TW202231626A - Radiation-sensitive resin composition and method for forming resist patter using same, and sulfonium salt compound and radiation-sensitive acid generator comprising same - Google Patents

Abstract

Provided are a method for forming a resist pattern having excellent performance including sensitivity during a light exposure process, LWR performance and CDU performance even when a next-generation light exposure technology is applied thereto; a radiation-sensitive resin composition; and others. The radiation-sensitive resin composition comprises: a sulfonium salt compound represented by formula (1) (wherein R1 represents a monovalent hydrocarbon group having a cyclic structure, in which a methylene group constituting a hydrocarbon group may be substituted by an ether bond; Rf1 and Rf2 independently represent a fluorine atom or a monovalent fluorinated hydrocarbon group; m1 represents an integer of 1 to 4, in which, when m1 is 2 to 4, some or all of a plurality of Rf1's and Rf2's are the same as or different from each other; R2 and R3 independently represent a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group, or a monovalent fluorinated hydrocarbon group; m2 represents an integer of 0 to 3, in which, when m2 is 2 to 3, some or all of a plurality of R2's and R3's are the same as or different from each other; X represents a single bond or a linker containing a bivalent hetero atom; R4 to R7 independently represent a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group, or an ester group; n1 and n2 independently represent an integer of 1 to 3, in which some or all of a plurality of R4's to R7's are the same as or different from each other; R8 represents a monovalent linear hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent fluorinated hydrocarbon group, a halogen atom, a monovalent aromatic hydrocarbon group, or a monovalent group represented by -Y-R8' (wherein Y represents -O-, -CO-, -COO-, or -OCO-; and R8' represents a monovalent hydrocarbon group having 1 to 20 carbon atoms); and l represents an integer of 0 to 5, in which, when l is 2 to 5, some or all of a plurality of R8's are the same as or different from each other); a resin containing a structural unit having an acid-dissociable group; and a solvent.

Description

Radiation-sensitive resin composition and method for forming resist pattern using the same, and pernium salt compound and radiation-sensitive acid generator containing the same

The present invention relates to a radiation-sensitive resin composition, a method for forming a resist pattern using the same, a perylene salt compound, a radiation-sensitive acid generator containing the perylene salt compound, and the like.

A photolithography technique using a resist composition is used for fine circuit formation of semiconductor elements. As a typical procedure, for example, an acid is generated by exposing the film of the resist composition by irradiation with radiation through a mask pattern, and the exposed part and the unexposed part are reacted with the acid as a catalyst. A difference in the solubility of the resin with respect to an alkali-based or organic-based developer is generated during the process, whereby a resist pattern is formed on the substrate.

In the photolithography technique, short-wavelength radiation such as an ArF excimer laser or the like is used, or a liquid immersion immersion method is used to perform exposure in a state where the space between the lens and the resist film of the exposure device is filled with a liquid medium. Exposure method (liquid immersion lithography) to advance pattern miniaturization. As next-generation technologies, lithography using shorter wavelength radiation such as electron beams, X-rays, and extreme ultraviolet (Extreme Ultraviolet, EUV) is also being studied.

Along with the progress of exposure technology, attempts to improve sensitivity, resolution, and the like have also been advanced with respect to the photoacid generator that is the main component of the resist composition. As a resist composition having a pattern resolution ranging from a micrometer unit to a submicrometer unit, it is proposed to include a hydroxystyrene-based polymer having high plasma etching resistance, and a secondary carbon to which a perionyl group is bonded is proposed. Photosensitive composition of photoacid generator of carbon or tertiary carbon (Patent Document 1).

In addition, in the ArF generation, a resin containing an alicyclic structure with little absorption as a protective group is used instead of the hydroxystyrene-based polymer, but the photoacid generator used in combination with the hydroxystyrene-based polymer is When deprotecting a resin having an alicyclic structure, the acid strength is insufficient. Therefore, as a photoacid generator that provides an acid having sufficient acid strength for deprotection, an acid in which the near-position carbon of a perylene group is substituted with fluorine is used. The generator is put into practical use (Patent Document 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 10-10715 [Patent Document 2] Japanese Patent Laid-Open No. 2002-214774

[The problem to be solved by the invention] In recent years, in the progress of miniaturization of resist patterns, further improvement of the resolution, including sensitivity in the exposure step, and line width roughness (Line Width Roughness) indicating the variation in the line width of the resist pattern, are required. , LWR) performance, critical dimension uniformity (Critical Dimension Uniformity, CDU) performance, etc., require further improvement of various properties of the resist. Furthermore, in the next-generation exposure technologies such as electron beam exposure, various performances of resists that are equal to or higher are required. However, with the conventional radiation-sensitive resin composition, it was not possible to obtain all the properties at a sufficient level. [Means of Solving Problems]

The inventors of the present invention have made repeated efforts to solve this problem, and as a result, they have found that the object can be achieved by using a perylene salt compound having a specific structure, and completed the present invention.

（式中， R ¹為具有環狀結構的一價烴基，且構成烴基的亞甲基可經取代為醚鍵， R ^f1及R ^f2分別獨立地為氟原子或一價氟化烴基， m ₁為1～4的整數，在m ₁為2～4的情況下，多個R ^f1及R ^f2的一部分或全部相同或不同， R ²及R ³分別獨立地為氫原子、氟原子、一價烴基或一價氟化烴基， m ₂為0～3的整數，在m ₂為2～3的情況下，多個R ²及R ³的一部分或全部相同或不同， X為單鍵或包含二價雜原子的連接基， R ⁴～R ⁷分別獨立地為氫原子、羥基、一價烴基、或者酯基， n ₁及n ₂分別獨立地為1～3的整數，多個R ⁴～R ⁷的一部分或全部相同或不同， R ⁸為一價鏈狀烴基、一價脂環式烴基、一價氟化烴基、鹵素原子、一價芳香族烴基、或-Y-R ^8'所表示的一價基， （Y表示-O-、-CO-、-COO-、-OCO-，R ^8'為碳數1～20的一價烴基） l為0～5的整數，在l為2～5的情況下，多個R ⁸的一部分或全部相同或不同）。 That is, in one embodiment, the present invention relates to a radiation-sensitive resin composition containing: a perylene salt compound represented by the following formula (1) (hereinafter, also referred to as "compound (1)"); A resin comprising a structural unit having an acid dissociable group; and a solvent, [Chem. 1]

(in the formula, R ¹ is a monovalent hydrocarbon group having a cyclic structure, and the methylene group constituting the hydrocarbon group may be substituted with an ether bond, R ^f1 and R ^f2 are independently a fluorine atom or a monovalent fluorinated hydrocarbon group, m ₁ is an integer of 1 to 4, and when m ₁ is 2 to 4, a part or all of a plurality of R ^f1 and R ^f2 are the same or different, and R ² and R ³ are each independently a hydrogen atom, a fluorine atom, a monovalent Hydrocarbon group or monovalent fluorinated hydrocarbon group, m ₂ is an integer of 0 to 3, when m ₂ is 2 to 3, some or all of a plurality of R ² and R ³ are the same or different, X is a single bond or contains two A linking group of a valence heteroatom, R ⁴ to R ⁷ are each independently a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group, or an ester group, n ₁ and n ₂ are each independently an integer of 1 to 3, and a plurality of R ⁴ to R A part or all of ⁷ are the same or different, R ⁸ is a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent fluorinated hydrocarbon group, a halogen atom, a monovalent aromatic hydrocarbon group, or a monovalent represented by -YR ^8' base, (Y represents -O-, -CO-, -COO-, -OCO-, R ^8' is a monovalent hydrocarbon group with 1-20 carbon atoms) l is an integer of 0-5, where l is 2-5 case, some or all of the plurality of R ⁸ are the same or different).

The radiation-sensitive resin composition contains the periconium salt compound represented by the above-mentioned formula (1), a resin containing a structural unit having an acid dissociable group, and a solvent, and thus a resist of the radiation-sensitive resin composition is used The sensitivity, LWR performance, CDU performance, and the like in the exposure step of the film or the like can be exhibited at an excellent level. The mechanism of action by which the effect is manifested is not clear, and the scope of the patent application of the present invention is not necessarily limited based on this presumption, but it is presumed that the radiation-sensitive resin composition contains a strong acid with enhanced hydrophobicity. Compounds, etc., can appropriately improve various properties of the resist.

In addition, in another embodiment, the present invention relates to a method for forming a resist pattern, comprising: a step of directly or indirectly coating the radiation-sensitive resin composition on a substrate to form a resist film; the step of exposing the resist film; and A step of developing the exposed resist film.

The method for forming a resist pattern includes directly or indirectly coating a radiation-sensitive resin composition containing the periconium salt compound represented by the formula (1), a resin containing a structural unit having an acid dissociable group, and a solvent In the step of forming a resist film on a substrate, the sensitivity in the exposure step, the line width roughness (LWR) performance indicating the variation in the line width of the resist pattern, and the CDU performance can be exhibited at an excellent level. The mechanism by which the effect appears is not yet clear, and the scope of the patent application of the present invention is not necessarily limited by this presumption, but it is presumed that the method for forming the resist pattern is performed by using a salt containing a specific structure with improved hydrophobicity and strong acidity. The radiation-sensitive resin composition of the compound and the like can appropriately improve various properties of the resist.

（式中， R ¹為具有環狀結構的一價烴基，且構成烴基的亞甲基可經取代為醚鍵， R ^f1及R ^f2分別獨立地為氟原子或一價氟化烴基， m ₁為1～4的整數，在m ₁為2～4的情況下，多個R ^f1及R ^f2的一部分或全部相同或不同， R ²及R ³分別獨立地為氫原子、氟原子、一價烴基或一價氟化烴基， m ₂為0～3的整數，在m ₂為2～3的情況下，多個R ²及R ³的一部分或全部相同或不同， X為單鍵或包含二價雜原子的連接基， R ⁴～R ⁷分別獨立地為氫原子、羥基、一價烴基、或者酯基， n ₁及n ₂分別獨立地為1～3的整數，多個R ⁴～R ⁷的一部分或全部相同或不同， R ⁸為一價鏈狀烴基、一價脂環式烴基、一價氟化烴基、鹵素原子、一價芳香族烴基、或-Y-R ^8'所表示的一價基， （Y表示-O-、-CO-、-COO-、-OCO-，R ^8'為碳數1～20的一價烴基） l為0～5的整數，在l為2～5的情況下，多個R ⁸的一部分或全部相同或不同）。 Furthermore, in another embodiment, the present invention relates to a perylene salt compound represented by the following formula (1). [hua 2]

(in the formula, R ¹ is a monovalent hydrocarbon group having a cyclic structure, and the methylene group constituting the hydrocarbon group may be substituted with an ether bond, R ^f1 and R ^f2 are independently a fluorine atom or a monovalent fluorinated hydrocarbon group, m ₁ is an integer of 1 to 4, and when m ₁ is 2 to 4, a part or all of a plurality of R ^f1 and R ^f2 are the same or different, and R ² and R ³ are each independently a hydrogen atom, a fluorine atom, a monovalent Hydrocarbon group or monovalent fluorinated hydrocarbon group, m ₂ is an integer of 0 to 3, when m ₂ is 2 to 3, some or all of a plurality of R ² and R ³ are the same or different, X is a single bond or contains two A linking group of a valence heteroatom, R ⁴ to R ⁷ are each independently a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group, or an ester group, n ₁ and n ₂ are each independently an integer of 1 to 3, and a plurality of R ⁴ to R A part or all of ⁷ are the same or different, R ⁸ is a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent fluorinated hydrocarbon group, a halogen atom, a monovalent aromatic hydrocarbon group, or a monovalent represented by -YR ^8' base, (Y represents -O-, -CO-, -COO-, -OCO-, R ^8' is a monovalent hydrocarbon group with 1-20 carbon atoms) l is an integer of 0-5, where l is 2-5 case, some or all of the plurality of R ⁸ are the same or different).

The perylene salt compound has the structure represented by the above formula (1). For example, by using a radiation-sensitive resin composition or a resist formation method containing the perylene salt compound, the sensitivity and LWR performance in the exposure step are , CDU performance, etc. can play an excellent level. The mechanism of action by which the effect is exhibited is not clear, and the scope of the patent application of the present invention is not necessarily limited based on this presumption. The radiation-sensitive resin composition and the like, for example, function as a preferable radiation-sensitive acid generator, and as a result, various properties of the resist are improved.

（式中， R ¹為具有環狀結構的一價烴基，且構成烴基的亞甲基可經取代為醚鍵， R ^f1及R ^f2分別獨立地為氟原子或一價氟化烴基， m ₁為1～4的整數，在m ₁為2～4的情況下，多個R ^f1及R ^f2的一部分或全部相同或不同， R ²及R ³分別獨立地為氫原子、氟原子、一價烴基或一價氟化烴基， m ₂為0～3的整數，在m ₂為2～3的情況下，多個R ²及R ³的一部分或全部相同或不同， X為單鍵或包含二價雜原子的連接基， R ⁴～R ⁷分別獨立地為氫原子、羥基、一價烴基、或者酯基， n ₁及n ₂分別獨立地為1～3的整數，多個R ⁴～R ⁷的一部分或全部相同或不同， R ⁸為一價鏈狀烴基、一價脂環式烴基、一價氟化烴基、鹵素原子、一價芳香族烴基、或-Y-R ^8'所表示的一價基， （Y表示-O-、-CO-、-COO-、-OCO-，R ^8'為碳數1～20的一價烴基） l為0～5的整數，在l為2～5的情況下，多個R ⁸的一部分或全部相同或不同）。 In addition, in another embodiment, the present invention relates to a radiation-sensitive acid generator comprising a perylene salt compound represented by the following formula (1). [hua 3]

(in the formula, R ¹ is a monovalent hydrocarbon group having a cyclic structure, and the methylene group constituting the hydrocarbon group may be substituted with an ether bond, R ^f1 and R ^f2 are independently a fluorine atom or a monovalent fluorinated hydrocarbon group, m ₁ is an integer of 1 to 4, and when m ₁ is 2 to 4, some or all of the plurality of R ^f1 and R ^f2 are the same or different, and R ² and R ³ are each independently a hydrogen atom, a fluorine atom, a monovalent Hydrocarbon group or monovalent fluorinated hydrocarbon group, m ₂ is an integer of 0 to 3, when m ₂ is 2 to 3, a part or all of a plurality of R ² and R ³ are the same or different, X is a single bond or contains two A linking group of a valent heteroatom, R ⁴ to R ⁷ are each independently a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group, or an ester group, n ₁ and n ₂ are each independently an integer of 1 to 3, and a plurality of R ⁴ to R A part or all of ⁷ are the same or different, R ⁸ is a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent fluorinated hydrocarbon group, a halogen atom, a monovalent aromatic hydrocarbon group, or a monovalent represented by -YR ^8' base, (Y represents -O-, -CO-, -COO-, -OCO-, R ^8' is a monovalent hydrocarbon group with 1-20 carbon atoms) l is an integer of 0-5, where l is 2-5 case, some or all of the plurality of R ⁸ are the same or different).

The radiation-sensitive acid generator has a structure represented by the above-mentioned formula (1). Therefore, for example, by using a radiation-sensitive resin composition or a resist formation method containing the radiation-sensitive acid generator, in the exposure step Sensitivity, LWR performance, CDU performance, etc. can all play an excellent level. The mechanism of action by which the effect is exhibited is not clear, and the scope of the patent application of the present invention is not necessarily limited based on this presumption. The radiation-sensitive resin composition or the like of the perylene salt compound acts as a preferable radiation-sensitive acid generator, and as a result, improves various properties of the resist.

Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments.

<Radiation sensitive resin composition> The radiation-sensitive resin composition (hereinafter, also simply referred to as "composition") of the present embodiment includes a resin (A), a periconium salt compound (B) (or a radiation-sensitive acid generator (B)), and a solvent (D ). As long as the effect of this invention is not impaired, the said composition may contain other arbitrary components.

(Resin (A)) The resin (A) is a resin containing a structural unit having an acid dissociable group (hereinafter, this resin is also referred to as a “base resin”). The resin (A) is an aggregate of polymers having a structural unit including an acid dissociable group (hereinafter, also referred to as "structural unit (I)"). The "acid-dissociable group" refers to a group that substitutes a hydrogen atom possessed by a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a sulfo group, or the like, and refers to a group that is dissociated by the action of an acid. This radiation-sensitive resin composition is excellent in pattern formability because the resin has the structural unit (I).

In addition to the structural unit (I), the base resin preferably also has a structural unit (II) including at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure, and a sultone structure, which will be described later, You may have other structural units other than the structural unit (I) and the structural unit (II). Hereinafter, each structural unit will be described.

[Structural unit (I)] The structural unit (I) is a structural unit containing an acid dissociable group. The structural unit (I) is not particularly limited as long as it contains an acid dissociable group, and examples thereof include a structural unit having a tertiary alkyl ester moiety, and a structure in which a hydrogen atom having a phenolic hydroxyl group is substituted with a tertiary alkyl group. The structural unit, the structural unit having an acetal bond, etc., are preferably a structural unit represented by the following formula (2) (hereinafter, also referred to as the is "structural unit (I-1)").

（式中， R ⁹為氫原子、氟原子、甲基或三氟甲基， R ¹⁰為碳數1～20的一價烴基， R ¹¹及R ¹²分別獨立地為碳數1～10的一價鏈狀烴基或碳數3～20的一價脂環式烴基、或者R ¹¹及R ¹²相互結合並與該些所鍵結的碳原子一起構成的碳數3～20的二價脂環式基）。 [hua 4]

(in the formula, R ⁹ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R ¹⁰ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. A valent chain hydrocarbon group or a monovalent alicyclic hydrocarbon group with 3 to 20 carbon atoms, or a bivalent alicyclic hydrocarbon group with 3 to 20 carbon atoms in which R ¹¹ and R ¹² are bonded to each other and together with these bonded carbon atoms base).

In the above formula (4), examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ include a methyl group, an ethyl group, and the like.

In the above formula (4), examples of the monovalent chain hydrocarbon group having 1 to 10 carbon atoms represented by R ¹¹ and R ¹² each independently include, for example, a methyl group, an ethyl group, and the like.

In the above formula (4), examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ¹¹ and R ¹² each independently include, for example, a cyclopentyl group, a cyclohexyl group, and the like.

In the above formula (4), as a divalent alicyclic group having 3 to 20 carbon atoms in which R ¹¹ and R ¹² are bonded to each other and constituted together with these bonded carbon atoms, as long as it is self-constituting the above carbon atoms The group obtained by removing two hydrogen atoms from the same carbon atom of the carbocyclic ring of the hydrocarbon is not particularly limited.

As the structural unit (I-1), for example, structural units represented by the following formulae (3-1) to (3-6) (hereinafter, also referred to as "structural unit (I-1-1) to unit (I-1-6)”), etc.

[hua 5]

In the above formulas (3-1) to (3-6), R ⁹ to R ¹² have the same meanings as in the above formula (2). i' and j' are each independently an integer of 0-16. k' is 0-1.

As i' and j', 1 is preferable. As R ¹⁰ , methyl, ethyl or isopropyl is preferred.

The base resin may contain one kind or two or more kinds of structural units (I) in combination.

With respect to all the structural units constituting the base resin, the content ratio of the structural unit (I) (the total content ratio when multiple types are included) is preferably 10 mol % or more, more preferably 20 mol % or more, and further Preferably, it is 30 mol % or more, and particularly preferably 35 mol % or more. In addition, it is preferably 80 mol % or less, more preferably 75 mol % or less, still more preferably 70 mol % or less, and particularly preferably 65 mol % or less. By making the content ratio of a structural unit (I) into the said range, the pattern formability of this radiation sensitive resin composition can be improved further.

[Structural unit (II)] The structural unit (II) is a structural unit containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure, and a sultone structure. By further having the structural unit (II), the base resin can adjust the solubility with respect to the developer, and as a result, the radiation-sensitive resin composition can improve lithography performance such as resolution. Moreover, the adhesiveness of the resist pattern formed with the base resin and a board|substrate can be improved.

As a structural unit (II), the structural unit etc. which are represented by following formula (T-1) - formula (T-10) are mentioned, for example.

[hua 6]

In the formula, R ^L1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ^L2 to R ^L5 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, a trifluoromethyl group, a methoxy group, a methoxycarbonyl group, a hydroxyl group, a hydroxymethyl group, and a dimethylamino group. R ^L4 and R ^L5 may be a divalent alicyclic group having 3 to 8 carbon atoms which are bonded to each other and constituted together with these bonded carbon atoms. L ² is a single bond or a divalent linking group. X is an oxygen atom or a methylene group. k is an integer of 0-3. m is an integer of 1-3.

Examples of the divalent alicyclic group having 3 to 8 carbon atoms in which the R ^L4 and R ^L5 are bonded to each other and constituted together with the bonded carbon atoms include those represented by R ⁸ in the formula (1). Among the divalent alicyclic groups with 3 to 20 carbon atoms, the chain-like hydrocarbon groups or alicyclic hydrocarbon groups are bonded to each other and together with these bonded carbon atoms. One or more hydrogen atoms on the alicyclic group may be substituted with a hydroxyl group.

Examples of the divalent linking group represented by L ² include a divalent linear or branched hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, or a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms. One or more of these hydrocarbon groups and at least one group of -CO-, -O-, -NH- and -S-, etc.

Among these, the structural unit (II) is preferably a structural unit containing a lactone structure, more preferably a structural unit containing a norbornane lactone structure, and further preferably a (meth)acrylate-derived norbornane lactone- The structural unit of the base ester.

The content ratio of the structural unit (II) is preferably 20 mol % or more, more preferably 25 mol % or more, and still more preferably 30 mol % or more with respect to all the structural units constituting the base resin. In addition, it is preferably 80 mol % or less, more preferably 75 mol % or less, still more preferably 70 mol % or less. By setting the content ratio of the structural unit (II) to the above-mentioned range, the radiation-sensitive resin composition can further improve the lithography performance such as resolution and the adhesion between the formed resist pattern and the substrate.

[Structural unit (III)] The base resin optionally has other structural units in addition to the structural unit (I) and the structural unit (II). As said other structural unit, the structural unit (III) containing a polar group etc. are mentioned, for example (however, the thing corresponding to a structural unit (II) is excluded). By further having the structural unit (III), the base resin can adjust the solubility with respect to the developing solution, and as a result, can improve the lithography performance such as the analytical properties of the radiation-sensitive resin composition. As said polar group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a sulfonamido group etc. are mentioned, for example. Among these, a hydroxyl group and a carboxyl group are preferable, and a hydroxyl group is more preferable.

As a structural unit (III), the structural unit etc. which are represented by the following formula are mentioned, for example.

[hua 7]

In the formula, ^RA is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

When the base resin contains the structural unit (III) having a polar group, the content of the structural unit (III) is preferably 5 mol% or more relative to all the structural units constituting the base resin, More preferably, it is 8 mol % or more, and still more preferably 10 mol % or more. In addition, it is preferably 40 mol % or less, more preferably 35 mol % or less, still more preferably 30 mol % or less. By setting the content ratio of the structural unit (III) to the above-mentioned range, the lithography performance such as the resolution of the radiation-sensitive resin composition can be further improved.

[Structural Unit (IV)] As other structural units, in addition to the structural unit (III) having a polar group, the base resin optionally has a structural unit derived from hydroxystyrene or a structural unit having a phenolic hydroxyl group (hereinafter, both are also referred to together). "Structural Unit (IV)"). The structural unit (IV) contributes to the improvement of etching resistance and the improvement of the difference in developer solubility (dissolution contrast) between the exposed part and the unexposed part. In particular, it can be preferably applied to pattern formation using exposure with radiation having a wavelength of 50 nm or less, such as electron beams or EUV. In this case, it is preferable that resin has a structural unit (IV) and a structural unit (I) together.

In this case, it is preferable to carry out the polymerization in a state in which the phenolic hydroxyl group is protected by a protecting group such as an alkali dissociable group during the polymerization, and then hydrolyze and deprotect, whereby the structural unit (IV) is obtained. The structural unit which provides the structural unit (IV) by hydrolysis is preferably represented by the following formula (4-1) and formula (4-2).

[hua 8]

In the formula (4-1) and formula (4-2), R ¹³ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ¹⁴ is a monovalent hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹⁴ include monovalent hydrocarbon groups having 1 to 20 carbon atoms in R ¹⁰ in the structural unit (I). As an alkoxy group, a methoxy group, an ethoxy group, a 3rd butoxy group, etc. are mentioned, for example.

As the R ¹⁴ , an alkyl group and an alkoxy group are preferable, and among them, a methyl group and a tert-butoxy group are more preferable.

In the case of a resin for exposure by radiation with a wavelength of 50 nm or less, the content ratio of the structural unit (IV) is preferably 10 mol % or more, more preferably 20 mol % with respect to all the structural units constituting the resin. %above. In addition, it is preferably 70 mol % or less, more preferably 60 mol % or less.

(Synthesis method of resin (A)) The resin (A) can be synthesized by, for example, polymerizing a monomer providing each structural unit in an appropriate solvent using a radical polymerization initiator or the like.

Examples of the radical polymerization initiator include: azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) , 2,2'-azobis(2-cyclopropylpropanenitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyric acid Azo-based radical polymerization initiators such as dimethyl ester; peroxide-based radical polymerization initiators such as benzyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc. Among these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferable, and AIBN is more preferable. These radical polymerization initiators may be used alone or in combination of two or more.

Examples of the solvent used in the polymerization include: n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other alkanes; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, hexamethylene dibromide, and chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate; Acetone, methyl ethyl ketone, 4-methyl-2-pentanone, 2-heptanone and other ketones; Ethers such as tetrahydrofuran, dimethoxyethane, and diethoxyethane; Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol, etc. These solvents used for the polymerization may be used alone or in combination of two or more.

The reaction temperature in the polymerization is usually 40°C to 150°C, preferably 50°C to 120°C. The reaction time is usually 1 hour to 48 hours, preferably 1 hour to 24 hours.

The molecular weight of the base resin is not particularly limited, and the polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) is preferably 1,000 or more and 50,000 or less, more preferably 2,000 or more. and 30,000 or less, more preferably 3,000 or more and 15,000 or less, and particularly preferably 4,000 or more and 12,000 or less. If the Mw of the base resin is less than the lower limit, the heat resistance of the obtained resist film may decrease. When Mw of a base resin exceeds the said upper limit, the developability of a resist film may fall.

The ratio (Mw/Mn) of Mw of the base resin to the number average molecular weight (Mn) in terms of polystyrene by GPC is usually 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less.

The Mw and Mn of the resin A are values measured using gel permeation chromatography (GPC) under the following conditions.

GPC columns: 2 G2000HXL, 1 G3000HXL, 1 G4000HXL (the above are manufactured by Tosoh Corporation) Column temperature: 40℃ Dissolution solvent: tetrahydrofuran Flow rate: 1.0 mL/min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Detector: Differential Refractometer Standard material: monodisperse polystyrene

The content ratio of the base resin is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 75% by mass or more with respect to the total solid content of the radiation-sensitive resin composition.

(other resins) The radiation-sensitive resin composition of the present embodiment may contain, as another resin, a resin having a larger mass content of fluorine atoms than the base resin (hereinafter, also referred to as "high fluorine content resin"). In the case where the radiation-sensitive resin composition contains a resin with a high fluorine content, it can be biased to exist in the surface layer of the resist film relative to the base resin, and as a result, the resistance of the resist film during immersion exposure can be improved. Water repellency of the surface.

The high fluorine content resin preferably has, for example, a structural unit represented by the following formula (5) (hereinafter, also referred to as "structural unit (V)"), and may have a structural unit in the base resin as necessary (I) or structural unit (II).

[Chemical 9]

In the formula (5), R ¹⁵ is a hydrogen atom, a methyl group or a trifluoromethyl group. GL is a single bond, an oxygen atom, a sulfur atom, -COO-, -SO ₂ ^ONH- , -CONH- or -OCONH-. R ¹⁶ is a monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms.

As said ^R15 , a hydrogen atom and a methyl group are preferable from a viewpoint of the copolymerizability of the monomer which provides a structural unit (V), and a methyl group is more preferable.

As said GL, a single bond and -COO- are preferable from a viewpoint of providing the copolymerizability of the monomer of a structural unit (V), and ^-COO- is more preferable.

As the monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁶ , a part or all of the hydrogen atoms of the linear or branched alkyl group having 1 to 20 carbon atoms are substituted with fluorine atoms. become.

Examples of the monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ¹⁶ include a part or all of the hydrogen atoms contained in the monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms that have undergone fluorine atoms. replaced by.

The R ¹⁶ is preferably a fluorinated chain hydrocarbon group, more preferably a fluorinated alkyl group, and still more preferably 2,2,2-trifluoroethyl, 1,1,1,3,3,3-hexa Fluoropropyl and 5,5,5-trifluoro-1,1-diethylpentyl.

When the high fluorine content resin has a structural unit (V), the content ratio of the structural unit (V) is preferably 30 mol % or more, more preferably 40 mol % with respect to all the structural units constituting the high fluorine content resin % or more, more preferably 45 mol % or more, and particularly preferably 50 mol % or more. In addition, it is preferably 95 mol % or less, more preferably 90 mol % or less, and still more preferably 85 mol % or less. By setting the content ratio of the structural unit (V) to the above-mentioned range, the mass content ratio of fluorine atoms in the resin with high fluorine content can be adjusted more appropriately, and the biased existence in the surface layer of the resist film can be further promoted, as a result. , the water repellency of the resist film during liquid immersion exposure can be further improved.

The high fluorine content resin may have a fluorine atom-containing structural unit (hereinafter, also referred to as a structural unit (VI) represented by the following formula (f-2) together with the structural unit (V) or in place of the structural unit (V). )). Since the high fluorine content resin has a structural unit (f-2), the solubility to an alkaline developer is improved, and the occurrence of development defects can be suppressed.

[Chemical 10]

The structural unit (VI) is roughly classified into those having (x) an alkali-soluble group, and those having (y) a group that is dissociated by the action of an alkali and has an increased solubility in an alkaline developer (hereinafter, also abbreviated as "alkali"). dissociative base") in both cases. Both (x) and (y) are common, and in the formula (f-2), R ^C is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ^D is a single bond, a (s+1)-valent hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, -NR ^dd -, a carbonyl group, -COO- or - is bonded to the terminal on the R ^E side of the hydrocarbon group. A structure formed of CONH- or a structure in which a part of hydrogen atoms contained in the hydrocarbon group is substituted with an organic group having a hetero atom. R ^dd is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. s is an integer of 1-3.

When the structural unit (VI) has (x) an alkali-soluble group, R ^F is a hydrogen atom, and A ¹ is an oxygen atom, -COO-* or -SO ₂ O-*. * ^Indicates the site bound to RF. W ¹ is a single bond, a hydrocarbon group having 1 to 20 carbon atoms, or a divalent fluorinated hydrocarbon group. When A ¹ is an oxygen atom, W ¹ is a fluorinated hydrocarbon group having a fluorine atom or a fluoroalkyl group on the carbon atom to which A ¹ is bonded. R ^E is a single bond or a divalent organic group having 1 to 20 carbon atoms. When s is 2 or 3, a plurality of RE, ^{W 1} , ^{A 1} and RF may be respectively the same or different. By having (x) an alkali-soluble group in the structural unit (VI), the affinity for an alkaline developer can be improved and development defects can be suppressed. The structural unit (VI) having (x) an alkali-soluble group is particularly preferably one in which A ¹ is an oxygen atom and W ¹ is 1,1,1,3,3,3-hexafluoro-2,2-methanediyl. Happening.

When the structural unit (VI) has a base-dissociable group (y), R ^F is a monovalent organic group having 1 to 30 carbon atoms, and A ¹ is an oxygen atom, -NR ^aa -, -COO-* or - SO ₂ O-*. R ^aa is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. * ^Indicates the site bound to RF. W ¹ is a single bond or a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms. R ^E is a single bond or a divalent organic group having 1 to 20 carbon atoms. When A ¹ is -COO-* or -SO ₂ O-*, W ¹ or R ^F has a fluorine atom on the carbon atom bonded to A ¹ or a carbon atom adjacent thereto. When A ¹ is an oxygen atom, W ¹ and R ^E are a single bond, R ^D is a structure in which a carbonyl group is bonded to the terminal on the R ^E side of a hydrocarbon group having 1 to 20 carbon atoms, and R ^F is a structure having a fluorine atom organic base. When s is 2 or 3, a plurality of RE, ^{W 1} , ^{A 1} and RF may be respectively the same or different. Since the structural unit (VI) has (y) an alkali dissociable group, in the alkali development step, the surface of the resist film is changed from hydrophobicity to hydrophilicity. As a result, the affinity for a developer can be greatly improved, and development defects can be suppressed more efficiently. As a structural unit (VI) which has a base dissociable group (y), A ¹ is -COO-*, and R ^F or W ¹ or both of these have a fluorine atom especially preferable.

As R ^C , a hydrogen atom and a methyl group are preferable, and a methyl group is more preferable from the viewpoint of the copolymerizability of the monomer which provides the structural unit (VI).

When ^RE is a divalent organic group, it is preferably a group having a lactone structure, more preferably a group having a polycyclic lactone structure, and still more preferably a group having a norbornane lactone structure.

When the high fluorine content resin has a structural unit (VI), the content ratio of the structural unit (VI) is preferably 50 mol % or more, more preferably 60 mol % with respect to all the structural units constituting the high fluorine content resin % or more, more preferably 70 mol % or more. In addition, it is preferably 95 mol % or less, more preferably 90 mol % or less, and still more preferably 85 mol % or less. By setting the content ratio of the structural unit (VI) to the above range, the water repellency of the resist film at the time of liquid immersion exposure can be further improved.

（所述式（6）中，R ^1α為氫原子、氟原子、甲基或三氟甲基。R ^2α為碳數3～20的一價脂環式烴基。） [Other Structural Units] The high fluorine-content resin may contain, as structural units other than those listed above, a structural unit having an alicyclic structure represented by the following formula (6). [Chemical 11]

(In the above formula (6), R ^1α is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ^2α is a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.)

In the above formula (6), as the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ^2α , a part of hydrogen atoms or All are substituted by fluorine atoms.

When the high fluorine content resin contains the structural unit having an alicyclic structure, the content ratio of the structural unit having an alicyclic structure is preferably 10 mol % relative to all the structural units constituting the high fluorine content resin Above, more preferably 20 mol % or more, still more preferably 30 mol % or more. In addition, it is preferably 70 mol % or less, more preferably 60 mol % or less, and still more preferably 50 mol % or less.

As a lower limit of Mw of a high fluorine content resin, 1,000 is preferable, 2,000 is more preferable, 3,000 is still more preferable, and 5,000 is especially preferable. The upper limit of the Mw is preferably 50,000, more preferably 30,000, still more preferably 20,000, and particularly preferably 15,000.

The lower limit of Mw/Mn of the high fluorine content resin is usually 1, and more preferably 1.1. The upper limit of the Mw/Mn is usually 5, preferably 3, more preferably 2, still more preferably 1.9.

The content of the high fluorine content resin is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and particularly preferably 1.5 part by mass or more, relative to 100 parts by mass of the base resin. Moreover, 15 mass parts or less are preferable, 12 mass parts or less are more preferable, 10 mass parts or less are still more preferable, and 8 mass parts or less are especially preferable.

The radiation-sensitive resin composition may contain one kind or two or more kinds of high fluorine content resins.

(Synthesis method of resin with high fluorine content) The high fluorine content resin can be synthesized by the same method as the synthesis method of the base resin.

（式中， R ¹為具有環狀結構的一價烴基，且構成烴基的亞甲基可經取代為醚鍵， R ^f1及R ^f2分別獨立地為氟原子或一價氟化烴基， m ₁為1～4的整數，在m ₁為2～4的情況下，多個R ^f1及R ^f2的一部分或全部相同或不同， R ²及R ³分別獨立地為氫原子、氟原子、一價烴基或一價氟化烴基， m ₂為0～3的整數，在m ₂為2～3的情況下，多個R ²及R ³的一部分或全部相同或不同， X為單鍵或包含二價雜原子的連接基， R ⁴～R ⁷分別獨立地為氫原子、羥基、一價烴基、或者酯基， n ₁及n ₂分別獨立地為1～3的整數，多個R ⁴～R ⁷的一部分或全部相同或不同， R ⁸為一價鏈狀烴基、一價脂環式烴基、一價氟化烴基、鹵素原子、一價芳香族烴基、或-Y-R ^8'所表示的一價基， （Y表示-O-、-CO-、-COO-、-OCO-，R ^8'為碳數1～20的一價烴基） l為0～5的整數，在l為2～5的情況下，多個R ⁸的一部分或全部相同或不同）。 (Perylium salt compound (B0)) The perylium salt compound (B0) in the present invention is a compound represented by the following formula (1). [Chemical 12]

(in the formula, R ¹ is a monovalent hydrocarbon group having a cyclic structure, and the methylene group constituting the hydrocarbon group may be substituted with an ether bond, R ^f1 and R ^f2 are independently a fluorine atom or a monovalent fluorinated hydrocarbon group, m ₁ is an integer of 1 to 4, and when m ₁ is 2 to 4, some or all of the plurality of R ^f1 and R ^f2 are the same or different, and R ² and R ³ are each independently a hydrogen atom, a fluorine atom, a monovalent Hydrocarbon group or monovalent fluorinated hydrocarbon group, m ₂ is an integer of 0 to 3, when m ₂ is 2 to 3, some or all of a plurality of R ² and R ³ are the same or different, X is a single bond or contains two A linking group of a valence heteroatom, R ⁴ to R ⁷ are each independently a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group, or an ester group, n ₁ and n ₂ are each independently an integer of 1 to 3, and a plurality of R ⁴ to R A part or all of ⁷ are the same or different, R ⁸ is a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent fluorinated hydrocarbon group, a halogen atom, a monovalent aromatic hydrocarbon group, or a monovalent represented by -YR ^8' base, (Y represents -O-, -CO-, -COO-, -OCO-, R ^8' is a monovalent hydrocarbon group with 1 to 20 carbon atoms) l is an integer of 0 to 5, where l is 2 to 5 case, some or all of the plurality of R ⁸ are the same or different).

In the above formula (1), as the monovalent hydrocarbon group having a cyclic structure represented by R ¹ , a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3 to 40 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 40 carbon atoms can be mentioned. The monovalent hydrocarbon groups having a cyclic structure, the methylene groups constituting these hydrocarbon groups may be substituted with ether bonds.

Examples of the alicyclic hydrocarbon group represented by R ¹ or the hydrocarbon group having a cyclic structure include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bornyl, norbornyl, adamantyl, Pinyl, limone (thuoyl group), charyl (caryl group), camphenyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, bornylmethyl, norbornyl methyl, and adamantyl methyl, etc.

Further, examples of the substituents of the alicyclic hydrocarbon group represented by R ¹ and the hydrocarbon group having a cyclic structure include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a hydroxyl group, a carboxyl group, A cyano group, a nitro group, an alkyl group (in the case of replacing a hydrogen atom of a cycloalkyl group or an aromatic hydrocarbon group), an aryl group (in the case of substituting a hydrogen atom in an alkyl group), an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyl group oxy, acyl, acyloxy, etc. Among these, a fluorine atom, an alkyl group, and an aryl group are preferable.

Examples of the alicyclic hydrocarbon group or hydrocarbon group having a cyclic structure substituted with such a substituent include 4-fluorocyclohexyl, 4-hydroxycyclohexyl, 4-methoxycyclohexyl, and 4-methoxycyclohexyl. ylcarbonylcyclohexyl, 3-hydroxy-1-adamantyl, 3-methoxycarbonyl-1-adamantyl, 3-hydroxycarbonyl-1-adamantyl, and 3-hydroxymethyl-1-adamantane methyl, etc.

In the above formula (1), examples of the monovalent fluorinated hydrocarbon groups represented by R ^f1 and R ^f2 each independently include, for example, monovalent fluorinated hydrocarbon groups having 1 to 10 carbon atoms.

Examples of the monovalent fluorinated hydrocarbon group having 1 to 10 carbon atoms represented by R ^f1 and R ^f2 include monovalent fluorinated chain hydrocarbon groups having 1 to 10 carbon atoms, and monovalent fluorine having 3 to 10 carbon atoms. Alicyclic hydrocarbon groups, etc.

Examples of the monovalent fluorinated chain hydrocarbon group having 1 to 10 carbon atoms represented by R ^f1 and R ^f2 include trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, Fluorinated alkyl groups such as 2,2,3,3,3-pentafluoropropyl, 1,1,1,3,3,3-hexafluoropropyl, heptafluoro-n-propyl; trifluorovinyl, pentafluoro Fluorinated alkenyl such as propenyl; fluorinated alkynyl such as fluoroethynyl, trifluoropropynyl, and the like.

Examples of the monovalent fluorinated alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ^f1 and R ^f2 include fluorocyclopentyl, difluorocyclopentyl, nonafluorocyclopentyl, and fluorocyclohexyl. , difluorocyclohexyl, undecafluorocyclohexylmethyl, fluoronorbornyl, fluoroadamantyl, fluorobornyl, fluoroisobornyl and other fluorinated cycloalkyl groups; fluorocyclopentenyl, nonafluorocyclohexene Fluorinated cycloalkenyl and the like.

The fluorinated hydrocarbon group represented by the R ^f1 and R ^f2 is preferably the monovalent fluorinated chain hydrocarbon group having 1 to 10 carbon atoms, more preferably the monovalent fluorinated alkyl group having 1 to 8 carbon atoms, Further preferred is a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferred is a linear perfluoroalkyl group having 1 to 6 carbon atoms.

In the above formula (1), m ₁ is an integer of 1 to 4, and may be 2 to 3. When m ₁ is 2 to 4, some or all of the plurality of R ^f1 and R ^f2 are the same or different.

In the above formula (1), R ² and R ³ are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group, or a monovalent fluorinated hydrocarbon group.

As the monovalent hydrocarbon group represented by R ² and R ³ , the same groups as the monovalent hydrocarbon group in R ¹ can be used independently of each other.

As the monovalent fluorinated hydrocarbon group represented by the above R ² and R ³ , the same groups as the monovalent fluorinated hydrocarbon groups in R ^f1 and R ^f2 can be used independently of each other.

In the above formula (1), m ₂ is an integer of 0 to 3, and may be 1 to 2. When m ₂ is 2 to 3, some or all of the plurality of R ² and R ³ are the same or different.

In the formula (1), X is a single bond or a linking group containing a divalent heteroatom.

Examples of the divalent hetero atom in the X include an oxygen atom, a sulfur atom, and the like.

Examples of the linking group containing a divalent hetero atom represented by the X include -O-, -(C=O)-, -(C=O)O-, -S-, -SO ₂ -, and combinations of these.

In the above formula (1), R ⁴ to R ⁷ are each independently a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group or an ester group.

As the monovalent hydrocarbon group represented by the above R ⁴ to R ⁷ , the same groups as the monovalent hydrocarbon group in R ¹ can be used independently of each other.

Examples of the ester groups represented by R ⁴ to R ⁷ each independently include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, and the like.

In the above formula (1), n ₁ and n ₂ are each independently an integer of 1 to 3, and may be 2. Some or all of the plurality of R ⁴ to R ⁷ are the same or different.

In the formula (1), R ⁸ is a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent fluorinated hydrocarbon group, a halogen atom, a monovalent aromatic hydrocarbon group, or a monovalent group represented by -YR ^8' . (Y represents -O-, -CO-, -COO-, -OCO-, and R ^8' is a monovalent hydrocarbon group having 1 to 20 carbon atoms.)

Examples of the monovalent chain hydrocarbon group represented by R ⁸ each independently include, for example, a methyl group, an ethyl group, and the like.

As the monovalent alicyclic hydrocarbon group represented by R ⁸ , each independently includes, for example, a cyclopentyl group, a cyclohexyl group, and the like.

As the monovalent fluorinated hydrocarbon group represented by the above R ⁸ , the same groups as the monovalent fluorinated hydrocarbon groups in R ^f1 and R ^f2 can be used independently of each other.

Examples of the halogen atom represented by R ⁸ include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.

Examples of the monovalent aromatic hydrocarbon group represented by R ⁸ include monovalent aromatic hydrocarbon groups having 6 to 12 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by R ⁸ each independently include, for example, aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthracenyl, benzyl, benzene, and the like. Aralkyl groups such as ethyl, naphthylmethyl, etc.

Examples of the alkylsilyl group represented by R ⁸ include trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, diethylisopropylsilyl, triisopropylsilyl Propylsilyl, dimethylhexylsilyl, tert-butyldiphenylsilyl, dimethylphenylsilyl, triphenylsilyl, tris(trimethylsilyl)silyl.

Examples of the group represented by -YR ^8' in R ⁸ include a hydrocarbon group having 1 to 20 carbon atoms, which is formed by a bonding group selected from the group consisting of -O-, -CO-, -COO-, and -OCO-. bonding base.

As a C1-C20 hydrocarbon group represented by said R ^8' , a methyl group, an ethyl group, etc. are mentioned, for example.

In the above formula (1), l is an integer of 0 to 5, and may be 1 to 4. When l is 2 to 5, some or all of the plurality of R ⁸ are the same or different.

In the above formula (1), it is preferable that at least one of R ⁸ is present at the para position with respect to the bonding position of S ⁺ in the formula.

As said compound (1), it is not limited to this, For example, the following compounds are mentioned. [Chemical 13]

In addition, in the present invention, the total content of the perylene salt compound (B0) in the resin composition is preferably 0.5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the resin (A), and can be set to 1 Parts by mass to 25 parts by mass can be set to 1.5 parts by mass to 20 parts by mass. In addition, the perylene salt compound (B0) may be used alone or in combination of two or more.

(Solvent (D)) The radiation-sensitive resin composition contains a solvent. The solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing at least the resin, the radiation-sensitive acid generator, and optionally, the acid diffusion control agent, and the like.

Examples of the solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, hydrocarbon-based solvents, and the like.

Examples of alcohol-based solvents include: Isopropanol, 4-methyl-2-pentanol, 3-methoxybutanol, n-hexanol, 2-ethylhexanol, furfuryl alcohol, cyclohexanol, 3,3,5-trimethylcyclohexanol , Diacetone alcohol and other monohydric alcohol solvents with carbon number of 1 to 18; Ethylene glycol, 1,2-propylene glycol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc. carbon number 2 ~18 polyol-based solvents; A polyhydric alcohol partial ether type solvent etc. which etherify a part of the hydroxyl group which the said polyhydric alcohol type solvent has.

Examples of ether-based solvents include: Dialkyl ether solvents such as diethyl ether, dipropyl ether, and dibutyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; Aromatic ring-containing ether solvents such as diphenyl ether and anisole (methyl phenyl ether); A polyol ether-based solvent or the like obtained by etherifying a hydroxyl group contained in the polyol-based solvent.

Examples of the ketone-based solvent include chain ketone-based solvents such as acetone, methyl ethyl ketone, and methyl-isobutyl ketone; Cyclic ketone solvents such as cyclopentanone, cyclohexanone, methyl cyclohexanone; 2,4-pentanedione, acetone acetone, acetophenone, etc.

Examples of the amide-based solvent include cyclic amide-based solvents such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide Chain amide solvents such as amide and N-methylpropionamide, etc.

Examples of ester-based solvents include: Monocarboxylate solvents such as n-butyl acetate and ethyl lactate; Diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and other polyhydric alcohol partial ether acetate solvents; Lactone solvents such as γ-butyrolactone and valerolactone; Carbonate-based solvents such as diethyl carbonate, ethylene carbonate, and propyl carbonate; Polycarboxylic acid diester-based solvents such as propylene glycol diacetate, methoxytriethylene glycol acetate, diethyl oxalate, ethyl acetate, ethyl lactate, and diethyl phthalate.

Examples of hydrocarbon-based solvents include: Aliphatic hydrocarbon solvents such as n-hexane, cyclohexane and methylcyclohexane; Aromatic hydrocarbon-based solvents such as benzene, toluene, diisopropylbenzene, n-pentylnaphthalene, and the like.

Among these, ester-based solvents and ketone-based solvents are preferred, polyol partial ether acetate-based solvents, cyclic ketone-based solvents, and lactone-based solvents are more preferred, and propylene glycol monomethyl ether acetate, Cyclohexanone, gamma-butyrolactone. The radiation-sensitive resin composition may contain one or two or more kinds of solvents.

(any other ingredients) The radiation-sensitive resin composition may contain other arbitrary components in addition to the above-mentioned components. Examples of the other optional components include an acid diffusion controller, a crosslinking agent, a localization accelerator, a surfactant, an alicyclic skeleton-containing compound, a sensitizer, and the like. These other optional components may be used alone or in combination of two or more.

(acid diffusion control agent) The radiation-sensitive resin composition may contain an acid diffusion control agent as needed. The acid diffusion control agent exerts the effects of controlling the diffusion phenomenon in the resist film of the acid generated by the radiation-sensitive acid generator by exposure, and suppressing the undesired chemical reaction in the non-exposed area. In addition, the storage stability of the obtained radiation-sensitive resin composition is improved. Furthermore, the resolution of the resist pattern is further improved, and the variation of the line width of the resist pattern caused by the variation of the standing time from exposure to development can be suppressed, so that radiation sensitivity excellent in process stability can be obtained. resin composition.

Examples of the acid diffusion control agent include a compound represented by the following formula (7) (hereinafter, also referred to as "nitrogen-containing compound (I)") and a compound having two nitrogen atoms in the same molecule (hereinafter, also referred to as "nitrogen-containing compound (I)"). referred to as "nitrogen-containing compound (II)"), compound having three nitrogen atoms (hereinafter, also referred to as "nitrogen-containing compound (III)"), amide group-containing compound, urea compound, nitrogen-containing heterocyclic compound Wait.

[Chemical 14]

In the formula (7), R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or substituted or unsubstituted aralkyl.

Examples of the nitrogen-containing compound (I) include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; and aromatics such as aniline. Amines, etc.

As a nitrogen-containing compound (II), ethylenediamine, N,N,N',N'- tetramethylethylenediamine, etc. are mentioned, for example.

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

Examples of the amide group-containing compound include carboxamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N - Dimethylacetamide, propionamide, benzylamide, pyrrolidone, N-methylpyrrolidone, etc.

As a urea compound, urea, methyl urea, 1, 1- dimethyl urea, 1, 3- dimethyl urea, 1, 1, 3, 3- tetramethyl urea, 1, 3- di- Phenyl urea, tributyl thiourea, etc.

Examples of nitrogen-containing heterocyclic compounds include pyridines such as pyridine and 2-picoline; morpholines such as N-propylmorpholine and N-(undecylcarbonyloxyethyl)morpholine; pyridines oxazine, pyrazole, etc.

Moreover, as said nitrogen-containing organic compound, the compound which has an acid dissociable group can also be used. Examples of the nitrogen-containing organic compound having such an acid dissociable group include N-tert-butoxycarbonylpiperidine, N-tert-butoxycarbonylimidazole, and N-tert-butoxycarbonylbenzimidazole. , N-tertiary butoxycarbonyl-2-phenylbenzimidazole, N-(tertiary butoxycarbonyl) di-n-octylamine, N-(tertiary butoxycarbonyl) diethanolamine, N-( tertiary butoxycarbonyl) dicyclohexylamine, N-(tertiary butoxycarbonyl) diphenylamine, N-tertiary butoxycarbonyl-4-hydroxypiperidine, N-tertiary pentoxycarbonyl -4-Hydroxypiperidine etc.

Moreover, as an acid diffusion control agent, the photodegradable base which produces|generates a weak acid by exposure can also be used suitably. Examples of the photodegradable base include compounds containing a radiosensitive onium cation decomposed by exposure and an anion of a weak acid. Since the photodegradable base generates a weak acid in the exposed portion by the proton generated by the decomposition of the radiosensitive onium cation and the anion of the weak acid, the acid diffusion controllability is lowered.

As a photodegradable base, the periconium salt compound represented by following formula (8-1), the iodonium salt compound represented by following formula (8-2), etc. are mentioned, for example.

[Chemical 15]

In the above formulas (8-1) and (8-2), J ⁺ is a perionium cation, and U ⁺ is an iodonium cation. The periconium cation or the iodonium cation is preferably represented by the following formulae (X-1) to (X-6). E ^- and Q ^- are each independently an anion represented by OH-, R ^α -COO ^- and R ^α -SO ₃ ^- . R ^α is an alkyl group, an aryl group or an aralkyl group. The hydrogen atom of the aromatic ring of the aryl group or aralkyl group represented by R ^α may also pass through a hydroxyl group, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. replace.

[Chemical 16]

In the formula (X-1), R ^a1 , R ^a2 and R ^a3 are each independently a substituted or unsubstituted linear or branched alkyl group, alkoxy group or alkane having 1 to 12 carbon atoms Oxycarbonyloxy, substituted or unsubstituted monocyclic or polycyclic cycloalkyl group with 3 to 12 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group with 6 to 12 carbon atoms, hydroxyl group, halogen atom , -OSO ₂ -R ^P , -SO ₂ -R ^Q or -SR ^T , or a ring structure formed by combining two or more of these groups. The ring structure may contain heteroatoms such as O or S between carbon-carbon bonds forming the skeleton. R ^P , R ^Q and R ^T are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alicyclic having 5 to 25 carbon atoms A hydrocarbon group of the formula or a substituted or unsubstituted aromatic hydrocarbon group with 6 to 12 carbon atoms. k1, k2, and k3 are each independently an integer of 0-5. When there are multiple R ^a1 to R ^a3 and R ^P , R ^Q and ^RT respectively, the multiple R ^a1 to R ^a3 and R ^P , R ^Q and RT may be the same or different, respectively ^.

In the formula (X-2), R ^b1 is a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms or an alkoxy group, a substituted or unsubstituted carbon number 2 -8 acyl group, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, or a hydroxyl group. n _k is 0 or 1. When n _k is 0, k4 is an integer of 0 to 4, and when n _k is 1, k4 is an integer of 0 to 7. When there are plural R ^b1s , the plural R ^b1s may be the same or different, and the plural R ^b1s may express a ring structure formed by bonding with each other. R ^b2 is a substituted or unsubstituted linear or branched alkyl group having 1 to 7 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 or 7 carbon atoms. L ^C is a single bond or a divalent linking group. k5 is an integer of 0-4. When a plurality of R ^b2s are present, the plurality of R ^b2s may be the same or different, and the plurality of R ^b2s may express a ring structure formed by combining with each other. q is an integer of 0-3. In the formula, the ring structure containing S ⁺ may contain heteroatoms such as O or S between the carbon-carbon bonds forming the skeleton.

In the formula (X-3), R ^c1 , R ^c2 and R ^c3 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms.

In the formula (X-4), R ^g1 is a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms or an alkoxy group, a substituted or unsubstituted carbon number 2 -8 acyl group, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, or a hydroxyl group. n _k2 is 0 or 1. When n _k2 is 0, k10 is an integer of 0 to 4, and when n _k2 is 1, k10 is an integer of 0 to 7. When there are plural R ^g1s , the plural R ^g1s may be the same or different, and the plural R ^g1s may express a ring structure formed by combining with each other. R ^g2 and R ^g3 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, an alkoxy group or an alkoxycarbonyloxy group, a substituted or unsubstituted A monocyclic or polycyclic cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a hydroxyl group, a halogen atom, or a ring structure formed by combining these groups with each other . k11 and k12 are each independently an integer of 0 to 4. When each of R ^g2 and R ^g3 is plural, the plural R ^g2 and R ^g3 may be the same or different, respectively.

In the formula (X-5), R ^d1 and R ^d2 are each independently a substituted or unsubstituted linear or branched alkyl group, alkoxy group or alkoxycarbonyl group having 1 to 12 carbon atoms , substituted or unsubstituted aromatic hydrocarbon groups with 6 to 12 carbon atoms, halogen atoms, halogenated alkyl groups with 1 to 4 carbon atoms, nitro groups, or a ring formed by combining two or more of these groups with each other structure. k6 and k7 are each independently an integer of 0-5. When each of R ^d1 and R ^d2 is plural, the plural R ^d1 and R ^d2 may be the same or different, respectively.

In the formula (X-6), R ^e1 and R ^e2 are each independently a halogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted alkyl group. A substituted aromatic hydrocarbon group having 6 to 12 carbon atoms. k8 and k9 are each independently an integer of 0-4.

Examples of substituents that may replace the hydrogen atoms possessed by the aforementioned groups include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, and alkyl groups (substituted by In the case of a hydrogen atom of a cycloalkyl group or an aromatic hydrocarbon group), an aryl group (in the case of a hydrogen atom substituted for an alkyl group), an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an aryl group, an aryloxy group, and the like . Among these, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an acyl group, and an acyloxy group are preferable, and an alkoxy group or an alkoxycarbonyl group is more preferable.

As said photodegradable base, the compound etc. which are represented by the following formula are mentioned, for example.

[Chemical 17]

Among these, the photodegradable base is preferably a perylene salt, more preferably a triaryl perylene salt, and still more preferably a triphenyl perylene salicylate and a triphenyl perylene 10-camphorsulfonate.

The lower limit of the content of the acid diffusion control agent is preferably 2 parts by mass, more preferably 3 parts by mass, and still more preferably 4 parts by mass with respect to 100 parts by mass in total of the radiation-sensitive acid generator. The upper limit of the content is preferably 150 parts by mass, more preferably 120 parts by mass, and still more preferably 110 parts by mass.

By setting the content of the acid diffusion control agent to the above-mentioned range, the lithography performance of the radiation-sensitive resin composition can be further improved. The radiation-sensitive resin composition may contain one or two or more acid diffusion control agents.

(crosslinking agent) The cross-linking agent is a compound having two or more functional groups. In the baking step after the overall exposure step, a cross-linking reaction is induced in the polymer component through an acid catalyst reaction, so that the molecular weight of the polymer component is increased, Thereby, the solubility with respect to a developing solution of a pattern exposure part is reduced. As said functional group, a (meth)acryloyl group, a hydroxymethyl group, an alkoxymethyl group, an epoxy group, a vinyl ether group, etc. are mentioned, for example.

(biased towards existential accelerators) The localization accelerator has the effect of making the high fluorine content resin more efficiently localized on the surface of the resist film. By making the radiation-sensitive resin composition contain the biased existence accelerator, the addition amount of the high-fluorine-content resin can be reduced compared with the conventional method. Therefore, while maintaining the lithography performance of the radiation-sensitive resin composition, the elution of components from the resist film to the liquid immersion medium can be further suppressed, or the liquid immersion exposure can be performed at a higher speed by high-speed scanning. As a result, It is possible to improve the hydrophobicity of the surface of the resist film which suppresses defects derived from liquid immersion such as watermark defects. As a thing which can be used as such a biasing accelerator, for example, a low molecular weight compound whose relative dielectric constant is 30 or more and 200 or less and whose boiling point under one atmospheric pressure is 100 degreeC or more is mentioned. As such a compound, a lactone compound, a carbonate compound, a nitrile compound, a polyhydric alcohol etc. are mentioned specifically,.

As said lactone compound, gamma-butyrolactone, valerolactone, mevalonic lactone, norbornane lactone etc. are mentioned, for example.

As said carbonate compound, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, etc. are mentioned, for example.

As said nitrile compound, succinonitrile etc. are mentioned, for example.

As said polyhydric alcohol, glycerol etc. are mentioned, for example.

The lower limit of the content of the biasing accelerator is preferably 10 parts by mass, more preferably 15 parts by mass, and still more preferably 20 parts by mass with respect to 100 parts by mass of the total resin in the radiation-sensitive resin composition. , especially preferably 25 parts by mass. The upper limit of the content is preferably 300 parts by mass, more preferably 200 parts by mass, still more preferably 100 parts by mass, and particularly preferably 80 parts by mass. The radiation-sensitive resin composition may also contain one or two or more kinds of biased existence accelerators.

(surfactant) The surfactant has the effect of improving coatability, striation, developability, and the like. As the surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyoxyethylene Nonionic surfactants such as ethylene glycol dilaurate and polyethylene glycol distearate; commercially available products include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75. Polyflow No.95 (above manufactured by Gongrongsha Chemical), Eftop EF301, Eftop EF303, Eftop EF352 (above by Taokai Tohchem Products), Megafac F171, Megafac F173 (above manufactured by DIC), Fluorad FC430, Fluorad FC431 (above manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon ) SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (the above are manufactured by Asahi Glass Industries), etc. The content of the surfactant in the radiation-sensitive resin composition is usually 2 parts by mass or less with respect to 100 parts by mass of the resin.

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

Examples of compounds containing an alicyclic skeleton include: Adamantane derivatives such as 1-adamantane carboxylic acid, 2-adamantanone, 1-adamantane carboxylic acid tert-butyl ester; Deoxycholate esters such as 3-butyl deoxycholate, 3-butoxycarbonyl deoxycholate, and 2-ethoxyethyl deoxycholate; Lithocholic acid 3-butyl ester, lithocholic acid 3-butoxycarbonyl methyl ester, lithocholic acid 2-ethoxyethyl ester and other lithocholic acid esters; 3-[2-Hydroxy-2,2-bis(trifluoromethyl)ethyl]tetracyclo[4.4.0.1(2,5).1(7,10)]dodecane, 2-hydroxy-9- Methoxycarbonyl-5-oxo-4-oxa-tricyclo[4.2.1.0(3,7)]nonane, etc. The content of the alicyclic skeleton-containing compound in the radiation-sensitive resin composition is usually 5 parts by mass or less with respect to 100 parts by mass of the resin.

(sensitizer) The sensitizer has the effect of increasing the amount of acid generated from the radiation-sensitive acid generator or the like, and has the effect of improving the "apparent sensitivity" of the radiation-sensitive resin composition.

Examples of sensitizers include: carbazoles, acetophenones, benzophenones, naphthalenes, phenols, diacetyl, eosin, rose Bengal, pyrenes, anthracenes, phenothiazine class etc. These sensitizers may be used alone or in combination of two or more. The content of the sensitizer in the radiation-sensitive resin composition is usually 2 parts by mass or less with respect to 100 parts by mass of the resin.

(composition) The radiation-sensitive resin composition is particularly suitable for use in organic solvent development, that is, in the case of forming a negative pattern by organic solvent development in the development step.

<Preparation method of radiation-sensitive resin composition> The radiation-sensitive resin composition can be prepared, for example, by mixing the resin, the pernium salt compound (or the radiation-sensitive acid generator), an optional acid diffusion control agent, a high fluorine content resin, etc., and a solvent in a predetermined ratio. Mix to prepare. The radiation-sensitive resin composition is preferably filtered, for example, with a filter having a pore size of about 0.05 μm after mixing. The solid content concentration of the radiation-sensitive resin composition is usually 0.1 to 50 mass %, preferably 0.5 to 30 mass %, and more preferably 1 to 20 mass %.

<Method for forming a resist pattern> The formation method of the resist pattern in the present invention includes: A step of directly or indirectly coating the radiation-sensitive resin composition on a substrate to form a resist film (hereinafter, also referred to as "resist film forming step"); a step of exposing the resist film (hereinafter, also referred to as an "exposure step"); and A step of developing the exposed resist film.

According to the method for forming a resist pattern, since the radiation-sensitive resin composition is used, a resist pattern capable of exhibiting sensitivity, LWR performance, and CDU performance in an exposure step at an excellent level can be formed. Hereinafter, each step will be described.

[Resist film formation step] In this step, a resist film is formed using the radiation-sensitive resin composition. More specifically, it is a step of directly or indirectly applying the radiation-sensitive resin composition on a substrate to form a resist film. As a substrate on which the resist film is formed, for example, conventionally known ones such as silicon wafers, silicon dioxide, and aluminum-coated wafers can be mentioned. In addition, an organic or inorganic antireflection film disclosed in, for example, Japanese Patent Laid-Open No. 6-12452, Japanese Patent Laid-Open No. 59-93448, etc. may be formed on the substrate. As a coating method, spin coating (spin coating), casting coating, roll coating, etc. are mentioned, for example. After coating, prebake (PB) may be performed as necessary to volatilize the solvent in the coating film. The PB temperature is usually 60°C to 140°C, preferably 80°C to 120°C. The PB time is usually 5 seconds to 600 seconds, preferably 10 seconds to 300 seconds. The thickness of the resist film to be formed is preferably 10 nm to 1,000 nm, and more preferably 10 nm to 500 nm.

In the case of liquid immersion exposure, regardless of the presence or absence of water-repellent polymer additives such as the high fluorine content resin in the radiation-sensitive resin composition, in order to avoid direct contact between the liquid immersion liquid and the resist film For the purpose of immersion, a liquid immersion protective film which is insoluble to the liquid immersion liquid may be provided on the formed resist film. As the protective film for liquid immersion, a solvent peeling type protective film that is peeled off with a solvent before the development step (for example, refer to Japanese Patent Laid-Open No. 2006-227632), and a developer peeling type that is peeled off simultaneously with the development of the developing step can also be used Any of the protective films (for example, refer to WO2005-069076 A and WO2006-035790). Among them, from the viewpoint of yield, it is preferable to use a developing solution peeling-type liquid immersion protective film.

In addition, when performing the exposure step as the next step with radiation having a wavelength of 50 nm or less, it is preferable to use a resin having the structural unit (I) and the structural unit (IV) as a base in the composition resin.

[Exposure step] In this step, the resist film formed in the resist film forming step is irradiated with radiation through a photomask (via a liquid immersion medium such as water as appropriate) for exposure. Examples of radiation used for exposure include electromagnetic waves such as visible rays, ultraviolet rays, extreme ultraviolet rays, extreme ultraviolet rays (EUV), X rays, and γ rays, and charged particle beams such as electron beams and α rays, depending on the line width of the target pattern. . Among them, far-ultraviolet rays, electron beams, EUV are preferred, ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), electron beams, EUV are more preferred, and further preferred are positioned as Electron beam and EUV with wavelengths below 50 nm for next-generation exposure technology.

When exposure is performed by liquid immersion exposure, as a liquid immersion liquid to be used, water, a fluorine-type inert liquid, etc. are mentioned, for example. The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a temperature coefficient of refractive index as small as possible to minimize the distortion of the optical image projected on the film, especially when the exposure light source is an ArF excimer laser. In the case of irradiated light (wavelength of 193 nm), it is preferable to use water from the viewpoints of easiness of acquisition, easiness of handling, and the like. In the case of using water, an additive which reduces the surface tension of water and increases the interfacial active force may be added at a slight ratio. The additive preferably does not dissolve the resist film on the wafer and has a negligible effect on the optical coating on the lower surface of the lens. As the water to be used, distilled water is preferred.

Preferably, a post exposure bake (PEB) is performed after the exposure, and in the exposed portion of the resist film, the acid generated by the self-inductive radiation acid generator by exposure is used to promote the resin Dissociation of acid dissociable groups, etc. Due to the PEB, the difference in solubility with respect to the developer occurs between the exposed portion and the unexposed portion. The PEB temperature is usually 50°C to 180°C, preferably 80°C to 130°C. The PEB time is usually 5 seconds to 600 seconds, preferably 10 seconds to 300 seconds.

Further, after the exposure step, a step of developing the exposed resist film (hereinafter, also referred to as a “development step”) may be included.

[Development step] In this step, the resist film exposed in the exposure step is developed. Thereby, a predetermined resist pattern can be formed. Generally, it wash|cleans with the rinse liquid, such as water or alcohol, after image development, and it is dried.

As the developing solution used for the development, in the case of alkali development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propyl amine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethyl ammonium hydroxide (TMAH), Bases such as pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene Alkaline aqueous solution of at least one kind of compound, etc. Among these, TMAH aqueous solution is preferable, and 2.38 mass % TMAH aqueous solution is more preferable.

Moreover, in the case of an organic solvent image development, organic solvents, such as a hydrocarbon type solvent, an ether type solvent, an ester type solvent, a ketone type solvent, and an alcohol type solvent, or the solvent containing an organic solvent are mentioned. As the organic solvent, for example, one or two or more of the solvents listed as the solvent of the radiation-sensitive resin composition may be mentioned. Among these, ester-based solvents and ketone-based solvents are preferred. As the ester-based solvent, an acetate-based solvent is preferable, and n-butyl acetate and amyl acetate are more preferable. The ketone-based solvent is preferably a chain ketone, more preferably 2-heptanone. The content of the organic solvent in the developer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 99% by mass or more. As a component other than the organic solvent in a developer, water, a silicone oil, etc. are mentioned, for example.

This method of forming a resist pattern is particularly suitable for the case where a negative pattern is formed by developing with an organic solvent in the developing step.

Examples of the developing method include: a method of immersing a substrate in a tank filled with a developing solution for a fixed period of time (dipping method); a method of developing by depositing a developing solution on the surface of the substrate by utilizing surface tension and standing still for a fixed period of time (overlay method) liquid (puddle) method); the method of spraying the developer on the surface of the substrate (spray method); the method of continuously applying the developer on the substrate rotating at a fixed speed while scanning the nozzle for the developer at a fixed speed (dynamic distribution method) etc.

<Processing Method of Substrate and Manufacturing Method of Metal Film Pattern> The processing method of the substrate of the present invention further comprises: The resist pattern formed by the method is used as a mask to form a pattern on the substrate.

Since the processing method of the substrate uses the radiation-sensitive resin composition, it is possible to form a high-quality substrate pattern.

The step is a step of masking the resist pattern formed by any one of the methods and forming a pattern on the substrate, as a step of masking the resist pattern and forming a pattern on the substrate. As a method, for example, after forming a resist pattern on a substrate, a method of forming a pattern on a substrate by a method such as dry etching in a part without resist; after forming a resist pattern, without resist The part of the agent is a method of forming a part or the whole of the substrate by evaporating the constituent components of the substrate by CVD or the like, or by attaching a metal by a method such as electroless plating.

In addition, the manufacturing method of the metal film pattern of the present invention further comprises: The resist pattern formed by the method is used as a mask to form a metal film.

Since the manufacturing method of the metal film pattern uses the radiation-sensitive resin composition, the metal film pattern can be processed.

The step is a step of forming a metal film using the resist pattern formed by the method described in any of the above as a mask, and the method of forming a metal film using the resist pattern as a mask includes, for example. After the resist pattern is formed, a metal film is formed by attaching metal to the part without the resist by methods such as electroless plating; a resist pattern is formed on the metal film and removed by a method such as dry etching A method of forming a metal film without a metal film of a resist portion.

(Radiation-sensitive acid generator (B)) The radiation-sensitive acid generator (B) of the present invention is a radiation-sensitive acid generator containing the periconium salt compound represented by the formula (1).

The radiation-sensitive acid generator (B) is a radiation-sensitive acid generator that generates acid by irradiation with radiation.

Each structure in the formula (1) is the same as that described in the item of the (perylium salt compound (B0)).

In addition, in the present invention, the total content of the radiation-sensitive acid generator (B) in the resin composition is preferably 0.5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the resin (A), It can be set as 1 mass part - 25 mass parts, and can be set as 1.5 mass parts - 20 mass parts. If the compounding amount or the content ratio is less than the lower limit, the sensitivity may be lowered. Conversely, when the compounding amount or the content ratio exceeds the upper limit, it may be difficult to form a resist film, or the rectangularity of the cross-sectional shape of the resist pattern may be lowered. In addition, the radiation-sensitive acid generator (B) may be used alone or in combination of two or more. Moreover, as long as the effects of the present invention are not impaired, known radiation-sensitive acid generators may be used in combination.

The radiation-sensitive acid generator (B) can be particularly suitably used in the case of an organic solvent development application, that is, when a negative pattern is formed by development with an organic solvent in the development step. [Example]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. The measurement methods of various physical property values are shown below.

[Measurement of weight average molecular weight (Mw), number average molecular weight (Mn) and degree of dispersion (Mw/Mn)] The Mw and Mn of the polymer were measured under the above-mentioned conditions. In addition, the degree of dispersion (Mw/Mn) was calculated from the measurement results of Mw and Mn.

[ ¹³ C-Nuclear Magnetic Resonance (NMR) Analysis] The ¹³ C-NMR analysis of the polymer was carried out using a nuclear magnetic resonance apparatus (“JNM-Delta400” from Japan Electron Co., Ltd.).

<Synthesis of [A] Resin and [E] High Fluorine Content Resin> The monomers used for the synthesis of each resin and high fluorine content resin in each Example and each Comparative Example are shown below. In addition, in the following synthesis examples, unless otherwise specified, the parts by mass refer to the value when the total mass of the monomers used is 100 parts by mass, and the mole % refers to the amount of the monomers used. The total number of moles of the body is set to the value when 100 mole%.

[Chemical 18]

[Synthesis Example 1] (Synthesis of Resin (A-1)) Monomer (M-1), Monomer (M-2), and Monomer (M-13) were molar ratio of 40/15 2-butanone (200 parts by mass) was dissolved in 2-butanone (200 parts by mass) so as to be /45 (mol %), and azobisisobutyronitrile (AIBN) was added as a starting agent (with respect to the total amount of monomers used) 100 mol % instead of 3 mol %) to prepare a monomer solution. 2-Butanone (100 parts by mass) was placed in the reaction vessel, and after 30 minutes of nitrogen flushing, the inside of the reaction vessel was set to 80° C., and the monomer solution was added dropwise over 3 hours while stirring. The start of dropwise addition was set as the start time of the polymerization reaction, and the polymerization reaction was carried out for 6 hours. After the completion of the polymerization reaction, the polymerization solution was cooled to 30°C or lower by water-cooling. The cooled polymerization solution was put into methanol (2,000 parts by mass), and the precipitated white powder was separated by filtration. After the white powder separated by filtration was washed twice with methanol, it was separated by filtration, and dried at 50° C. for 24 hours to obtain a white powdery resin (A-1) (yield: 80%). Mw of resin (A-1) was 8,800, and Mw/Mn was 1.50. In addition, as a result of ¹³ C-NMR analysis, the content ratios of the respective structural units derived from (M-1), (M-2) and (M-13) were 41.3 mol %, 13.8 mol % and 44.9 mol %, respectively. Ear%.

[Synthesis Example 1 to Synthesis Example 11] (Synthesis of resin (A-2) to resin (A-11)) Resin (A-2) to resin (A-11) were synthesized in the same manner as in Synthesis Example 1, except that the monomers of the types and compounding ratios shown in the following Table 1 were used. The content ratio (mol %), yield (%), and physical property values (Mw and Mw/Mn) of each structural unit of the obtained resin are collectively shown in Table 1 below. In addition, "-" in the following Table 1 means that the corresponding monomer is not used (the same applies to the following tables).

[Table 1] [A] Polymer Monomers that provide structural units (I) Monomers that provide structural unit (II) Monomers that provide structural unit (III) Mw Mw/Mn type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) Synthesis Example 1 A-1 M-1 40 41.3 M-13 45 44.9 - - - 8800 1.50 M-2 15 13.8 Synthesis Example 2 A-2 M-1 30 31.4 M-6 60 60.6 - - - 9000 1.44 M-2 10 8.0 Synthesis Example 3 A-3 M-1 30 31.9 M-5 60 61.7 - - - 8900 1.39 M-3 10 6.4 Synthesis Example 4 A-4 M-1 35 32.3 M-12 45 49.6 - - - 8000 1.56 M-3 20 18.1 Synthesis Example 5 A-5 M-1 40 41.1 M-10 45 45.7 - - - 8700 1.44 M-4 15 13.2 Synthesis Example 6 A-6 M-1 40 41.6 M-11 45 46.1 - - - 7700 1.51 M-4 15 12.3 Synthesis Example 7 A-7 M-1 40 42.4 M-10 45 39.5 M-14 15 18.1 7800 1.59 Synthesis Example 8 A-8 M-1 40 41.1 M-7 40 35.7 M-15 20 23.2 8500 1.61 Synthesis Example 9 A-9 M-1 50 51.0 M-8 50 49.0 - - - 7800 1.55 Synthesis Example 10 A-10 M-1 40 44.4 M-9 60 55.6 - - - 7900 1.59 Synthesis Example 11 A-11 M-1 40 42.8 M-6 60 57.2 - - - 8000 1.43

[Synthesis Example 12] (Synthesis of Resin (A-12)) Monomer (M-1) and Monomer (M-18) were dissolved in a molar ratio of 50/50 (mol %). To 1-methoxy-2-propanol (200 parts by mass), AIBN (5 mol %) as a starting agent was added to prepare a single-body solution. 1-Methoxy-2-propanol (100 parts by mass) was placed in the reaction vessel, and after 30 minutes of nitrogen flushing, the inside of the reaction vessel was set to 80°C, and the monomer was added dropwise over 3 hours while stirring. solution. The start of dropwise addition was set as the start time of the polymerization reaction, and the polymerization reaction was carried out for 6 hours. After the completion of the polymerization reaction, the polymerization solution was cooled to 30°C or lower by water-cooling. The cooled polymerization solution was put into hexane (2,000 parts by mass), and the precipitated white powder was separated by filtration. After the white powder separated by filtration was washed twice with hexane, it was separated by filtration and dissolved in 1-methoxy-2-propanol (300 parts by mass). Next, methanol (500 parts by mass), triethylamine (50 parts by mass), and ultrapure water (10 parts by mass) were added, and a hydrolysis reaction was performed at 70° C. for 6 hours while stirring. After the completion of the reaction, the residual solvent was distilled off, the obtained solid was dissolved in acetone (100 parts by mass), and added dropwise to water (500 parts by mass) to solidify the resin. The obtained solid was separated by filtration, and dried at 50° C. for 13 hours to obtain a white powdery resin (A-12) (yield: 79%). Resin (A-12) had Mw of 5,200 and Mw/Mn of 1.60. In addition, as a result of ¹³ C-NMR analysis, the content ratios of the respective structural units derived from (M-1) and (M-18) were 51.3 mol % and 48.7 mol %, respectively.

[Synthesis Example 13 to Synthesis Example 15] (Synthesis of resin (A-13) to resin (A-15)) Resin (A-13) to resin (A-15) were synthesized in the same manner as in Synthesis Example 12, except that the monomers of the types and compounding ratios shown in the following Table 2 were used. The content ratio (mol %), yield (%), and physical property values (Mw and Mw/Mn) of each structural unit of the obtained resin are collectively shown in Table 2 below.

[Table 2] [A] Polymer Monomers that provide structural units (I) Monomers that provide structural unit (II) Monomers that provide structural unit (III) Mw Mw/Mn type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) Synthesis Example 12 A-12 M-1 50 51.3 - - - M-18 50 48.7 5200 1.60 Synthesis Example 13 A-13 M-3 50 46.6 M-14 10 11.1 M-19 40 42.3 5600 1.55 Synthesis Example 14 A-14 M-2 50 48.1 M-17 20 21.3 M-18 30 30.6 5100 1.59 Synthesis Example 15 A-15 M-1 55 55.7 M-17 15 15.1 M-19 30 29.2 6100 1.50

[Synthesis Example 16] (Synthesis of High Fluorine Content Resin (E-1)) Monomer (M-1) and Monomer (M-20) were prepared in a molar ratio of 20/80 (mol %). It was dissolved in 2-butanone (200 parts by mass), and AIBN (4 mol %) was added as a starting agent to prepare a single-body solution. 2-Butanone (100 parts by mass) was placed in the reaction vessel, and after 30 minutes of nitrogen flushing, the inside of the reaction vessel was set to 80° C., and the monomer solution was added dropwise over 3 hours while stirring. The start of dropwise addition was set as the start time of the polymerization reaction, and the polymerization reaction was carried out for 6 hours. After the completion of the polymerization reaction, the polymerization solution was cooled to 30°C or lower by water-cooling. After replacing the solvent with acetonitrile (400 parts by mass), hexane (100 parts by mass) was added and stirred, and the acetonitrile layer was recovered, and the operation was repeated three times. By replacing the solvent with propylene glycol monomethyl ether acetate, a solution (yield: 69%) of the high fluorine content resin (E-1) was obtained. The high fluorine content resin (E-1) had Mw of 6,000 and Mw/Mn of 1.62. In addition, as a result of ¹³ C-NMR analysis, the content ratios of the respective structural units derived from (M-1) and (M-20) were 19.9 mol % and 80.1 mol %, respectively.

[Synthesis Example 17 to Synthesis Example 20] (Synthesis of high fluorine content resin (E-2) to high fluorine content resin (E-5)) The high fluorine content resin (E-2) to the high fluorine content resin (E-5) were synthesized in the same manner as in Synthesis Example 16, except that the monomers of the types and compounding ratios shown in the following Table 3 were used. The content ratio (mol %), yield (%), and physical property values (Mw and Mw/Mn) of each structural unit of the obtained high-fluorine-content resin are collectively shown in Table 3 below.

[table 3] [E] Polymer Monomers that provide building blocks (F) Monomers that provide structural units (I) Monomers that provide structural unit (II) Monomers that provide other building blocks Mw Mw/Mn type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) Synthesis Example 16 E-1 M-20 80 80.1 M-1 20 19.9 - - - - - - 6000 1.62 Synthesis Example 17 E-2 M-21 80 81.9 M-1 20 18.1 - - - - - - 7200 1.77 Synthesis Example 18 E-3 M-22 60 62.3 - - - - - - M-16 40 38.7 6300 1.82 Synthesis Example 19 E-4 M-22 70 68.7 - - - M-14 30 31.3 - - - 6500 1.81 Synthesis Example 20 E-5 M-20 60 59.2 M-2 10 10.3 M-17 30 30.5 - - - 6100 1.86

<[B] Synthesis of radioactive acid generator> [Synthesis Example 21] <Synthesis of Compound (B-1)> Compound (B-1) was synthesized according to the following synthesis scheme.

[Chemical 19]

To the reaction vessel were added 20.0 mmol of iodine, 40.0 mmol of tert-amylbenzene, 40.0 mmol of m-chloroperoxybenzoic acid, 40.0 mmol of p-toluenesulfonic acid monohydrate and 100 g of chloroform, and the mixture was stirred at room temperature for 24 hours. After dilution with water, dichloromethane was added for extraction, and the organic layer was separated. The obtained organic layer was washed with a saturated aqueous sodium chloride solution. After drying with sodium sulfate, the solvent was distilled off, and the salt represented by the formula (B-1-a) was obtained in good yield by recrystallization and purification with diethyl ether.

To the salt represented by the formula (B-1-a), 20.0 mmol of the sulfonic acid sodium salt compound was added, and a mixed solution of water:dichloromethane (1:1 (mass ratio)) was added to prepare 0.5 M solution. After vigorous stirring at room temperature for 3 hours, dichloromethane was added for extraction, and the organic layer was separated. After drying the obtained organic layer with sodium sulfate, the solvent was distilled off and purified by column chromatography, whereby the salt represented by the formula (B-1-b) was obtained in good yield. .

To the salt represented by the formula (B-1-a) were added 20.0 mmol of 1,4-thioxane, 2.00 mmol of copper(II) acetate, and 50 g of chloroform, followed by stirring at room temperature for 24 hours. After removing impurities by filtration through celite, the solvent was distilled off, and the compound (B-1) represented by the formula (B-1) was obtained in a good yield by purification by column chromatography.

[Synthesis Example 22 to Synthesis Example 41] (Synthesis of Compound (B-2) to Compound (B-21)) The radiation-sensitive acid generators represented by the following formulae (B-2) to (B-21) were synthesized in the same manner as in Synthesis Example 21, except that the raw materials and precursors were appropriately changed.

[hua 20]

[Radiation-sensitive acid generators other than compounds (B-1) to (B-16)] b-1 to b-19: compounds represented by the following formulae (b-1) to (b-19) (hereinafter, the compounds represented by formulas (b-1) to (b-19) may be referred to as They are respectively described as "compound (b-1)" to "compound (b-19)").

[Chemical 21]

[[C] Acid Diffusion Control Agent] C-1 to C-5: compounds represented by the following formulae (C-1) to (C-5).

[Chemical 22]

[[D]solvent] D-1: Propylene glycol monomethyl ether acetate D-2: Propylene Glycol Monomethyl Ether D-3: γ-Butyrolactone D-4: Ethyl lactate

[Preparation of Negative Radiation Sensitive Resin Composition for ArF Exposure] [Example 1] 100 parts by mass of (A-1) as [A] resin, 12.0 parts by mass of (B-1) as [B] radiation-sensitive acid generator, and (C-1) as [C] acid diffusion control agent were mixed 6.0 parts by mass, (E-1) 3.0 parts by mass (solid content) as [E] high fluorine content resin, and (D-1)/(D-2)/(D-3) as [D] solvent 3,230 parts by mass of the mixed solvent was filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive resin composition (J-1).

[Example 2 to Example 46 and Comparative Example 1 to Comparative Example 19] A radiation-sensitive resin composition (J-2) to a radiation-sensitive resin composition (J-46) and a radiation-sensitive resin composition (J-46) and a radiation-sensitive resin composition (J-46) and a radiation-sensitive resin composition were prepared in the same manner as in Example 1, except that each component of the type and content shown in the following Table 4 was used. Radiation resin composition (CJ-1) to radiation sensitive resin composition (CJ-19).

[Table 4] Radiation sensitive resin composition [A] Polymer [B] Acid generator [C] Acid diffusion control agent [E] Polymer [D] Organic solvent type Content (mass parts) type Content (mass parts) type Content (mass parts) type Content (mass parts) type Content (mass parts) Example 1 J-1 A-1 100 B-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 2 J-2 A-1 100 B-2 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 3 J-3 A-1 100 B-3 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 4 J-4 A-1 100 B-4 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 5 J-5 A-1 100 B-5 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 6 J-6 A-1 100 B-6 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 7 J-7 A-1 100 B-7 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 8 J-8 A-1 100 B-8 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 9 J-9 A-1 100 B-9 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 10 J-10 A-1 100 B-10 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 11 J-11 A-1 100 B-11 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 12 J-12 A-1 100 B-12 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 13 J-13 A-1 100 B-13 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 14 J-14 A-1 100 B-14 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 15 J-15 A-1 100 B-15 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 16 J-16 A-1 100 B-16 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 17 J-17 A-1 100 B-17 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 18 J-18 A-1 100 B-18 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 19 J-19 A-1 100 B-19 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 20 J-20 A-1 100 B-20 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 21 J-21 A-1 100 B-21 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 22 J-22 A-2 100 B-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 23 J-23 A-3 100 B-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 24 J-24 A-4 100 B-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 25 J-25 A-5 100 B-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 26 J-26 A-6 100 B-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 27 J-27 A-7 100 B-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 28 J-28 A-8 100 B-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 29 J-29 A-9 100 B-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 30 J-30 A-10 100 B-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 31 J-31 A-11 100 B-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 32 J-32 A-1 100 B-1 12.0 C-2 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 33 J-33 A-1 100 B-1 12.0 C-3 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 34 J-34 A-1 100 B-1 12.0 C-4 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 35 J-35 A-1 100 B-1 12.0 C-5 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 36 J-36 A-1 100 B-1 12.0 C-1 6.0 E-2 3.0 D-1/D-2/D-3 2240/960/30 Example 37 J-37 A-1 100 B-1 12.0 C-1 6.0 E-3 3.0 D-1/D-2/D-3 2240/960/30 Example 38 J-38 A-1 100 B-1 12.0 C-1 6.0 E-4 3.0 D-1/D-2/D-3 2240/960/30 Example 39 J-39 A-1 100 B-1 2.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 40 J-40 A-1 100 B-1 7.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 41 J-41 A-1 100 B-1 20.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 42 J-42 A-1 100 B-1 12.0 C-1/C-4 3.0/3.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 43 J-43 A-1 100 B-1 12.0 C-4/C-5 3.0/3.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 44 J-44 A-1 100 B-1/b-1 8.0/4.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 45 J-45 A-1 100 B-1/b-2 8.0/4.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 46 J-46 A-1 100 B-1/b-3 8.0/4.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 1 CJ-1 A-1 100 b-1 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 2 CJ-2 A-1 100 b-2 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 3 CJ-3 A-1 100 b-3 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 4 CJ-4 A-1 100 b-4 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 5 CJ-5 A-1 100 b-5 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 6 CJ-6 A-1 100 b-6 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 7 CJ-7 A-1 100 b-7 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 8 CJ-8 A-1 100 b-8 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 9 CJ-9 A-1 100 b-9 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 10 CJ-10 A-1 100 b-10 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 11 CJ-11 A-1 100 b-11 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 12 CJ-12 A-1 100 b-12 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 13 CJ-13 A-1 100 b-13 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 14 CJ-14 A-1 100 b-14 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 15 CJ-15 A-1 100 b-15 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 16 CJ-16 A-1 100 b-16 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 17 CJ-17 A-1 100 b-17 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 18 CJ-18 A-1 100 b-18 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 19 CJ-19 A-1 100 b-19 12.0 C-1 6.0 E-1 3.0 D-1/D-2/D-3 2240/960/30

<Formation of a resist pattern using a negative radiation-sensitive resin composition for ArF exposure> Using a spin coater (“CLEAN TRACK ACT12” from Tokyo Electron Co., Ltd.), a composition for forming a lower layer antireflection film (“ARC66” from Brewer Science Co., Ltd.) was applied on 12 After being deposited on a silicon wafer of 1 inch, it was heated at 205° C. for 60 seconds to form a lower anti-reflection film with an average thickness of 100 nm. Use the spin coater to coat the prepared negative radiation-sensitive resin composition (J-63) for ArF exposure on the lower anti-reflection film, and pre-bake at 100°C for 60 seconds (PB). Then, it cooled at 23 degreeC for 30 second, and formed the resist film with an average thickness of 90 nm.

Next, an ArF excimer laser liquid immersion exposure device (“TWINSCAN XT-1900i” from ASML) was used, under the optical conditions of NA=1.35, Annular (σ=0.8/0.6), with a hole of 40 nm apart, The resist film was exposed to a mask pattern of 105 nm pitch. After exposure, a post-exposure bake (PEB) was performed at 100°C for 60 seconds. Thereafter, the resist film was developed with an organic solvent using n-butyl acetate as an organic solvent developer, and dried to form a negative-type resist pattern (40 nm hole, 105 nm pitch).

＜Evaluation＞ With respect to the resist pattern formed using the negative radiation-sensitive resin composition for ArF exposure, sensitivity, CDU performance, pattern squareness, and etching resistance were evaluated according to the following methods. The results are shown in Table 5 below. In addition, for the length measurement of the resist pattern, a scanning electron microscope (“CG-5000” of Hitachi High-Technologies Co., Ltd.) was used.

[Sensitivity] In the formation of the resist pattern using the negative radiation-sensitive resin composition for ArF exposure, the exposure amount for forming a 40 nm hole pattern was set as the optimum exposure amount, and the optimum exposure amount was set as the optimum exposure amount. is the sensitivity (mJ/cm ² ). Regarding the sensitivity, the case of 30 mJ/cm ² or less was evaluated as "good", and the case of more than 30 mJ/cm ² was evaluated as "poor".

[CDU performance] Using the scanning electron microscope, a total of 1,800 resist patterns with holes of 40 nm and a pitch of 105 nm were measured at arbitrary points from the top of the pattern. Variation in size (3σ) was obtained and set as CDU performance (nm). The smaller the value of CDU, the smaller the deviation of the pore diameter in the long period, and the better. Regarding CDU performance, the case of 2.5 nm or less was evaluated as "good", and the case of more than 2.5 nm was evaluated as "poor".

[Depth of Focus] The size of the resist pattern analyzed in the optimum exposure amount obtained in the evaluation of the sensitivity was observed when the focal point was changed in the depth direction, and the size of the pattern was measured when there was no bridge or residue. The depth direction margin (margin) of 90% to 110% of the reference, and the measured value is referred to as the depth of focus (nm). The larger the value, the better the depth of focus. Regarding the depth of focus, the case of 50 nm or more can be evaluated as "good", and the case of less than 50 nm can be evaluated as "poor".

[pattern rectangularity] The 40 nm hole space of the resist pattern formed by irradiating the optimum exposure amount determined in the evaluation of the sensitivity was observed using the scanning electron microscope, and the cross-sectional shape of the hole pattern was evaluated. Regarding the rectangularity of the resist pattern, when the ratio of the length of the lower side to the length of the upper side in the cross-sectional shape was 1 or more and 1.05 or less, it was evaluated as "A" (extremely good), and when it exceeded 1.05 and 1.10 or less, it was evaluated as "A" (very good). B" (good), and if it exceeded 1.10, it was evaluated as "C" (bad).

[Etching Resistance] The prepared resist composition was applied on a silicon wafer substrate by a spin coating method. Next, heating was performed at 100° C. for 60 seconds in an atmospheric environment to form a resist film having an average thickness of 100 nm to obtain a substrate with a resist film in which a resist film was formed on the substrate. The resist film in the obtained resist film-attached substrate was subjected to O ₂ =100 sccm, PRESS using an etching apparatus (“TACTRAS” from Tokyo Electron Co., Ltd.). .=100 mT, HF RF=200 W, LF RF=0 W, DCS=0 V, and the etching rate (nm/min) was calculated from the time required for the disappearance of the resist film to obtain The ratio with respect to the etching rate of the comparative example 1 was made into the standard of etching resistance. Regarding the etching resistance, when the ratio was 0.90 or more and 0.95 or less, it was evaluated as "A" (very good), when it exceeded 0.95 and 1.00 or less, it was evaluated as "B" (good), and when it exceeded 1.00, it was evaluated as "B" (good) "C" (defective). In addition, "-" in Table 5 shows that the comparative example 1 is the reference|standard of the evaluation of etching resistance.

[Number of development defects] The resist film was exposed with the optimum exposure amount to form a hole pattern of 40 nm, and it was used as a wafer for defect inspection. The number of defects on the wafer for defect inspection was measured using a defect inspection apparatus (“KLA2810” from KLA-Tencor Corporation). Then, the measured defects were classified into defects judged to be derived from the resist film and foreign matter originating from the outside, and the number of defects judged to be derived from the resist film was calculated. The number of defects after development was evaluated as "good" when the number of defects judged to be derived from the resist film was 50 or less, and "defective" when it exceeded 50.

[table 5] Radiation sensitive resin composition Sensitivity (mJ/cm ² ) CDU (nm) Depth of focus (nm) pattern rectangle Etch resistance Number of developing defects (pieces) Example 1 J-1 25 1.8 80 A A 30 Example 2 J-2 20 1.9 100 A A 35 Example 3 J-3 26 2.3 70 A A 34 Example 4 J-4 twenty one 2.0 110 A A 46 Example 5 J-5 twenty four 2.2 80 A A 29 Example 6 J-6 twenty three 1.7 90 A A 32 Example 7 J-7 26 2.4 70 A A 30 Example 8 J-8 25 2.1 70 A A 43 Example 9 J-9 twenty three 1.8 100 A A 40 Example 10 J-10 20 2.3 100 A A 29 Example 11 J-11 twenty four 2.0 90 A A twenty two Example 12 J-12 twenty three 2.1 70 A A 45 Example 13 J-13 28 1.7 110 A A 34 Example 14 J-14 twenty three 1.9 100 A A 33 Example 15 J-15 27 2.1 70 A A 27 Example 16 J-16 27 2.3 80 A A 39 Example 17 J-17 25 2.2 90 A A 20 Example 18 J-18 26 2.3 90 A A 29 Example 19 J-19 twenty two 1.8 100 A A 13 Example 20 J-20 25 2.1 90 A A 34 Example 21 J-21 27 2.3 80 A A twenty two Example 22 J-22 twenty four 1.9 80 A A 35 Example 23 J-23 twenty three 2.0 80 A A 32 Example 24 J-24 25 2.0 90 A A 28 Example 25 J-25 25 2.1 70 A A 29 Example 26 J-26 26 1.8 90 A A 39 Example 27 J-27 twenty four 1.7 80 A A 26 Example 28 J-28 25 2.0 90 A A 31 Example 29 J-29 twenty four 2.1 80 A A 30 Example 30 J-30 twenty three 2.0 80 A A 26 Example 31 J-31 twenty three 1.8 70 A A 32 Example 32 J-32 27 1.8 70 A A 33 Example 33 J-33 28 1.9 70 A A 31 Example 34 J-34 twenty four 2.0 80 A A 40 Example 35 J-35 25 1.9 70 A A 32 Example 36 J-36 25 1.8 80 A A 35 Example 37 J-37 25 1.8 80 A A 43 Example 38 J-38 26 1.9 80 A A 25 Example 39 J-39 28 2.3 70 A A 40 Example 40 J-40 26 2.0 70 A A 34 Example 41 J-41 twenty two 2.2 80 A A 38 Example 42 J-42 25 1.9 80 A A 33 Example 43 J-43 26 2.1 90 A A 30 Example 44 J-44 twenty three 2.3 90 A A 43 Example 45 J-45 25 2.2 70 A A 44 Example 46 J-46 twenty four 2.4 70 A A 39 Comparative Example 1 CJ-1 35 3.1 40 B - 72 Comparative Example 2 CJ-2 33 3.3 30 C C 110 Comparative Example 3 CJ-3 32 3.4 40 C C 131 Comparative Example 4 CJ-4 40 3.0 40 C B 148 Comparative Example 5 CJ-5 35 2.7 30 B C 152 Comparative Example 6 CJ-6 36 2.8 30 C C 124 Comparative Example 7 CJ-7 33 2.9 40 C C 111 Comparative Example 8 CJ-8 32 3.0 30 C C 138 Comparative Example 9 CJ-9 33 2.6 30 B C 67 Comparative Example 10 CJ-10 31 2.8 40 C C 89 Comparative Example 11 CJ-11 35 2.6 30 C C 92 Comparative Example 12 CJ-12 32 2.9 20 B C 123 Comparative Example 13 CJ-13 33 2.7 40 C C 78 Comparative Example 14 CJ-14 34 2.8 30 B C 67 Comparative Example 15 CJ-15 34 2.7 30 C B 77 Comparative Example 16 CJ-16 33 2.7 40 C C 161 Comparative Example 17 CJ-17 35 3.0 30 C B 88 Comparative Example 18 CJ-18 36 2.7 40 C C 69 Comparative Example 19 CJ-19 34 2.9 30 C C 157

As is clear from the results in Table 5, when the radiation-sensitive resin compositions of the examples were used for ArF exposure, the sensitivity, CDU performance, depth of focus, pattern squareness, etching resistance and development defect performance were good, relatively Here, in the comparative example, each characteristic is inferior to that of the example. Therefore, when the radiation-sensitive resin composition of the Example is used for ArF exposure, a resist pattern with good CDU performance and cross-sectional shape can be formed with high sensitivity.

[Preparation of radiation-sensitive resin composition for extreme ultraviolet (EUV) exposure] [Example 47] 100 parts by mass of (A-12) as [A] resin, 17.0 parts by mass of (B-1) as [B] radiation-sensitive acid generator, and (C-2) as [C] acid diffusion control agent were mixed 10.0 parts by mass, 3.0 parts by mass (solid content) of (E-5) as [E] high fluorine content resin, and 6,110 parts by mass of a mixed solvent of (D-1)/(D-4) as [D] solvent , and filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive resin composition (J-47).

[Example 48 to Example 59 and Comparative Example 20 to Comparative Example 27] A radiation-sensitive resin composition (J-48) to a radiation-sensitive resin composition (J-59) and a radiation-sensitive resin composition (J-59) and a radiation-sensitive resin composition (J-59) were prepared in the same manner as in Example 42, except that each component of the type and content shown in the following Table 6 was used. Radiation resin composition (CJ-20) to radiation sensitive resin composition (CJ-27).

[Table 6] Radiation sensitive resin composition [A] Polymer [B] Acid generator [C] Acid diffusion control agent [E] Polymer [D] Organic solvent type Content (mass parts) type Content (mass parts) type Content (mass parts) type Content (mass parts) type Content (mass parts) Example 47 J-47 A-12 100 B-1 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 48 J-48 A-12 100 B-2 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 49 J-49 A-12 100 B-4 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 50 J-50 A-12 100 B-9 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 51 J-51 A-12 100 B-10 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 52 J-52 A-12 100 B-11 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 53 J-53 A-12 100 B-12 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 54 J-54 A-12 100 B-13 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 55 J-55 A-12 100 B-14 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 56 J-56 A-13 100 B-1 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 57 J-57 A-14 100 B-1 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 58 J-58 A-15 100 B-1 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Example 59 J-59 A-12 100 B-1 17.0 C-4 10.0 E-5 3.0 D-1/D-4 4280/1830 Comparative Example 20 CJ-20 A-12 100 b-4 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Comparative Example 21 CJ-21 A-12 100 b-5 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Comparative Example 22 CJ-22 A-12 100 b-6 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Comparative Example 23 CJ-23 A-12 100 b-9 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Comparative Example 24 CJ-24 A-12 100 b-12 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Comparative Example 25 CJ-25 A-12 100 b-14 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Comparative Example 26 CJ-26 A-12 100 b-15 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830 Comparative Example 27 CJ-27 A-12 100 b-18 17.0 C-2 10.0 E-5 3.0 D-1/D-4 4280/1830

<Formation of resist pattern using radiation-sensitive resin composition for EUV exposure> Using a spin coater (“CLEAN TRACK ACT12” from Tokyo Electron Co., Ltd.), a composition for forming a lower layer antireflection film (“ARC66” from Brewer Science Co., Ltd.) was applied on 12 After being deposited on a silicon wafer of 1.5 inches, it was heated at 205°C for 60 seconds to form a lower anti-reflection film with an average thickness of 105 nm. The prepared radiation-sensitive resin composition for EUV exposure was coated on the lower antireflection film using the spin coater, and PB was performed at 130° C. for 60 seconds. Then, it cooled at 23 degreeC for 30 second, and formed the resist film with an average thickness of 55 nm.

Next, using an EUV exposure apparatus (“NXE3300” from ASML), the resist film was exposed to NA=0.33, illumination condition: Conventional s=0.89, mask: imecDEFECT32FFR02 . After exposure, PEB was performed at 120°C for 60 seconds. Then, using 2.38 mass % TMAH aqueous solution as an alkaline developer, the resist film was subjected to alkaline development, washed with water after development, and further dried to form a positive-type resist pattern ( 32 nm line and space pattern).

＜Evaluation＞ With respect to the resist pattern formed using the radiation-sensitive resin composition for EUV exposure, sensitivity, LWR performance, pattern squareness, and etching resistance were evaluated according to the following methods. The results are shown in Table 7 below. In addition, for the length measurement of the resist pattern, a scanning electron microscope (“CG-5000” of Hitachi High-Technologies Co., Ltd.) was used.

[Sensitivity] In the formation of the resist pattern using the radiation-sensitive resin composition for EUV exposure, the exposure amount for forming a 32 nm line and space pattern was set as the optimum exposure amount, and the optimum exposure amount was set as the optimum exposure amount. Let it be the sensitivity (mJ/cm ² ). Regarding the sensitivity, the case of 30 mJ/cm ² or less was evaluated as "good", and the case of more than 30 mJ/cm ² was evaluated as "poor".

[LWR performance] The optimum exposure amount determined in the evaluation of the sensitivity was irradiated, and the mask size was adjusted so as to form a 32 nm line-and-space pattern to form a resist pattern. Using the scanning electron microscope, the formed resist pattern was observed from the upper part of the pattern. A total of 500 line width deviations were measured, and a 3-sigma value was obtained from the distribution of the measured values, and the 3-sigma value was defined as LWR (nm). The smaller the value of LWR is, the smaller the deviation of the line is and the better. Regarding the LWR performance, the case of 3.0 nm or less was evaluated as "good", and the case of more than 3.0 nm was evaluated as "poor".

[pattern rectangularity] The 32 nm line-and-space resist pattern formed by irradiating the optimum exposure amount obtained in the evaluation of the sensitivity was observed using the scanning electron microscope, and the cross-sectional shape of the line-and-space pattern was evaluated. . Regarding the rectangularity of the resist pattern, when the ratio of the length of the lower side to the length of the upper side in the cross-sectional shape was 1 or more and 1.05 or less, it was evaluated as "A" (extremely good), and when it exceeded 1.05 and 1.10 or less, it was evaluated as "A" (very good). B" (good), and if it exceeded 1.10, it was evaluated as "C" (bad).

[Etching Resistance] The prepared resist composition was applied on a silicon wafer substrate by a spin coating method. Next, heating was performed at 100° C. for 60 seconds in an atmospheric environment to form a resist film having an average thickness of 100 nm to obtain a substrate with a resist film in which a resist film was formed on the substrate. The resist film in the obtained substrate with a resist film was subjected to O ₂ =100 sccm, PRESS using an etching apparatus (“TACTRAS” from Tokyo Electron Co., Ltd.). .=100 mT, HF RF=200 W, LF RF=0 W, DCS=0 V, and the etching rate (nm/min) was calculated from the time required for the disappearance of the resist film to obtain The ratio with respect to the etching rate of the comparative example 20 was made into the standard of etching resistance. Regarding the etching resistance, when the ratio was 0.90 or more and 0.95 or less, it was evaluated as "A" (very good), when it exceeded 0.95 and 1.00 or less, it was evaluated as "B" (good), and when it exceeded 1.00, it was evaluated as "B" (good) "C" (defective). In addition, "-" in Table 7 shows that the comparative example 20 is the reference|standard of the evaluation of etching resistance.

[Table 7] Radiation sensitive resin composition Sensitivity (mJ/cm ² ) LWR (nm) pattern rectangle Etch resistance Example 47 J-47 28 2.7 A A Example 48 J-48 twenty three 2.5 A A Example 49 J-49 twenty four 2.6 A A Example 50 J-50 27 2.6 A A Example 51 J-51 25 2.8 A A Example 52 J-52 27 2.5 A A Example 53 J-53 26 2.7 A A Example 54 J-54 27 2.5 A A Example 55 J-55 28 2.5 A A Example 56 J-56 27 2.6 A A Example 57 J-57 28 2.7 A A Example 58 J-58 28 2.6 A A Example 59 J-59 twenty three 2.7 A A Comparative Example 20 CJ-20 33 3.4 B - Comparative Example 21 CJ-21 34 3.2 C C Comparative Example 22 CJ-22 32 3.3 C C Comparative Example 23 CJ-23 37 3.5 C C Comparative Example 24 CJ-24 33 3.4 B C Comparative Example 25 CJ-25 32 3.4 C B Comparative Example 26 CJ-26 35 3.8 C B Comparative Example 27 CJ-27 36 3.3 C C

As is clear from the results in Table 7, when the radiation-sensitive resin compositions of Examples are used for EUV exposure, the sensitivity, LWR performance, pattern squareness, and etching resistance are good. Each characteristic is inferior to the Example.

[Preparation of positive radiation-sensitive resin composition for ArF exposure, formation and evaluation of resist pattern using the composition] [Example 60] 100 parts by mass of (A-5) as [A] resin, 11.0 parts by mass of (B-2) as [B] radiation-sensitive acid generator, and (C-3) as [C] acid diffusion control agent were mixed 3.0 parts by mass, (E-2) 3.0 parts by mass (solid content) as [E] high fluorine content resin, and (D-1)/(D-2)/(D-3) as [D] solvent 3,230 parts by mass of the mixed solvent was filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive resin composition (J-60).

Using a spin coater (“CLEAN TRACK ACT12” from Tokyo Electron Co., Ltd.), a composition for forming a lower layer antireflection film (“ARC66” from Brewer Science Co., Ltd.) was applied on 12 After being deposited on a silicon wafer of 1 inch, it was heated at 205° C. for 60 seconds to form a lower anti-reflection film with an average thickness of 100 nm. Use the spin coater to coat the prepared positive-type radiation-sensitive resin composition (J-60) for ArF exposure on the lower anti-reflection film, and pre-bake at 100° C. for 60 seconds (PB). Then, it cooled at 23 degreeC for 30 second, and formed the resist film with an average thickness of 90 nm.

Next, an ArF excimer laser liquid immersion exposure device (“TWINSCAN XT-1900i” from ASML) was used, under the optical conditions of NA=1.35, Annular (σ=0.8/0.6), with a hole of 40 nm apart, The resist film was exposed to a mask pattern of 105 nm pitch. After exposure, a post-exposure bake (PEB) was performed at 100°C for 60 seconds. Then, using 2.38 mass % TMAH aqueous solution as an alkaline developer, the resist film was subjected to alkaline development, washed with water after development, and further dried to form a positive-type resist pattern ( 32 nm line and space pattern).

The resist pattern using the positive radiation-sensitive resin composition for ArF exposure was evaluated in the same manner as the evaluation of the resist pattern using the positive radiation-sensitive resin composition for EUV exposure. As a result, the radiation-sensitive resin composition of Example 60 was excellent in sensitivity, LWR performance, pattern squareness, and etching resistance even when a positive-type resist pattern was formed by ArF exposure.

[Preparation of negative radiation-sensitive resin composition for EUV exposure, formation and evaluation of resist pattern using the composition] [Example 61] 100 parts by mass of (A-15) as [A] resin, 15.0 parts by mass of (B-4) as [B] radiation-sensitive acid generator, and (C-2) as [C] acid diffusion control agent were mixed 10.0 parts by mass, 3.0 parts by mass (solid content) of (E-5) as [E] high fluorine content resin, and 6,110 parts by mass of a mixed solvent of (D-1)/(D-4) as [D] solvent , and filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive resin composition (J-61).

Using a spin coater (“CLEAN TRACK ACT12” from Tokyo Electron Co., Ltd.), a composition for forming a lower layer antireflection film (“ARC66” from Brewer Science Co., Ltd.) was applied on 12 After being deposited on a silicon wafer of 1.5 inches, it was heated at 205°C for 60 seconds to form a lower anti-reflection film with an average thickness of 105 nm. The prepared radiation-sensitive resin composition for EUV exposure (J-61) was coated on the lower antireflection film using the spin coater, and PB was performed at 130° C. for 60 seconds. Then, it cooled at 23 degreeC for 30 second, and formed the resist film with an average thickness of 55 nm.

Next, using an EUV exposure apparatus (“NXE3300” from ASML), the resist film was exposed to NA=0.33, illumination condition: Conventional s=0.89, mask: imecDEFECT32FFR02 . After exposure, PEB was performed at 120°C for 60 seconds. Thereafter, the resist film was developed with an organic solvent using n-butyl acetate as an organic solvent developer, and dried to form a negative-type resist pattern (40 nm hole, 105 nm pitch).

The resist pattern using the negative radiation-sensitive resin composition for EUV exposure was evaluated in the same manner as the evaluation of the resist pattern using the negative radiation-sensitive resin composition for ArF exposure. As a result, the radiation-sensitive resin composition of Example 61 was excellent in sensitivity, CDU performance, depth of focus, and pattern squareness even when a negative resist pattern was formed by EUV exposure. [Industrial Availability]

According to the radiation-sensitive resin composition and the method for forming a resist pattern described above, a resist pattern having good sensitivity to exposure light and excellent LWR performance and CDU performance can be formed. Therefore, these can be preferably used in the processing and the like of semiconductor devices which are expected to be further miniaturized in the future.

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Claims (14)

A radiation-sensitive resin composition comprising: a periconium salt compound represented by the following formula (1); a resin including a structural unit having an acid dissociable group; and a solvent;

(in the formula, R ¹ is a monovalent hydrocarbon group having a cyclic structure, and the methylene group constituting the hydrocarbon group may be substituted with an ether bond, R ^f1 and R ^f2 are independently a fluorine atom or a monovalent fluorinated hydrocarbon group, m ₁ is an integer of 1 to 4, and when m ₁ is 2 to 4, some or all of the plurality of R ^f1 and R ^f2 are the same or different, and R ² and R ³ are each independently a hydrogen atom, a fluorine atom, a monovalent Hydrocarbon group or monovalent fluorinated hydrocarbon group, m ₂ is an integer of 0 to 3, when m ₂ is 2 to 3, a part or all of a plurality of R ² and R ³ are the same or different, X is a single bond or contains two A linking group of a valent heteroatom, R ⁴ to R ⁷ are each independently a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group, or an ester group, n ₁ and n ₂ are each independently an integer of 1 to 3, and a plurality of R ⁴ to R A part or all of ⁷ are the same or different, R ⁸ is a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent fluorinated hydrocarbon group, a halogen atom, a monovalent aromatic hydrocarbon group, or a monovalent represented by -YR ^8' base, (Y represents -O-, -CO-, -COO-, -OCO-, R ^8' is a monovalent hydrocarbon group with 1 to 20 carbon atoms) l is an integer of 0 to 5, where l is 2 to 5 case, some or all of the plurality of R ⁸ are the same or different). The radiation-sensitive resin composition according to claim 1, wherein R ¹ is a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3 to 40 carbon atoms. The radiation-sensitive resin composition according to claim 1 or claim 2, wherein at least one of R ⁸ is present at the para position with respect to the bonding position of S ⁺ in the formula. The radiation-sensitive resin composition according to claim 1 or claim 2, wherein the divalent heteroatom is an oxygen atom or a sulfur atom. The radiation-sensitive resin composition according to claim 1 or claim 2, wherein the total number of n ₁ and n ₂ is 4 or 5. The radiation-sensitive resin composition according to claim 1 or claim 2, wherein the resin further comprises at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure. a structural unit. The radiation-sensitive resin composition according to claim 1 or claim 2, wherein the structural unit having an acid dissociable group in the resin is represented by the following formula (2),

(in the formula, R ⁹ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R ¹⁰ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. A valent chain hydrocarbon group or a monovalent alicyclic hydrocarbon group with 3 to 20 carbon atoms, or a bivalent alicyclic hydrocarbon group with 3 to 20 carbon atoms in which R ¹¹ and R ¹² are bonded to each other and together with these bonded carbon atoms base). The radiation-sensitive resin composition according to claim 1 or claim 2, further comprising a photodegradable base. The radiation-sensitive resin composition according to claim 1 or claim 2, which is used for organic solvent development. A method for forming a resist pattern, comprising: The step of directly or indirectly coating the radiation-sensitive resin composition according to any one of claim 1 to claim 9 on a substrate to form a resist film; the step of exposing the resist film; and A developing step of developing the exposed resist film. The method for forming a resist pattern according to claim 10, wherein in the developing step, a negative pattern is formed by developing with an organic solvent. A perylium salt compound represented by the following formula (1),

(in the formula, R ¹ is a monovalent hydrocarbon group having a cyclic structure, and the methylene group constituting the hydrocarbon group may be substituted with an ether bond, R ^f1 and R ^f2 are independently a fluorine atom or a monovalent fluorinated hydrocarbon group, m ₁ is an integer of 1 to 4, and when m ₁ is 2 to 4, some or all of the plurality of R ^f1 and R ^f2 are the same or different, and R ² and R ³ are each independently a hydrogen atom, a fluorine atom, a monovalent Hydrocarbon group or monovalent fluorinated hydrocarbon group, m ₂ is an integer of 0 to 3, when m ₂ is 2 to 3, a part or all of a plurality of R ² and R ³ are the same or different, X is a single bond or contains two A linking group of a valent heteroatom, R ⁴ to R ⁷ are each independently a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group, or an ester group, n ₁ and n ₂ are each independently an integer of 1 to 3, and a plurality of R ⁴ to R A part or all of ⁷ are the same or different, R ⁸ is a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent fluorinated hydrocarbon group, a halogen atom, a monovalent aromatic hydrocarbon group, or a monovalent represented by -YR ^8' base, (Y represents -O-, -CO-, -COO-, -OCO-, R ^8' is a monovalent hydrocarbon group with 1 to 20 carbon atoms) l is an integer of 0 to 5, where l is 2 to 5 case, some or all of the plurality of R ⁸ are the same or different). A radiation-sensitive acid generator comprising a periconium salt compound represented by the following formula (1),

(in the formula, R ¹ is a monovalent hydrocarbon group having a cyclic structure, and the methylene group constituting the hydrocarbon group may be substituted with an ether bond, R ^f1 and R ^f2 are independently a fluorine atom or a monovalent fluorinated hydrocarbon group, m ₁ is an integer of 1 to 4, and when m ₁ is 2 to 4, some or all of the plurality of R ^f1 and R ^f2 are the same or different, and R ² and R ³ are each independently a hydrogen atom, a fluorine atom, a monovalent Hydrocarbon group or monovalent fluorinated hydrocarbon group, m ₂ is an integer of 0 to 3, when m ₂ is 2 to 3, a part or all of a plurality of R ² and R ³ are the same or different, X is a single bond or contains two A linking group of a valent heteroatom, R ⁴ to R ⁷ are each independently a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group, or an ester group, n ₁ and n ₂ are each independently an integer of 1 to 3, and a plurality of R ⁴ to R A part or all of ⁷ are the same or different, R ⁸ is a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent fluorinated hydrocarbon group, a halogen atom, a monovalent aromatic hydrocarbon group, or a monovalent represented by -YR ^8' base, (Y represents -O-, -CO-, -COO-, -OCO-, R ^8' is a monovalent hydrocarbon group with 1 to 20 carbon atoms) l is an integer of 0 to 5, where l is 2 to 5 case, some or all of the plurality of R ⁸ are the same or different). The radiation-sensitive acid generator according to claim 13, which is used for organic solvent development.