of -COO ^- , -SO ₃ ^- , -SO ₂ ^- , -N ^- -R ₄ . R ₄ represents a group having a carbonyl group at a point of bonding to an adjacent N atom: -C(=O)-, a sulfonyl group: -S(=O) ₂ -, a sulfinyl group: -S(=O)- Valency substituent.

R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be bonded to each other to form a ring structure. Further, in (E-3), two of R ₁ to R ₃ may be combined to form a double bond with the N atom.

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, and an alkylamino group. A carbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group or the like. Preferred are an alkyl group, a cycloalkyl group, and an aryl group.

The L ₁ system which is a divalent linking group may, for example, be a linear or branched alkyl group, a cycloalkyl group, an extended aryl group, a carbonyl group, an ether bond, an ester bond, a guanamine bond, a urethane bond, or a urea. A key or a combination of two or more of these types. L _{1 is more} preferably an alkyl group, an aryl group, an ether bond, an ester bond, or a combination of two or more of these.

Preferred examples of the compound represented by the formula (E-1) include paragraphs [0037] to [0039] of JP-A-2013-6827, and paragraphs of JP-A-2013-8020. [0027] ~ [0029] The compounds exemplified.

Preferred examples of the compound represented by the formula (E-2) include the compounds exemplified in paragraphs [0012] to [0013] of JP-A-2012-189977.

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

The content of the cerium salt which is a relatively weak acid with respect to the photoacid generator is preferably 0.5 to 10.0% by mass, more preferably 0.5 to 8.0% by mass, and more preferably 1.0 to 8.0% by mass based on the total solid content of the composition. Better yet.

(hydrophobic resin)

In particular, when the composition of the present invention is suitable for liquid immersion exposure, it may contain a hydrophobic resin (hereinafter also referred to as "hydrophobic resin (D)" or simply "resin (D)"). Further, it is preferred that the hydrophobic resin (D) is different from the resin (B).

Accordingly, the hydrophobic resin (D) is locally present on the surface layer of the film, and when the liquid immersion medium is water, the static/dynamic contact angle of the surface of the photoresist film to water can be increased to improve the immersion compliance.

The hydrophobic resin (D) is preferably designed to be locally present at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and may not contribute to the polar/nonpolar substance. Evenly mixed.

In view of the fact that the hydrophobic resin (D) has a "fluorine atom", a "ruthenium atom", and a "CH ₃ partial structure contained in a side chain portion of the resin", the hydrophobic resin (D) is one or more. Preferably, it is more preferable to have two or more types.

In the case where the hydrophobic resin (D) contains a fluorine atom and/or a ruthenium atom, the fluorine atom and/or the ruthenium atom in the hydrophobic resin (D) may be contained in the main chain of the resin or may be contained in the side chain. .

In the case of the fluorine-containing atom of the hydrophobic resin (D), 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 is preferred.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may have a fluorine atom. Substituent.

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may have a substituent other than a fluorine atom.

In the aryl group having a fluorine atom, at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group may be substituted with a fluorine atom, or may 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 those represented by the following formulas (F2) to (F4), but the present invention is Not limited to this.

In the general formulae (F2) to (F4), R ₅₇ to R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight chain or branched). However, at least one of R ₅₇ to R ₆₁ , at least one of R ₆₂ to R ₆₄ , and at least one of R ₆₅ to R ₆₈ each independently represent a fluorine atom or at least one hydrogen atom substituted by a fluorine atom. The alkyl group (preferably having a carbon number of 1 to 4).

It is preferred 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 in which at least one hydrogen atom is substituted by a fluorine atom (preferably having 1 to 4 carbon atoms), and a perfluoroalkyl group having 1 to 4 carbon atoms is more preferable. R ₆₂ and R ₆₃ may be bonded to each other to form a ring.

Specific examples of the group represented by the formula (F2) include, for example, p-fluorophenyl group, pentafluorophenyl group, and 3,5-bis(trifluoromethyl)phenyl group.

Specific examples of the group represented by the formula (F3) include those exemplified in the paragraph [0500] of the specification of the U.S. Patent Application Publication No. 2012/0251948.

Specific examples of the group represented by the formula (F4) include, for example, -C(CF ₃ ) ₂ OH, -C(C ₂ F ₅ ) ₂ OH, -C(CF ₃ )(CH ₃ ). OH, -CH(CF ₃ )OH or the like, -C(CF ₃ ) ₂ OH is preferred.

The partial structure of the fluorine-containing atom may be directly bonded to the main chain, and may also be selected from the group consisting of an alkyl group, a phenyl group, an ether bond, a thioether bond, a carbonyl group, an ester bond, a guanamine bond, and an amine. A group of a group of a urethane bond and a ureido bond, or a combination of two or more of these groups, and bonded to the main chain.

The hydrophobic resin (D) may contain a ruthenium atom. A resin having an alkyl fluorenyl group structure (preferably a trialkyl decyl group) or a cyclic siloxane structure as a partial structure having a ruthenium atom is preferred.

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

Further, as described above, it is also preferred that the hydrophobic resin (D) has a CH ₃ moiety structure in the side chain portion.

Wherein the side chain portion of the hydrophobic resin (D) in CH ₃ has the partial structure (hereinafter, also sometimes referred to as "side chain CH ₃ partial structure") is comprising a portion of the CH ₃ ethyl, propyl, etc. structure.

On the other hand, a methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, an α-methyl group having a repeating unit of a methacrylic acid structure) is a hydrophobic resin due to the influence of the main chain ( The surface localization of D) is small and is not included in the CH ₃ partial structure in the present invention.

More specifically, the hydrophobic resin (D) is, for example, a repeating unit containing a monomer derived from a polymerizable moiety having a carbon-carbon double bond such as a repeating unit represented by the following formula (M). R ₁₁ to R ₁₄ are cases where CH _{3 is} "self", and CH _{3 is} not included in the CH ₃ moiety structure of the side chain moiety in the present invention.

On the other hand, CH ₃ lines from the partial structure by a CC backbone atoms present in line with the structure CH ₃ part of the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it has a "one" structure of a CH ₃ moiety in the present invention.

In the above 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, a monovalent organic group and the like.

Examples of the monovalent organic group of R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkyl group. An aminocarbonyl group, an arylaminocarbonyl group or the like may further have a substituent.

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

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

In the above formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₂ represents a stable organic group having one or more CH ₃ partial structures. Among them, an organic group which is a stable organic group, more specifically, an "acid-decomposable group" which is not described in the resin (B) is preferred.

The alkyl group of X _b1 is preferably a carbon number of 1 to 4, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and a methyl group is preferred.

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

The R ₂ may, for example, be an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group may further have an alkyl group as a substituent.

R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures.

It is preferable that the organic group having a structure of one or more CH ₃ moieties having R ₂ has two or more and ten or less CH ₃ partial structures, and two or more and eight or less are more preferable. good.

Preferred specific examples of the repeating unit represented by the 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 repeating unit in which the acid is stable (non-acid decomposable), specifically, a repeating unit which does not have a group which decomposes to generate a polar group via the action of an acid. It is better.

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

In the above formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₃ represents a stable organic group having one or more CH ₃ partial structures, and n represents 1 to 5 Integer.

The alkyl group having a carbon number of X _b2 is preferably 1 to 4, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group. However, a hydrogen atom is preferred. The X _{b 2} -based hydrogen atom is preferred.

R ₃ is preferably an organic group which is a stable organic group, and more specifically, an organic group which does not have an "acid-decomposable group" described by the hydrophobic resin (B).

Examples of R ₃ include an alkyl group having one or more CH ₃ partial structures.

It is preferred that the organic acid having a structure of a CH ₃ moiety having one or more CH ₃ moieties as R ₃ has one or more and ten or less CH ₃ partial structures, and one or more and eight or less are more preferred. It is better to have one or more and four or less.

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

Preferred specific examples of the repeating unit represented by the formula (III) are listed below. Further, the present invention is not limited to these examples.

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

The hydrophobic resin (D) is a case where the side chain moiety contains a CH ₃ moiety structure, and particularly has no fluorine atom or a ruthenium atom, the repeating unit represented by the formula (II), and the formula (III) The content of the repeating unit (x) of at least one of the repeating units is preferably 90 mol% or more, and more preferably 95 mol% or more, based on all the repeating units of the hydrophobic resin (D). The content is usually 100 mol% or less based on the total repeating unit of the hydrophobic resin (D).

The hydrophobic resin (D) is a repeating unit (x) of at least one of the repeating unit represented by the formula (II) and the repeating unit represented by the formula (III), with respect to the hydrophobic resin (D) All of the repeating units are contained in an amount of 90 mol% or more, and the surface free energy of the hydrophobic resin (D) is increased. As a result, the hydrophobic resin (D) becomes difficult to locally exist on the surface of the photoresist film, so that the static/dynamic contact angle of the photoresist film against water is surely increased, and the liquid immersion liquid followability can be improved.

Further, the hydrophobic resin (D) may have at least one selected from the group consisting of (i) containing a fluorine atom and/or a ruthenium atom, or (ii) a side chain moiety having a CH ₃ moiety structure. The basis of the group of (x) to (z) below.

(x) an acid group, (y) a group having a lactone structure, an acid anhydride group, or a hydrazide imine group, and (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 sulfonylamino group, a sulfonyl fluorenylene group, or an alkylsulfonyl group. Methyl carbonyl) methylene, (alkyl sulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl) fluorenylene, bis (alkyl sulfonate) Mercapto) methylene, bis(alkylsulfonyl)phosphonium imino group, ginseng (alkylcarbonyl) methylene group, ginseng (alkylsulfonyl) methylene group, and the like.

The preferred acid group may, for example, be a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group or a bis(alkylcarbonyl)methylene group.

The repeating unit having an acid group (x) may be exemplified by a repeating unit which directly bonds an acid group to a main chain of a resin such as a repeating unit of acrylic acid or methacrylic acid, or by a linking group. a repeating unit in which an acid group is bonded to a main chain of the resin, or a polymerization initiator or a chain transfer agent having an acid group may be used in the polymerization to introduce the end of the polymer chain, either of which is the case good. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a germanium 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%, based on all the repeating units in the hydrophobic resin (D), more preferably 5~20 mol%.

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

As the group having a lactone structure, an acid anhydride group, or an acid sulfonimide group (y), a group having a lactone structure is particularly preferable.

The repeating unit containing such a group is, for example, a repeating unit which is directly bonded to the main chain of the resin by a repeating unit of acrylate or methacrylate. Alternatively, the repeating unit may be a repeating unit bonded to the main chain of the resin by a linking group. Alternatively, the repeating unit may be a polymerization initiator or a chain-rotating agent having such a group during polymerization, or may be introduced into the end of the resin.

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

The content of the repeating unit having a lactone structure, an acid anhydride group, or an acid sulfonium imino group is preferably from 1 to 100 mol% based on all the repeating units in the hydrophobic resin (D), and ~98 mole% is better, and 5~95 mole% is better.

The repeating unit having a group (z) which is decomposed by an acid action in the hydrophobic resin (D) may be a repeating unit having an acid-decomposable group as exemplified in the resin (B) (preferably, a formula (nI) ) The repeating unit indicated is the same. The repeating unit having a group (z) which is decomposed by an acid action may have at least one of a fluorine atom and a germanium atom. The content of the repeating unit of the group (z) having a decomposition by acid action in the hydrophobic resin (D) is preferably from 1 to 80 mol%, more preferably all the repeating units in the resin (D). It is 10 to 80% by mole, and more preferably 20 to 60% by mole.

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

In the formula (III), R _c31 represents a hydrogen atom, an alkyl group (which may be substituted by a fluorine atom or the like), a cyano group or a -CH ₂ -O-Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and a hydrogen atom or a methyl group is particularly preferred.

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 fluorine atom or a ruthenium atom.

L _c3 represents a single bond or a divalent linking group.

The alkyl group of R _c32 in the formula (III) is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.

A cycloalkyl group having 3 to 20 carbon atoms is preferred.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these may have a substituent.

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

The divalent linking group of L _c3 is preferably an alkyl group (preferably having a carbon number of 1 to 5), an ether bond, a phenyl group, and an ester bond (the group represented by -COO-).

The content of the repeating unit represented by the formula (III) is preferably from 1 to 100 mol%, more preferably from 10 to 90 mol%, based on all the repeating units in the hydrophobic resin (D). 70% of the mole is better.

The hydrophobic resin (D) may further have a repeating unit represented by the following formula (CII-AB).

In 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' represents a bond containing two carbon atoms (C-C) and is used to form an alicyclic structure.

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

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

When the hydrophobic resin (D) has a fluorine atom, the content of the fluorine atom is preferably from 5 to 80% by mass, more preferably from 10 to 80% by mass, based on the weight average molecular weight of the hydrophobic resin (D). Further, the repeating unit of the fluorine atom-containing repeating unit is preferably 10 to 100 mol% of all the repeating units contained in the hydrophobic resin (D), and more preferably 30 to 100 mol%.

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

On the other hand, in particular, when the hydrophobic resin (D) has a CH ₃ partial structure in the side chain portion, the hydrophobic resin (D) is preferably a form which does not substantially contain a fluorine atom or a ruthenium atom, and in this case, The content of the repeating unit having a fluorine atom or a ruthenium atom is preferably 5 mol% or less with respect to all the repeating units in the hydrophobic resin (D), and more preferably 3 mol% or less, more preferably 1 mol. % or less is more preferably, ideally, 0% by mole, that is, does not contain a fluorine atom and a halogen atom. Further, the hydrophobic resin (D) is preferably composed of only a repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom. More specifically, 95 mol% or more of all repeating units of the repeating unit-based hydrophobic resin (D) composed of only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is Preferably, 97% by mole or more is more preferably, and 99% by mole or more is more preferably, and desirably 100% by mole.

Further, the effect of the present invention is more excellent, and the hydrophobic resin (D) may have a repeating unit represented by the formula (nI) described in the above resin (B).

The definition of the repeating unit represented by the formula (nI) is as described above.

When the hydrophobic resin (D) contains a repeating unit represented by the formula (nI), the content of the repeating unit represented by the formula (nI) is based on all repeating units of the hydrophobic resin (D), and is 10~ 60% by mole is preferred, and 20 to 50% by mole is more preferred.

The weight average molecular weight of the hydrophobic resin (D) in terms of standard polystyrene is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, still more preferably from 2,000 to 15,000.

Further, the hydrophobic resin (D) may be used alone or in combination of plural kinds.

The content of the composition of the hydrophobic resin (D) is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, more preferably 0.1 to 7% by mass, based on the total solid content of the composition. .

Hydrophobic resin (D) is similar to resin (B), metal, etc. It is preferable that the amount of impurities is 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass, while the residual monomer or oligomer component is 0.01 to 5% by mass. According to this, a composition which does not have a change with time in foreign matter, sensitivity, or the like in the liquid can be obtained. Further, the molecular weight distribution (Mw/Mn, also referred to as the degree of dispersion) is preferably in the range of 1 to 5, preferably 1 to 5, from the viewpoints of the resolution, the photoresist shape, the side wall of the photoresist pattern, and the roughness. 3, and more preferably in the range of 1~2.

The hydrophobic resin (D) can also be synthesized by a usual method (for example, radical polymerization) using various commercially available products. For example, a general synthesis method includes a monolithic polymerization method in which a monomer species and a starter are dissolved in a solvent, and polymerization is carried out by heating, and a monomer species is added dropwise in a heating solvent over a period of 1 to 10 hours. The dropwise addition polymerization method of the solution of the initiator is preferably carried out by a dropwise addition polymerization method.

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

(solvent)

The composition may contain a solvent.

Examples of the solvent which can be used in the preparation of the composition include an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether, an alkyl lactate, and an alkoxypropionic acid. An alkyl ester, a lactone (preferably having a carbon number of 4 to 10), a monoketone compound which may have a ring (preferably having a carbon number of 4 to 10), an alkylene carbonate, an alkyl alkoxyacetate, and acetone. An organic solvent such as an acid alkyl ester.

In particular, a chain or a cyclic ketone solvent or a lactone solvent is preferable because the effect of the present invention is more excellent. More preferably, it is a cyclic ketone solvent or a lactone solvent, and cyclohexanone or γ-butyrolactone is particularly preferable.

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

In the present invention, a mixed solvent of a solvent containing a hydroxyl group in a structure as an organic solvent and a solvent containing no hydroxyl group may be used.

The solvent containing a hydroxyl group and the solvent containing no hydroxyl group can be suitably selected, but in the case of a solvent containing a hydroxyl group, an alkylene glycol monoalkyl ether, an alkyl lactate or the like is preferable, and propylene glycol monomethyl ether is preferable. (PGME, alias 1-methoxy-2-propanol), ethyl lactate is more preferred. Further, in the case of a solvent not containing a hydroxyl group, an alkyl diol monoalkyl ether acetate, an alkyl alkoxy propionate, a ring-containing monoketone compound, a cyclic lactone, an alkyl acetate And preferably, propylene glycol monomethyl ether acetate (PGMEA, alias 1-methoxy-2-ethoxypropane propane), ethyl ethoxy propionate, 2-heptanone, Γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, and 2-heptanone are preferred.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent containing no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. It is particularly preferable to coat the uniformity with a mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group.

The solvent is preferably propylene glycol monomethyl ether acetate, and a mixture of two or more types of propylene glycol monomethyl ether acetate alone solvent or propylene glycol monomethyl ether acetate is preferred.

(surfactant)

The composition may further or may not contain a surfactant, and in the case of a fluorine-and/or lanthanum surfactant (fluorine-based surfactant, lanthanide surfactant, surfactant having both fluorine atoms and ruthenium atoms) Any one of them or two or more types is more preferable.

When the composition contains a surfactant and is used at an exposure light source of 250 nm or less, particularly 220 nm or less, a photoresist pattern having less adhesion and development defects can be obtained with good sensitivity and resolution.

Examples of the fluorine-based and/or lanthanoid surfactants include the surfactants described in paragraph [0276] of the specification of U.S. Patent Application Publication No. 2008/0248425.

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

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

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

On the other hand, when the amount of the surfactant added is 10 ppm or less with respect to the total amount of the composition (excluding the solvent), the surface localization of the hydrophobic resin is increased, whereby the surface of the photoresist film can be made more hydrophobic. Sexually, the water followability during immersion exposure can be improved.

(other)

The composition of the present invention may or may not contain a cerium carboxylate salt. in this way The carboxylic acid sulfonium salt can be described in paragraphs [0605] to [0606] of the specification of the US Patent Application Publication No. 2008/0187860.

These carboxylic acid sulfonium salts can be synthesized by reacting hydrazine hydroxide, iodonium hydroxide, ammonium hydroxide with a carboxylic acid in a suitable solvent with silver oxide.

In the case where the composition contains a cerium carboxylate salt, the content thereof is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 1 to 7% by mass based on the total solid content of the composition.

The composition may further contain an acid multiplier, a dye, a plasticizer, a photosensitizer, a light absorbing agent, an alkali-soluble resin, a dissolution inhibitor, and a compound which promotes solubility in a developing solution (for example, a molecular weight of 1,000 or less). A phenol compound, an alicyclic group having a carboxyl group, or an aliphatic compound).

Such a phenolic compound having a molecular weight of 1,000 or less is described in, for example, Japanese Patent Application Laid-Open No. Hei-4-122938, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei. Knowledge workers can easily synthesize.

Specific examples of the alicyclic group or the aliphatic compound having a carboxyl group include a carboxylic acid derivative having a steroid structure such as cholic acid, deoxycholic acid, and lithic acid, an adamantanecarboxylic acid derivative, and a diamond. The alkyl dicarboxylic acid, cyclohexanecarboxylic acid, cyclohexane dicarboxylic acid, etc. are not limited to these examples.

From the viewpoint of improvement in resolution, it is preferred that the composition of the present invention is formed into a photoresist film having a film thickness of 80 nm or less. The solid content concentration in the composition is set to an appropriate range and has a moderate viscosity, and the film thickness can be increased by improving the coatability and film formability.

The solid content concentration of the composition of the present invention is preferably from 1.0 to 10% by mass, more preferably from 2.0 to 5.7% by mass, still more preferably from 2.0 to 5.3% by mass. When the solid content concentration is in the above range, the composition can be uniformly applied onto the substrate, and a photoresist pattern having excellent line width roughness can be formed. Although the reason is not clear, it is considered that, when the solid content concentration is 10% by mass or less, preferably 5.7 mass% or less, the aggregation of the material in the photoresist solution, particularly the photoacid generator (A), is suppressed. As a result, a uniform photoresist film can be formed.

The solid content concentration means the weight percentage of the weight of the other photoresist component other than the solvent with respect to the total weight of the composition.

In the composition of the present invention, the above components are dissolved in a predetermined organic solvent, preferably a mixed solvent, filtered through a filter, and applied to a predetermined support (substrate). The filter used for the filtration of the filter has a pore size of 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less, and is preferably made of polytetrafluoroethylene, polyethylene or nylon. In the filter filtration, for example, by cyclic filtration as disclosed in JP-A-2002-62667, a plurality of types of filters may be filtered in series or in parallel. Alternatively, the composition may be filtered a plurality of times. Further, the composition may be subjected to a degassing treatment or the like before and after the filter is filtered.

The composition of the present invention relates to a sensitized ray-sensitive or radiation-sensitive resin composition which reacts by irradiation with actinic rays or radiation and whose properties change. More specifically, the present invention relates to a semiconductor manufacturing process for an IC or the like, a circuit substrate for manufacturing a liquid crystal, a thermal head, etc., a fabrication of a mold structure for imprinting, and even other photosensitive etching processing steps and lithography. A photosensitive ray-sensitive or radiation-sensitive resin composition used for a printing plate or an acid-curable composition.

<pattern forming method>

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

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

(i) a film forming step of forming a film (hereinafter also referred to as a photoresist film) by the above composition, (ii) an exposure step of irradiating the film with actinic rays or radiation, and (iii) irradiating the above with a developing solution A development step of film development of actinic rays or radiation.

The exposure in the above step (ii) may be a liquid immersion exposure.

The pattern forming method of the present invention is preferably carried out after (ii) the step of exposing the step comprising the heating step (iv).

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

The pattern forming method of the present invention may contain a plurality of (iv) heating steps.

The photoresist film of the present invention is preferably formed of the above-described composition of the present invention, and more specifically, a film formed by coating the above composition on a substrate. In the pattern forming method of the present invention, the step of forming a film made of a composition on a substrate, the step of exposing the film, and the developing step can be carried out by a generally known method.

In the present invention, the substrate on which the film is formed is not particularly limited, and an inorganic substrate such as ruthenium, SiN, SiO ₂ or SiN, a coated inorganic substrate such as SOG, or the like, a semiconductor production step such as IC, a liquid crystal, a thermal head or the like can be used. The substrate used in the manufacturing steps of the circuit substrate and the other lithography steps of the photosensitive etching process. Further, an anti-reflection film may be formed between the photoresist film and the substrate as necessary. As the antireflection film, a well-known organic or inorganic antireflection film can be suitably used.

After the film formation, it is also preferred to include a pre-heating step (PB; Prebake) before the exposure step.

Further, after the exposure step and before the development step, the post-exposure heating step (PEB; Post Exposure Bake) is also preferred.

The heating temperature is preferably carried out at 70 to 130 ° C together with PB and PEB, and more preferably at 80 to 120 ° C.

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

The heating can be carried out by means of a usual exposure/developer, and a heating plate or the like can also be used.

The reaction of the exposed portion is promoted by baking, and the sensitivity or pattern profile is improved.

The wavelength of the light source used in the exposure apparatus of the present invention is not limited, but examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc., preferably 250 nm or less, more preferably Below 220 nm, particularly good wavelengths of ultraviolet light of 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X Ray, EUV (13 nm), electron beam, etc., KrF excimer laser, ArF excimer laser, EUV or electron beam are preferred, and ArF excimer laser is better.

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

In the case of performing immersion exposure, after (1) forming a film on the substrate, before the exposing step, and/or (2) exposing the film through the liquid immersion liquid, the step of heating the film may be performed before the step of heating the film. The surface of the membrane is washed with a water-based chemical solution.

Preferably, the liquid immersion liquid is transparent to the exposure wavelength, and the distortion of the optical image projected on the film is minimized, and the temperature coefficient of the refractive index is as small as possible, and the exposure light source is an ArF excimer laser ( In the case of the wavelength; 193 nm), in addition to the above viewpoint, it is preferable to use water from the point of easiness of obtaining and easy handling.

In the case of using water, an additive (liquid) which reduces the surface tension of water and increases the interfacial activity can also be added in a small ratio. This additive is preferred for not dissolving the photoresist film on the wafer and neglecting the effect on the optical coating beneath the lens element.

As the additive, for example, an aliphatic alcohol having a refractive index almost equal to that of water is preferable, and specific examples thereof include methanol, ethanol, and isopropyl alcohol. By adding an alcohol having a refractive index almost equal to that of water, even if the alcohol component in the water evaporates and the concentration changes, the refractive index change of the entire liquid can be minimized.

On the other hand, when a substance which is opaque to 193 nm light or an impurity whose refractive index is substantially different from water is mixed, distortion of an optical image projected onto the photoresist film is caused, and therefore, water to be used is preferably Distilled water. Pure water which is further filtered by an ion exchange filter or the like can also be used.

The electric resistance of the water used as the liquid immersion liquid is preferably 18.3 MQcm or more, and the TOC (organic matter concentration) is preferably 20 ppb or less, and preferably is taken off. Gas treatment.

Moreover, it is possible to improve the performance of the lithography by increasing the refractive index of the liquid immersion liquid. From this point of view, it is possible to add an additive for increasing the refractive index to water or to use water (D ₂ O) instead of water.

It is preferable that the film (photoresist film) formed by using the composition of the present invention has a back contact angle of at least 23±3° C. and a humidity of 45±5% of 70° or more, and is interposed with a liquid immersion medium. The case of exposure is suitable, preferably 75° or more, and 75 to 85° is more preferable.

When the receding contact angle is too small, it is not suitable for exposure to a liquid immersion medium, and the effect of reducing water mark (watermark) defects is not sufficiently exerted. In order to achieve a preferable receding contact angle, it is preferred to contain the hydrophobic resin (D) in the composition. Alternatively, a coating layer (so-called "top coat") formed by forming a hydrophobic resin composition on the photoresist film may also increase the receding contact angle.

In the immersion exposure step, since it is necessary to follow the action of continuously forming the exposure pattern by scanning the exposure head on the wafer at a high speed, and the liquid immersion liquid is moved on the wafer, it is important that the liquid immersion is in a dynamic state. The contact angle of the liquid to the photoresist film, so that the photoresist does not remain in the droplet, and can follow the performance of the high-speed scanning of the exposure head.

As the developer used in the step of developing the photoresist film formed by using the composition of the present invention, a developer containing an organic solvent (hereinafter also referred to as an organic developer) is used.

As the organic developer, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent or an ether solvent, or a hydrocarbon solvent can be used.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), and 4-heptanone. 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetonyl acetone, acetone Acetone, ionone, diacetone alcohol, acetonitrile methanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, and B. Glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxybutyl acetic acid Ester, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, and the like.

Examples of the alcohol-based solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, and isobutylene. An alcohol such as an alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol or n-nonanol; or a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; or Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxy group A glycol ether solvent such as butylbutanol or the like.

Examples of the ether solvent include, for example, the above glycol ether solvent. Alkane, tetrahydrofuran, and the like.

As the amide solvent, for example, N-methyl-2- can be used. Pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, trimethylamine hexamethylphosphate, 1,3-dimethyl-2-imidazolidinone, and the like.

The hydrocarbon-based solvent may, for example, be an aromatic hydrocarbon solvent such as toluene or xylene; or an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane.

The above solvents may be mixed in plural kinds, or may be used in combination with a solvent or water other than the above. However, in order to fully exert the effects of the present invention, it is preferred that the water content of the entire developing solution is less than 10% by mass, and it is more preferable that the water content is substantially not contained.

In other words, the amount of the organic solvent to be used in the organic developer is preferably 90% by mass or more and 100% by mass or less based on the total amount of the developer, and more preferably 95% by mass or more and 100% by mass or less.

In particular, the organic developing solution is preferably a developing solution containing at least one type of organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

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

An appropriate amount of surfactant may be added to the organic developer as necessary.

The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. For such fluorine and/or lanthanide surfactants, for example, Japanese special patents can be cited. Japanese Laid-Open Patent Publication No. SHO-61-226746, JP-A-61-226745, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-63-34540 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The surfactant described in the specification No. 5,296,330, the specification of No. 5, 546, 998, the specification of No. 5, 576, 143, the specification of No. 5,294, 211, and the specification of No. 5,842,451 is preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, but a fluorine-based surfactant or a lanthanoid 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, and more preferably 0.01 to 0.5% by mass based on the total amount of the developer.

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

In the development method, for example, a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dipping method), and developing the developing solution by surface tension by a surface tension for a certain period of time can be applied. (liquid coating method), a method of spraying a developer on a surface of a substrate (spraying method), a method of continuously discharging a developer while scanning a developing solution discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic liquid method).

In the above various development methods, the step of ejecting the developer from the developing nozzle of the developing device to the photoresist film is performed, and the discharge pressure of the discharged developing solution (the flow rate per unit area of the discharged developing solution) is preferably 2 mL/sec/mm. ² or less, more preferably 1.5 mL/sec/mm ² or less, still more preferably 1 mL/sec/mm ² or less. There is no lower limit to the flow rate, but in consideration of the production amount, 0.2 mL/sec/mm ² or more is preferable.

By discharging the discharged developing solution to the above range, pattern defects from the photoresist residue after development can be remarkably reduced.

Although the details of the mechanism have not been determined, it is considered that the reason may be that, by making the discharge pressure within the above range, the pressure of the developer on the photoresist film is reduced, and the photoresist film/resist pattern can be suppressed from being inadvertently cut or collapsed. Case.

Further, the discharge pressure (mL/sec/mm ² ) of the developer is a value in the developing nozzle outlet in the developing device.

In the method of adjusting the discharge pressure of the developer, for example, a method of adjusting the discharge pressure by a pump or the like, a method of adjusting the pressure by supply from the pressure tank, and the like may be mentioned.

Further, after the step of developing using the developer containing the organic solvent, the step of simultaneously stopping the development while replacing the other solvent can be carried out.

After the step of developing using a developer containing an organic solvent, it is preferred to include a step of washing with a rinse liquid.

The rinse liquid used in the rinsing step after the step of developing using the developer containing the organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. In the case of the rinsing liquid, the use contains a solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, A rinse liquid of at least one type of organic solvent of a group of an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent is preferred.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent are the same as those described in the developer containing the organic solvent.

After the step of developing using a developer containing an organic solvent, it is more preferred to use a rinse containing at least one type of organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. The step of washing the liquid is more preferably a step of washing with a rinse liquid containing an alcohol solvent or an ester solvent, and particularly preferably a step of washing with a rinse liquid containing monohydric alcohol. The step of washing with a rinse liquid containing one or more carbon atoms of carbon.

Here, as the monohydric alcohol used in the rinsing step, a linear, branched, or cyclic monohydric alcohol may be mentioned, and specifically, 1-butanol, 2-butanol, and 3-methyl-1 may be used. -butanol, tertiary butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, Cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, etc., as a particularly preferred one having a carbon number of 5 or more, 1- Hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

The components may be mixed in plural kinds or may be used in combination with an organic solvent other than the above.

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

The vapor pressure of the rinse liquid used after the step of developing using the developer containing the organic solvent is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. good. When the vapor pressure of the rinse liquid is made 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is increased, and the swelling due to the immersion of the rinsing liquid is suppressed, and the dimensional uniformity of the wafer surface is good.

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

In the rinsing step, a developing wafer using a developing solution containing an organic solvent is used, and the wafer is washed with a rinsing liquid containing the above organic solvent. The method of the washing treatment is not particularly limited, and for example, it can be applied to a method of continuously discharging a rinsing liquid on a substrate rotating at a constant speed (spin coating method), and immersing the substrate in a tank filled with a rinsing liquid for a certain period of time (impregnation) The method of spraying the rinsing liquid on the surface of the substrate (spraying method), etc., wherein it is also preferably subjected to a washing treatment by a spin coating method, and after the cleaning, the substrate is rotated at a rotation number of 2000 rpm to 4000 rpm, and the rinsing liquid is self-cleaned. Removed on the substrate. Further, it is preferred to include a heating step (Post Bake) after the rinsing step. The developing liquid and the rinsing liquid remaining between the patterns and the inside of the pattern are removed by baking. The heating step after the rinsing step is generally carried out at 40 to 160 ° C, preferably 70 to 95 ° C, and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The pattern forming method of the present invention can be used in combination with a step of developing using an alkali developing solution (alkali developing step) and a step of performing development using an organic solvent-containing developing (organic solvent developing step). According to this, a finer pattern can be formed.

In the present invention, the portion having a weak exposure intensity is removed by the organic solvent developing step, but the portion having a high exposure intensity by the alkali development step is also removed. By performing the multiple development process in which the development is performed in plural times, since only the region of the intermediate exposure intensity is left undissolved and the pattern remains, a more fine pattern can be formed (with the paragraph of JP-A-2008-292975 [ 0077] The same mechanism).

The alkali development step can be carried out after any of the organic solvent development, but it is more preferably carried out before the organic solvent development step.

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

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

[Examples]

The examples are shown below, but the present invention is not limited to these examples.

<Preparation of composition (photoresist composition)>

The components shown in the following Table 3 were dissolved in the solvent shown in the same table at a solid content of 3.5% by mass, and each was filtered with a polyethylene filter having a pore diameter of 0.03 μm to prepare a sensitized ray-sensitive or radiation-sensitive resin composition. (Photoresist composition).

The various components used in Table 3 above were prepared and presented below.

Various compounds such as the following resins A-1 to A-5 and PAG-1 to PAG-5 are referred to the well-known literature (for example, JP-A-2011-252148, JP-A-2009-258586, JP-A-2010) -256879, etc.) and synthesized.

In the above table, the composition ratio shows the molar ratio of the repeating unit contained in the above resins A-1 to A-5, and the composition ratio of the repeating unit in the above-described chemical formula is sequentially shown from the left.

In the above chemical formula, "F" represents the content ratio of the fluorine atom in the anion [(total molecular weight of fluorine atom / total molecular weight of anion) × 100].

In the above table, the composition ratio shows the molar ratio of the repeating unit contained in the above resins HR-1 to HR-3, and the composition ratio of the repeating units in the above-mentioned chemical formula is sequentially presented from the left.

[solvent]

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

SL-2: cyclohexanone

SL-1: γ-butyrolactone

[Surfactant]

W-1: PF656 (made by OMNOVA)

<evaluation>

(pattern formation)

ARC29SR (manufactured by Nissan Chemical Co., Ltd.) for forming an organic anti-reflection film was applied onto a tantalum wafer, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 95 nm. Each of the photosensitive ray-sensitive or radiation-sensitive resin compositions shown in Table 3 was applied thereon, and baked at 100 ° C for 60 seconds (PB: Prebake) to form a photoresist film having a film thickness of 100 nm.

The wafer on which the photoresist film was formed was an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, external mean square deviation (outer sigma) 0.900, internal mean square deviation (inner) Sigma (0.812, XY deflection), the hole portion is 45 nm, and the gap between the holes is a half-tone mask arranged in a square arrangement of 90 nm (wherein, for the negative image formation, the portion corresponding to the hole is shielded) , for pattern exposure. Ultrapure water was used as the liquid immersion liquid. Thereafter, heating was performed at 105 ° C for 60 seconds (PEB: Post Exposure Bake). Next, development was carried out by using an organic solvent-based developing solution (butyl acetate) for 30 seconds, and rinsing with a rinse liquid (4-methyl-2-pentanol) for 30 seconds. Next, the wafer was rotated for 30 seconds at a number of revolutions of 4000 rpm to obtain a contact hole pattern having a hole diameter of 45 nm.

(development defect evaluation)

The number of development defects was measured by a defect inspection apparatus KLA2360 (manufactured by KLA Tencor Co., Ltd.) on the tantalum wafer of the contact hole pattern formed by the above method, and the number of development defects per unit area [cm ² ] was calculated. The smaller the value, the better. The finishing results are presented in Table 3.

(Exposure latitude (EL))

The aperture was observed by a length-measuring scanning electron microscope (SEM Hitachi, Ltd.), and the optimum exposure amount when the hole portion was 45 nm was analyzed as a sensitivity (E _opt ) (mJ/cm ² ). The optimum exposure amount (E _opt ) obtained was used as a reference, and the amount of exposure when the aperture became ±10% (i.e., 40.5 nm and 49.5 nm) of 45 nm of the target value was determined. Further, the exposure latitude (EL, %) defined by the following formula was calculated. The larger the value of EL, the smaller the change in performance due to the change in exposure amount is preferable. The results are summarized and presented in Table 3.

[EL(%)]=[[(the hole portion becomes an exposure amount of 40.5 nm)-(the hole portion becomes an exposure amount of 49.5 nm)]/E _opt ]×100

(pattern shape evaluation)

The cross-sectional shape of the contact hole pattern obtained by the above method was observed using a scanning electron microscope, and the aperture Lb in the bottom portion of the photoresist pattern and the aperture La in the upper portion of the photoresist pattern were measured. The closer the ratio of La to Lb (La/Lb) is to 1, the better the pattern shape. The absolute value of the difference between La and Lb (La/Lb) and 1 is distinguished by the following five stages. The results are shown 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, when the pattern forming method of the present invention was used, it was confirmed that a pattern having an exposure latitude, a developing property, and a pattern outline having a good shape was formed.

Moreover, as is clear from the comparison of Examples 1 to 4, it was confirmed that the resin (B) had a repeating unit represented by the formula (VIII) (Example 4), and the above characteristics were more excellent.

Further, as is clear from the comparison between Example 1 and Example 7, it is confirmed that the compound represented by the formula (A-1) and the compound which generates an acid by irradiation with actinic rays or radiation different from the compound are used in combination. In the case (Example 7), the above characteristics were more excellent.

Further, as is clear from the comparison between Example 1 and Example 10, it was found that the solvent contained the lactone-based solvent (Example 1), and the above characteristics were more excellent.

Further, as is clear from the comparison between Example 1 and Example 11, it was confirmed that the solvent contained a ketone solvent (Example 1), and the above characteristics were more excellent.

Further, as is clear from the comparison between Example 1 and Examples 12 to 13, it was confirmed that an onium salt which is a relatively weak acid with respect to the photoacid generator (A) or an amine group represented by the formula (d-1) is used. In the case where the basic compound of the protecting group of the formate group is used as the acid diffusion controlling agent (Examples 12 and 13), the above characteristics are more excellent.

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

Claims (19)

A pattern forming method comprising the steps of: (i) forming a film by a photosensitive ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B): (A) Formula (A) -1) a compound which generates an acid by irradiation with actinic rays or radiation, (B) having a repeating unit represented by the formula (nI), which is increased in polarity by an action of an acid and which is soluble in an organic solvent a resin having reduced solubility of the developer; (ii) a step of irradiating the film with actinic rays or radiation; and (iii) developing the film irradiated with actinic rays or radiation using a developing solution containing an organic solvent. step, In the 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 is a fluorine atom or an alkyl group substituted with 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 2 to 8; and L ¹ represents a single bond, -O-, -COO-, or -OCO-; ² represents a single bond or a divalent linking group; Y represents a group having a cyclic structure having a carbon number of 3 to 18 which may have a substituent; Z ¹⁺ represents a cation; an anion in the formula (A-1), a fluorine atom The content rate is 0-20% by mass; In the formula (nI), R ₁₃ '~R ₁₆ ' each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or an alkyl group. a carbonyl group, a group having a lactone structure, or a group having an acid-decomposable group; and X ₁ and X ₂ each independently represent a methylene group, an ethyl group, an oxygen atom or a sulfur atom; and n represents an integer of 0 to 2. The pattern forming method of claim 1, wherein the compound represented by the formula (A-1) is a compound represented by the following formula (A-2), In the formula (A-2), R ¹ and R ² each independently represent a hydrogen atom and an organic group which is not fluorine-substituted; q represents an integer of 2 to 8; and L ² represents a single bond or a divalent linking group; The group having a cyclic structure having a carbon number of 3 to 18 which may have a substituent; and the anion of the formula (A-2), the content of the fluorine atom is 0 to 20% by mass or less; and Z ¹ represents a cation. The pattern forming method of claim 1, wherein the Y-based polycyclic aliphatic group. The pattern forming method of claim 1, wherein at least one of the formula (nI), R ₁₃ ' to R ₁₆ ' is a group having an acid-decomposable group. The requested item 4 of the pattern forming method, wherein the group having an acid-decomposable group-based * ¹ -L ³ -AD group represented by the; and, L ³ represents an alkylene group; the AD represents an acid decomposable group; * represents ¹ The bonding position with the aforementioned resin. The pattern forming method of claim 1, wherein the resin (B) has a repeating unit represented by the following 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 Camphor residue. The pattern forming method of claim 1, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains a hydrophobic resin, and the content of the hydrophobic resin in the sensitizing ray-sensitive or radiation-sensitive resin composition is The solid content standard is 0.01 to 10% by mass. The pattern forming method according to claim 7, wherein the hydrophobic resin has at least one selected from the group consisting of a fluorine atom, a ruthenium atom, and a CH ₃ partial structure contained in a side chain portion of the hydrophobic resin. . The pattern forming method of claim 7, wherein the hydrophobic resin has a repeating unit represented by the formula (nI), In the formula (nI), R ₁₃ '~R ₁₆ ' each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or an alkyl group. a carbonyl group, a group having a lactone structure, or a group having an acid-decomposable group; and X ₁ and X ₂ each independently represent a methylene group, an ethyl group, an oxygen atom or a sulfur atom; and n represents an integer of 0 to 2. The pattern forming method of claim 1, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains a chain or cyclic ketone solvent. The pattern forming method of claim 1, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains a lactone-based solvent. The pattern forming method of claim 1, wherein the Z ¹⁺ is any one of the cations represented by the formula (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; further, at least one of R ³ to R ⁹ represents a hydroxyl group, a carboxyl group or a halogen. An 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-sided oxyalkyl group, a 2-sided oxycycloalkyl group, an alkoxycarbonyl alkane. Or alkoxycarbonylcycloalkyl; further, any two of R ³ to R ⁷ may be bonded to each other to form a ring; further, R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ may be bonded to each other to form ring; In the formula (C-2), R ¹² and R ¹³ each independently represent an alkyl group, a cycloalkyl group or a naphthyl group; and R ¹⁴ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group or an alkoxy group; An alkoxycarbonyl group, a monocyclic or polycyclic group having a 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 0 An integer of ~8; further, R ¹² and R ¹³ may be bonded to each other to form a ring; 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; m16 to m18 each independently represent an integer of 0 to 5; and any of R ¹⁶ to R ¹⁸ Two of them 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 pattern forming method of claim 1, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains an acid generated by irradiation with actinic rays or radiation represented by the general formula (A-1). A compound in which a compound differs by the irradiation of actinic rays or radiation to produce an acid. A sensitizing ray-sensitive or radiation-sensitive resin composition which is the sensitized ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of claim 1, which further contains a hydrophobic resin. A sensitizing ray-sensitive or radiation-sensitive resin composition, which is the sensitized ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of claim 1, which further contains a chain or cyclic ketone a solvent, the Z ¹⁺ being any one of the cations represented by the formula (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; further, at least one of R ³ to R ⁹ represents a hydroxyl group, a carboxyl group or a halogen. An 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-sided oxyalkyl group, a 2-sided oxycycloalkyl group, an alkoxycarbonyl alkane. Or an alkoxycarbonylcycloalkyl group; further, any two of R ³ to R ⁷ may be bonded to each other to form a ring; further, R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ may be bonded to each other. Forming 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; and R ¹⁴ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group or an alkoxy group; An alkoxycarbonyl group, a monocyclic or polycyclic group having a 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 0 An integer of ~8; in addition, R ¹² and R ¹³ 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 represent an integer of 0 to 5; and any of R ¹⁶ to R ¹⁸ One may be bonded to each other to form a ring; and at least one of m16 to m18 is represented as an integer of 1 or more. A sensitizing ray-sensitive or radiation-sensitive resin composition, which is the sensitized ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of claim 1, further comprising a lactone-based solvent, Z ¹⁺ is any one of the cations represented by the general formulae (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; further, at least one of R ³ to R ⁹ represents a hydroxyl group, a carboxyl group or a halogen. An 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-sided oxyalkyl group, a 2-sided oxycycloalkyl group, an alkoxycarbonyl alkane. Or alkoxycarbonylcycloalkyl; further, any two of R ³ to R ⁷ may be bonded to each other to form a ring; further, R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ may be bonded to each other to form ring; In the formula (C-2), R ¹² and R ¹³ each independently represent an alkyl group, a cycloalkyl group or a naphthyl group; and R ¹⁴ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group or an alkoxy group; An alkoxycarbonyl group, a monocyclic or polycyclic group having a 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 0 An integer of ~8; further, R ¹² and R ¹³ 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; and m16 to m18 each independently represent an integer of 0 to 5; further, R ¹⁶ to R ¹⁸ Any two of them may be bonded to each other to form a ring. A sensitizing ray-sensitive or radiation-sensitive resin composition which is the sensitized ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of claim 1, which further contains the formula (A- 1) A compound which generates an acid by irradiation with actinic rays or radiation is different from a compound which generates an acid by irradiation with actinic rays or radiation. A method of manufacturing an electronic device, comprising the pattern forming method according to any one of claims 1 to 13. An electronic device manufactured by the method of manufacturing an electronic device as claimed in claim 18.