KR20170070198A - Radiation-sensitive or actinic-light-sensitive composition; and film, mask blank, resist pattern formation method, and electronic device manufacturing method using same - Google Patents

Abstract

A radiation-sensitive or light-sensitive radiation-sensitive composition containing a compound represented by the general formula (I) described in the specification and having a molecular weight of 450 to 2000 and an acid generator which generates an acid upon irradiation with an actinic ray or radiation, A mask blank, a resist pattern forming method, and a manufacturing method of an electronic device.

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation-sensitive or actinic ray-sensitive composition, a film using the same, a mask blank, a method of forming a resist pattern, and a method of manufacturing an electronic device. AND FILM, MASK BLANK, RESIST PATTERN FORMATION METHOD, AND ELECTRONIC DEVICE MANUFACTURING METHOD USING SAME}

The present invention relates to a super-microlithography process applicable to a manufacturing process such as the manufacture of a large scale integrated circuit (large-scale integrated circuit) or a high-capacity microchip, a process for producing a mold for a nanoimprint and a process for manufacturing a high- Sensitive radiation sensitive composition which can be suitably used for other photofabrication processes and which can form a pattern with high definition by using electron beam EB or extreme ultraviolet (EUV) A mask blank, a resist pattern forming method, and a method of manufacturing an electronic device.

2. Description of the Related Art Conventionally, in a manufacturing process of a semiconductor device such as an IC (Integrated Circuit) or an LSI, fine processing by lithography using a photoresist composition is performed. In recent years, with the increase in integration of integrated circuits, ultrafine pattern formation in a submicron region or a quarter micron region has been required. As a result, the exposure wavelength tends to be shorter in the wavelength range from g-line to i-line, and further to excimer laser light, and lithography using electron beams or X-rays is under development at present.

Particularly, electron beam or extreme ultraviolet lithography has been established as a next-generation or next-generation pattern formation technology, and since it is high-resolution, it is widely used for manufacturing a photomask used for semiconductor exposure. For example, in the step of fabricating the photomask by electron beam lithography, a resist layer is formed on a shielding substrate provided with a shielding layer mainly composed of chromium or the like on a transparent substrate, selectively subjected to electron beam exposure, Thereby forming a resist pattern. Next, a photomask having a shielding layer having a predetermined pattern on the transparent substrate can be obtained by etching the shielding layer using this resist pattern as a mask and forming a pattern on the shielding layer.

However, since the electron beam can not perform batch exposure such as ultraviolet ray, a resist having high sensitivity is required for shortening the processing time. As a resist suitable for electron beam lithography, a so-called positive type resist A so-called negative resist composition in which a crosslinking polymer compound and a crosslinking agent are combined is effectively used.

For example, Patent Document 1 discloses a negative resist composition having an alicyclic alcohol as a crosslinking agent.

Patent Document 1: JP-A-2010-198024

However, the negative resist composition described in Patent Document 1 has a problem of sensitivity, resolution, pattern shape, line edge roughness performance, PEB (Post Exposure Bake) time dependency, PED stability (PEB) (Dry etching resistance) and in-plane uniformity (CDU) of the line width at a very high level, there was room for improvement.

That is, an object of the present invention is to provide a method of forming a pattern having excellent sensitivity, resolution, pattern shape, line edge roughness performance, PEB time dependency, PED stability, dry etching resistance, A mask blank, a method of forming a resist pattern, a method of manufacturing an electronic device, and an electronic device using the same. .

That is, the present invention is as follows.

<1>

A compound represented by the general formula (I) and having a molecular weight of 450 or more and 2000 or less,

A radiation-sensitive or light-sensitive radiation-sensitive composition containing an acid generator which generates an acid upon irradiation with an actinic ray or radiation.

[Chemical Formula 1]

Wherein,

X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an acyl group.

A represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or an alicyclic group.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Provided that not all R ₁ and all R ₂ are hydrogen atoms at the same time.

m and n each independently represent an integer of 1 or more.

When at least one of m and n represents an integer of 2 or more, a plurality of R ₁ , a plurality of R _2, and a plurality of X may be the same or different.

When m represents an integer of 2 or more, a plurality of A may be the same or different.

Y represents an m-valent group having a hetero atom.

At least one of A and R ₁ and R ₂ may be bonded to form a ring.

R ₁ and R ₂ may bond together to form a ring together with the carbon atom to which they are bonded.

&Lt; 2 &

And Y is an m-valent group having a heteroatom and a cyclic structure.

&Lt; 3 &

The radiation sensitive or sensitive radiation ray composition according to < 1 > or < 2 > further comprising a polymer compound having a structural unit represented by formula (II).

(2)

Wherein,

R ₄ represents a hydrogen atom, an organic group, or a halogen atom.

D ₁ represents a single bond or a divalent linking group.

Ar ₂ represents aromatic ring.

m ₁ represents an integer of 1 or more.

&Lt; 4 &

The radiation-sensitive or light-sensitive radiation-sensitive composition according to any one of <1> to <3>, wherein the acid generator is a sulfonium salt.

&Lt; 5 &

The radiation-sensitive or light-sensitive radiation-sensitive composition according to any one of <1> to <4>, further comprising a basic compound or an ammonium salt compound, the basicity of which is lowered by irradiation with an actinic ray or radiation.

&Lt; 6 &

The radiation-sensitive or light-sensitive radiation-sensitive composition according to any one of <1> to <5>, which is a chemical amplification negative resist composition for electron beam or extreme ultraviolet exposure.

&Lt; 7 &

A radiation-sensitive or actinic ray-forming film formed using the radiation-sensitive or light-sensitive radiation-sensitive composition according to any one of <1> to <6>.

&Lt; 8 &

The mask blank as set forth in <7>, wherein the mask blank has the radiation-sensitive or actinic ray-forming film.

&Lt; 9 &

A process for producing a film by applying the radiation sensitive or light sensitive radiation ray composition described in any one of < 1 > to < 6 >

A step of exposing the film, and

And developing the exposed film to form a negative resist pattern.

&Lt; 10 &

A step of exposing the mask blank having the radiation sensitive or light sensitive actinic radiation film described in < 7 >, and

And developing the exposed mask blank.

&Lt; 11 &

The method for forming a resist pattern according to any one of <1> to <10>, wherein the exposure is performed using an electron beam or an extreme ultraviolet ray.

&Lt; 12 &

The method of manufacturing an electronic device according to < 9 >

According to the present invention, it is possible to improve the sensitivity, resolution, pattern shape, line edge roughness performance, PEB time dependency, PED stability, dry etching resistance, and linewidth in the pattern formation of a very fine (for example, a line width of 50 nm or less) A mask blank, a method of forming a resist pattern, a method of manufacturing an electronic device, and an electronic device can be provided by using a radiation-sensitive or actinic ray-sensitive composition having a very high level of radiation uniformity (CDU) have.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

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

In the present invention, "actinic ray" or "radiation" means, for example, a line spectrum of a mercury lamp, far ultraviolet ray represented by an excimer laser, extreme ultraviolet ray (EUV light), X ray or electron ray. In the present invention, "light" means an actinic ray or radiation. The term "exposure" in this specification refers to not only exposure by deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also imaging by particle beams such as electron beams and ion beams, .

In the present specification, the weight average molecular weight of the polymer compound is the polystyrene reduced value measured by the GPC method. Gel Permeation Chromatography (GPC) was carried out by using TSK Gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID x 30.0 cm) as a column using HLC-8120 (manufactured by TOSOH CORPORATION) The method using N-methyl-2-pyrrolidone (NMP) as the eluent can be used.

The molecular weight of the non-polymeric compound is calculated by calculating the molecular weight of the non-polymeric compound. The term " non-polymeric "indicates a polymeric compound different from a polymeric compound having a repeating unit formed by polymerizing a monomer.

The radiation-sensitive or light-sensitive radiation-sensitive composition (also referred to as a composition) of the present invention is a compound having a specific structure and having a molecular weight of 450 or more and 2000 or less (also referred to as a compound (A)), Containing acid generator.

The compound (A) in the present invention is a compound having a specific structure (-CR ₁ R ₂ OX) having a group capable of reacting with a polar group, that is, a carbon atom to which OX is bonded is a secondary or tertiary carbon It is believed that the photoreactive or sensitive active ray-sensitive composition having high reaction efficiency and high image contrast and high sensitivity and high resolution can be obtained.

Since the compound (A) has a larger molecular weight than a general crosslinking agent, it is possible to suppress the volatilization and the diffusion of the reactive group unit in the resist film, and the stability of the PED (Post Exposure Time Delay) It is possible to further improve the stability of the post-coating delay (PCD) of the film, and it is possible to prevent the fluctuation of the sensitivity and the variation of the pattern size.

Further, since the compound (A) has a heteroatom, the interaction with the polymer in the film is high, uniform distribution and curing proceeds, and it is considered that the pattern roughness is excellent and a high-resolution pattern can be formed . Here, the PED stability is considered to be the stability of the coating film when it is left to stand until the heating operation (PEB) is carried out after the irradiation of the radiation.

The radiation-sensitive or light-sensitive radiation sensitive composition of the present invention is typically a resist composition, and is preferably a negative resist composition. Further, the radiation-sensitive or actinic ray-sensitive composition of the present invention is preferably a chemically amplified resist composition, more preferably a chemically amplified negative resist composition.

The radiation-sensitive or light-sensitive radiation-sensitive composition of the present invention is preferably for electron beam or extreme ultraviolet ray exposure, and more preferably for electron beam.

Hereinafter, each component of the radiation-sensitive or light-sensitive radiation sensitive composition of the present invention will be described in detail.

[Compound (A)] represented by the general formula (I) and having a molecular weight of 450 or more and 2000 or less]

(3)

Wherein,

X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an acyl group.

A represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or an alicyclic group.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Provided that not all R ₁ and all R ₂ are hydrogen atoms at the same time.

m and n each independently represent an integer of 1 or more.

When at least one of m and n represents an integer of 2 or more, a plurality of R ₁ , a plurality of R _2, and a plurality of X may be the same or different.

When m represents an integer of 2 or more, a plurality of A may be the same or different.

Y represents an m-valent group having a hetero atom.

At least one of A and R ₁ and R ₂ may be bonded to form a ring.

R ₁ and R ₂ may bond together to form a ring together with the carbon atom to which they are bonded.

When A represents an aromatic hydrocarbon group, it is preferable that n + 1 hydrogen atoms are removed from monocyclic or polycyclic aromatic hydrocarbons (n represents an integer of 1 or more).

Examples of the aromatic hydrocarbon include aromatic hydrocarbons such as benzene, naphthalene, anthracene, fluorene and phenanthrene (preferably having 6 to 18 carbon atoms), benzene and naphthalene are preferred from the viewpoint of resolution, desirable.

When A represents an alicyclic group, the alicyclic group may be monocyclic or polycyclic. Specifically, a group obtained by removing n + 1 hydrogen atoms from a monocyclic or polycyclic alicyclic ring (preferably having 3 to 18 carbon atoms) , And more preferably a group corresponding to a monocyclic or polycyclic monovalent heterocyclic group (a group obtained by removing n hydrogen atoms from a monovalent heterocyclic group).

Examples of monocyclic heterocyclic groups include cyclopropyl group, cyclobutyl group, cycloheptyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, cyclononyl group, cyclodenyl group, cyclododynyl group, cyclododecanyl group, cyclohexene group, A group corresponding to a cycloalkyl group such as a cyclohexadienyl group, a cyclohexadienyl group, a cyclopentenyl group, or a cyclopentadienyl group, and a group corresponding to a cyclohexyl group or a cyclopentyl group is preferable.

Examples of the polycyclic ring include groups having a bicyclo, tricyclo, tetracyclo structure, etc., and examples thereof include a bicyclobutyl group, a bicyclooctyl group, a bicyclooctyl group, a bicyclooctyl group, A cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentadecyl group, a cyclopentadecyl group, a cyclopentadecyl group, a cyclopentadecyl group, a cyclopentadecyl group, a cyclopentadecyl group, And the like. More preferably a group corresponding to an adamantyl group, a decalin group, a norbornyl group, a sidolyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group or a tricyclodecanyl group , The group corresponding to the adamantyl group is most preferable in view of the dry etching resistance.

Further, a part of the carbon atoms in the monocyclic or polycyclic ring may be substituted by a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, and specific examples thereof include a thiophene ring, a furan ring, a pyrrole ring, .

When A represents an aromatic heterocyclic group, an aromatic heterocyclic group containing an oxygen atom, a nitrogen atom, or a sulfur atom is preferable. Further, an aromatic heterocyclic group having 3 to 18 carbon atoms is preferable, and specific examples thereof include pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, A pyridazin ring, an indolizin ring, an indole ring, a benzofuran ring, a benzothiophen ring, an isobenzofuran ring, a quinolin ring, a quinoline ring, a phthalazin ring, a naphthyridine ring, a quinoxaline ring, A group having a heterocyclic structure such as a quinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a cromene ring, a zentylene ring, a phenoxathiine ring, a phenothiazine ring, However, the present invention is not limited thereto.

At least one of A and R ₁ and R ₂ may be bonded to form a ring.

The aromatic hydrocarbon group, aromatic heterocyclic group or alicyclic group of A may have a substituent and examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkyl A carbonyloxy group, an alkylsulfonyloxy group, and an arylcarbonyl group.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ₁ and R ₂ may bond together to form a ring together with the carbon atom to which they are bonded.

R ₁ and R ₂ each independently represent an alkyl group or a cycloalkyl group, more preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, Is more preferable.

R ₁ and R ₂ each may have a substituent and examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, And an arylcarbonyl group.

Examples of R ₁ and R _{2 in the} case of having a substituent include a benzyl group and a cyclohexylmethyl group.

All R ₁ and all R ₂ are not simultaneously hydrogen atoms. When all R ₁ and all R ₂ are not hydrogen atoms at the same time, the reaction efficiency increases and the sensitivity improves.

X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an acyl group. X is preferably a hydrogen atom, an alkyl group or an acyl group, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acyl group having 2 to 5 carbon atoms.

Examples of the m-valent group containing a hetero atom of Y include -S-, -O-, -CO-, -SO ₂ -, -N (R ₀ ) -, -SO ₂ - Or an m-valent group obtained by combining these groups and a hydrocarbon group, or an m-valent heterocyclic group. R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl or octyl). Examples of the hydrocarbon group include an alkylene group (e.g., methylene, ethylene, propylene, butylene, hexylene, and octylene), a cycloalkylene Etc.), an alkenylene group (e.g., an ethylene group, a propenylene group, and a butenylene group), an arylene group (e.g., a phenylene group, a tolylene group and a naphthylene group).

As the m-valent group containing a hetero atom of Y, an m-valent group having a hetero atom and a ring structure is more preferable from the viewpoints of interaction with the polymer and resolution and etching resistance, and -O-, -CO-, -SO ₂ - and an m-valent group having a t-aryl group in which a plurality of these groups are combined is most preferable.

m and n each independently represent an integer of 1 or more. m is preferably an integer of 1 to 3, and m is most preferably 2 from the viewpoints of reaction efficiency and solubility in a developing solution. n is preferably an integer of 1 to 3, more preferably an integer of 1 to 2.

The preferable range of the molecular weight of the compound represented by the general formula (I) and having a molecular weight of 450 to 2000 is that the volatilization and the diffusion of the reactive group unit in the resist film can be suppressed and the PED (Post Exposure Time Delay) From the viewpoint of stability and stability of post-coating delay (PCD: Post Coating Delay) stability, and from the viewpoint of preventing fluctuation in sensitivity and variation in pattern size, a range of 500 or more and 1500 or less, 550 or more and 1000 or less.

The compound represented by the general formula (I) and having a molecular weight of not less than 450 but not more than 2000 is a non-polymeric compound, and is preferably a compound having a constant molecular weight within a range of from 450 to 2,000 (a compound having no substantial molecular weight distribution) .

As the compound represented by the general formula (I) and having a molecular weight of 450 or more and 2000 or less, a compound represented by the following general formula (I-1) is preferable from the viewpoints of resolution and etching resistance.

[Chemical Formula 4]

In the general formula (I-1)

X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an acyl group.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Provided that not all R ₁ and all R ₂ are hydrogen atoms at the same time.

Ly represents a divalent group formed by combining -S-, -O-, -CO-, -SO ₂ -, -N (R ₀ ) -, -SO ₂ -, an alkylene group, and a plurality of these.

m and n each independently represent an integer of 1 or more.

When at least one of m and n represents an integer of 2 or more, a plurality of R ₁ , a plurality of R _2, and a plurality of X may be the same or different.

When m represents an integer of 2 or more, the plurality of Lys may be the same or different.

R ₁ and R ₂ may bond together to form a ring together with the carbon atom to which they are bonded.

By represents an m-valent group having one kind of structure selected from the following six structures.

[Chemical Formula 5]

Specific examples and preferable ranges of X, R ₁ , R ₂ , R ₀ , m and n in the general formula (I-1) are X, R ₁ and R ₂ , R &lt; ₀ &gt;, m, n.

Ly represents a divalent group formed by combining -S-, -O-, -CO-, -SO ₂ -, -N (R ₀ ) -, -SO ₂ -, an alkylene group, and a plurality of these. The alkylene group is preferably an alkylene group having 1 to 5 carbon atoms.

The content of the compound (A) is preferably 5 to 70 mass%, more preferably 10 to 60 mass%, and still more preferably 15 to 50 mass%, based on the total solid content of the composition.

The compound (A) can be prepared, for example, by reacting 2,2 '- (5- (4'-fluorophenyl) (Hydroxy) -1,3-phenylene) dipropan-2-ol (ol).

Specific examples of the compound (A) are shown below, but the present invention is not limited thereto. Me represents a methyl group, and Ac represents an acetyl group.

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

&Lt; Acid generator generating an acid by irradiation of an actinic ray or radiation >

The composition of the present invention contains, in addition to the compound (A), an acid generator (also referred to as a photoacid generator) which generates an acid upon irradiation with an actinic ray or radiation.

The content of the acid generator is preferably from 0.1 to 40 mass%, more preferably from 0.5 to 30 mass%, and still more preferably from 1 to 20 mass%, based on the total solid content of the composition.

A preferable example of the acid generator is an onium salt compound. As such onium salt compounds, for example, sulfonium salts, iodonium salts, and phosphonium salts can be mentioned, and sulfonium salts are preferred.

Another preferred form of the acid generator is a compound which generates sulfonic acid, imidic acid or metaic acid by irradiation with an actinic ray or radiation. Examples of the acid generator in the form include a sulfonium salt, an iodonium salt, a phosphonium salt, an oxime sulfonate, an imide sulfonate, and the like.

The composition of the present invention may contain only one acid generator or two or more acid generators.

As the acid generator which can be used in the present invention, not only a low molecular compound but also a compound in which a group capable of generating an acid upon irradiation with an actinic ray or radiation is introduced into the main chain or side chain of the polymer compound can be used.

When the acid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

In the present invention, the acid generator is preferably in the form of a low-molecular compound.

When the composition of the present invention contains two or more acid generators, the total content of the acid generators is preferably within the above range.

The acid generator is preferably a compound which generates an acid by irradiation with an electron beam or an extreme ultraviolet ray.

In the present invention, the preferable onium salt compounds include a sulfonium compound represented by the following general formula (7) or an iodonium compound represented by the general formula (8).

(11)

In the general formulas (7) and (8)

R _a1 , R _a2 , R _a3 , R _a4 and R _a5 each independently represent an organic group.

X ^- represents an organic anion.

Hereinafter, the sulfonium compound represented by formula (7) and the iodonium compound represented by formula (8) will be described in more detail.

R _a1 , R _a2 and R _a3 in the general formula (7) and R _a4 and R _a5 in the general formula (8) each independently represent an organic group, and preferably R _a1 , R _a2 and R _a3 , and at least one of R &lt; _a4 &gt; and R &lt; _a5 &gt; are each an aryl group. The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

Examples of the organic anion of X ^- in formulas (7) and (8) include sulfonic acid anion, carboxylic acid anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) And is preferably an organic anion represented by the following general formula (9), (10) or (11), more preferably an organic anion represented by the following general formula (9).

[Chemical Formula 12]

In the formula (9), (10) and _{(11), Rc 1, Rc} 2, Rc 3 and Rc ₄ are, each independently, it represents an organic group.

The organic anion of X &lt; ^- &gt; corresponds to sulfonic acid, imidic acid, metaic acid, etc., which are generated by actinic rays such as electron beams or extreme ultraviolet rays or radiation.

Examples of the organic group of Rc ₁ , Rc ₂ , Rc ₃ and Rc ₄ include an alkyl group, an aryl group or a group in which a plurality of these groups are connected. Of these organic groups, the phenyl group is more preferably an alkyl group substituted by a fluorine atom or a fluoroalkyl group, or a phenyl group substituted by a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity generated by the light irradiation is increased, and the sensitivity is improved. However, it is preferable that the terminal group does not contain a fluorine atom as a substituent.

In the present invention, from the viewpoint of suppressing the diffusion of the exposed acid into the non-exposed portion and improving the resolution and pattern shape in the present invention, an acid generator having a volume of 130 Å ³ or more (more preferably, preferably a compound capable of generating an acid), and the volume of 190Å, and more preferably a compound capable of generating the ^three or more sizes acid (preferably an acid than a), preferably a sulfonic acid than the volume 270Å of ^three or more sizes acid ( ), And it is particularly preferable to be a compound which generates an acid (more preferably, a sulfonic acid) having a size of 400 Å ³ or more in volume. However, in view of the sensitivity and the solubility in coating solvent, the volume is more preferably not more than preferably ³ 2000Å and 1500Å ³ or less. The value of the volume was obtained using "WinMOPAC" manufactured by Fujitsu Kabushiki Kaisha. That is, first, the chemical structure of the acid for each compound is input, and then the structure is used as an initial structure to determine the most stable stereoisomer of each acid by calculation of the molecular force field using the MM3 method, The "accessible volume" of each acid can be calculated by performing molecular orbital calculation using the PM3 method for the stable three-dimensional fundus. 1 Å (Angstrom) is 10 ^-10 m.

In the present invention, particularly preferred acid generators are shown below. In some of the examples, the calculated value of the volume is added (unit A ³ ). The calculated value obtained here is the volume value of the acid to which the proton is bonded to the anion portion.

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

Examples of the acid generator (preferably an onium compound) used in the present invention include a polymeric acid generator system in which a group (photoacid generator) generating an acid by irradiation of an actinic ray or radiation is introduced into a main chain or side chain of a polymer compound Can be used.

Hereinafter, the polymeric acid generator will be described.

In the present invention, when a polymeric acid generator in which a photoacid generator is introduced into a main chain or side chain of a polymer compound is used, the repeating unit of the acid generator is preferably a repeating unit which generates an acid upon irradiation with an actinic ray or radiation Is not particularly limited, and conventionally known repeating units can be used. The repeating unit is preferably a repeating unit having an ionic structural moiety that generates an acid upon irradiation with an actinic ray or radiation on the side chain of the polymer compound. The ionic structural moiety is preferably an ionic moiety, (So-called onium salt) is preferable. As the form of the repeating unit having such an ionic structure moiety in the side chain of the polymer compound, the moiety introduced into the side chain of the polymer compound through the covalent bond is either one of an acid anion and an onium cation, It is divided into the following three according to the recognition.

(1) The polymer compound has only a repeating unit (a1) having an ionic structural moiety that generates an acid anion at the side chain by irradiation with an actinic ray or radiation as a repeating unit (that is, An embodiment introduced into the side chain of the compound)

(2) The polymer compound has only a repeating unit (a2) having an ionic structural moiety that generates an onium cation on the side chain by irradiation with an actinic ray or radiation as a repeating unit (that is, An embodiment introduced into the side chain of the compound)

(3) The polymer compound has both of the repeating units (a1) and (a2) as repeating units (that is, each of the acid anion and onium cations is introduced into the side chain of the polymer compound through a covalent bond)

The polymeric acid generator is preferably a polymeric acid generator having repeating units (a1) having an ionic structural moiety that generates acid anions at the side chains by irradiation with an actinic ray or radiation (that is, the repeating units (1) or (3) ) Is preferable in that a good resolving power can be obtained. When the polymeric acid generator has the repeating unit (a1), it is considered that the acid generated is extremely low in diffusion and the resolution (particularly, resolution) is greatly improved.

The acid anion is preferably a sulfonic acid anion, a sulfonimidic acid anion, or a sulfonic acid anionic acid, and the sulfonic acid anion is highly hydrophilic and is most preferable from the viewpoint of development defects.

The onium cation is preferably a sulfonium cation, an iodonium cation or a pyridinium cation, more preferably a sulfonium cation or an iodonium cation, and most preferably a sulfonium cation.

The repeating unit (a1) is preferably a repeating unit represented by the following formula (XXI).

In general formula (XXI)

[Chemical Formula 17]

R ¹⁰ represents a hydrogen atom, an alkyl group or a halogen atom.

A ₁ represents a divalent linking group.

D represents a sulfonic acid anion, a sulfonimide acid anion or a sulfonimide acid anion.

M represents an onium cation.

As the polymeric acid generator, the compounds described in JP-A-2009-93137 and JP-A-2006-178317 can be used.

[Compound having a phenolic hydroxyl group]

The radiation-sensitive or actinic ray-sensitive composition of the present invention preferably contains a compound having a phenolic hydroxyl group (hereinafter also referred to as a compound (D)) in one embodiment. The compound (D) is not particularly limited as long as it contains a phenolic hydroxyl group, and may be a relatively low molecular compound such as a molecular resist, or a polymer compound. As the molecular resists, for example, low molecular weight cyclic polyphenol compounds described in JP-A-2009-173623 and JP-A-2009-173625 can be used.

In the present invention, the phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic ring with a hydroxy group. The aromatic ring of the aromatic ring is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

The polymeric acid generator described above may be a polymer compound as a compound having a phenolic hydroxyl group.

In the case where the composition of the present invention contains the compound (D), the compound (D) containing the phenolic hydroxyl group and the compound (D) containing the phenolic hydroxyl group are reacted with each other by the action of an acid generated from the acid generator by irradiation of an actinic ray or radiation, The cross-linking reaction proceeds between the above-mentioned compound (A) to form a negative pattern.

When the compound (D) containing a phenolic hydroxyl group is a polymer compound, the polymer compound preferably contains a repeating unit having at least one phenolic hydroxyl group. The repeating unit having a phenolic hydroxyl group is not particularly limited, but preferably has a structural unit represented by the following general formula (II).

[Chemical Formula 18]

Wherein,

R ₄ represents a hydrogen atom, an organic group or a halogen atom.

D ₁ represents a single bond or a divalent linking group.

Ar ₂ represents aromatic ring.

m ₁ represents an integer of 1 or more.

When R ₄ in the general formula (II) represents an organic group, as the organic group, an alkyl group, a cycloalkyl group and an aryl group are preferable, and a straight chain or branched alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, More preferably a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group or a norbornyl group), an aryl group having 6 to 10 carbon atoms (e.g., phenyl or naphthyl) Do.

The organic group may further have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom), a carboxyl group, a hydroxyl group, an amino group and a cyano group, but are not limited thereto. As the substituent, a fluorine atom and a hydroxyl group are particularly preferable.

Examples of the organic group having a substituent include a trifluoromethyl group and a hydroxymethyl group.

R ₄ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

When D ₁ represents a divalent linking group, a divalent linking group is preferably a carbonyl group, an alkylene group, an arylene group, a sulfonyl group, -O-, -NH-, or a combination thereof (for example, an ester bond) Do.

D ₁ is preferably a single bond or a carbonyloxy group, more preferably a single bond.

The aromatic ring represented by Ar ₂ is preferably a group obtained by removing n + 1 hydrogen atoms from a monocyclic or polycyclic aromatic ring (n represents an integer of 1 or more).

Examples of the aromatic ring include an aromatic hydrocarbon ring (preferably having 6 to 18 carbon atoms) which may have a substituent such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring and a phenanthrene ring, Include heterocyclic rings such as furan ring, pyrrole ring, benzothiophen ring, benzofuran ring, benzopyrrole ring, triazin ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring and thiazole ring Aromatic heterocyclic ring. Among them, a benzene ring and a naphthalene ring are preferred from the viewpoint of resolution, and a benzene ring is most preferable.

m ₁ is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.

When m ₁ represents 1 and Ar ₂ represents a benzene ring, the substitution position of -OH may be para, meta or ortho relative to the bonding position of the benzene ring with the polymer main chain, Paragraphs are preferred from a gender perspective.

The aromatic ring in the aromatic ring of Ar ₂ may have a substituent other than the group represented by -OH. Examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, , An alkylcarbonyloxy group, an alkylsulfonyloxy group, and an arylcarbonyl group.

The general formula (II) is preferably the following general formula (II-1).

[Chemical Formula 19]

Wherein,

R ₄ represents a hydrogen atom, an organic group or a halogen atom.

D ₁ represents a single bond or a divalent linking group.

General formula (II-1) R ₄ and D ₁ is R ₄ and D ₁ and agree in general formula (II) in, are also the same preferable range.

It is more preferable that the formula (II) is represented by the following formula (II-2).

[Chemical Formula 20]

In the formula, R ₄ represents a hydrogen atom, an organic group or a halogen atom.

R ₄ in the general formula (II-2) is synonymous with R ₄ in the general formula (II), a preferred range is also the same.

Specific examples of the repeating unit represented by formula (II) are shown below, but the present invention is not limited thereto. Me represents a methyl group.

[Chemical Formula 21]

When the compound (D) is a polymer compound, it may be composed only of a repeating unit having a phenolic hydroxyl group as described above. The compound (D) may have a repeating unit as described below in addition to the repeating unit having a phenolic hydroxyl group as described above. In this case, the content of the repeating unit having a phenolic hydroxyl group is preferably 10 to 98 mol%, more preferably 30 to 97 mol%, and more preferably 40 to 95 mol%, based on the total repeating units of the compound (D) % Is more preferable. Thus, in particular, when the resist film is a thin film (for example, when the thickness of the resist film is 10 to 150 nm), the dissolution rate of the exposed portion of the resist film of the present invention formed using the compound (D) (That is, the dissolution rate of the resist film using the compound (D) can be more reliably controlled to be optimum). As a result, the sensitivity can be more reliably improved.

The compound (D) is a group having a non-acid decomposable polycyclic alicyclic hydrocarbon structure and has a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted. From the viewpoint that a high glass transition temperature (Tg) is obtained and dry etching resistance becomes good desirable.

When the compound (D) has the above-described specific structure, the glass transition temperature (Tg) of the compound (D) becomes high and a very hard resist film can be formed and the acid diffusibility and dry etching resistance can be controlled . Therefore, the diffusibility of the acid in the exposed portion of the actinic ray or radiation such as an electron beam or an extreme ultraviolet ray is very suppressed, so that the resolution, pattern shape and LER performance in a fine pattern are superior. It is considered that the compound (D) having a non-acid decomposable polycyclic alicyclic hydrocarbon structure contributes to further improvement in dry etching resistance. Although the details are unclear, the polycyclic alicyclic hydrocarbon structure has high hydrogen radicals and is a source of hydrogen at the decomposition of the photoacid generator, thereby further improving the decomposition efficiency of the photoacid generator, increasing the acid generation efficiency And it is believed that this contributes to better sensitivity.

The above-mentioned specific structure that the compound (D) may have is connected to an aromatic ring such as a benzene ring and a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure via an oxygen atom derived from a phenolic hydroxyl group. As described above, it is presumed that the above structure not only contributes to high dry etching resistance but also can increase the glass transition temperature (Tg) of the compound (D), and a higher resolution is provided by the effect of these combinations.

In the present invention, the non-acid decomposability means a property that a decomposition reaction does not occur due to an acid generated by a photo acid generator.

More specifically, the group having a non-acid decomposable polycyclic alicyclic hydrocarbon structure is preferably a group stable to an acid and an alkali. Acid and alkaline stable groups mean groups which do not exhibit acid decomposability and alkali decomposability. Here, the acid decomposability means a property of causing a decomposition reaction by the action of an acid generated by a photoacid generator.

The alkali decomposability means a property of causing a decomposition reaction by the action of an alkali developing solution. Examples of the group exhibiting alkali decomposability include a conventionally known alkaline developer contained in a resin suitably used in a positive chemical amplification type resist composition (For example, a group having a lactone structure) which is decomposed by the action of an alkali developing agent to increase the dissolution rate into an alkali developing solution.

The group having a polycyclic alicyclic hydrocarbon structure is not particularly limited as long as it is a monovalent group having a polycyclic alicyclic hydrocarbon structure, but preferably has a total carbon number of 5 to 40, more preferably 7 to 30. The polycyclic alicyclic hydrocarbon structure may have an unsaturated bond in the ring.

The polycyclic alicyclic hydrocarbon structure in the group having a polycyclic alicyclic hydrocarbon structure means a structure having a plurality of monocyclic alicyclic hydrocarbon groups or a polycyclic alicyclic hydrocarbon structure and may be a polycyclic structure. The monocyclic alicyclic hydrocarbon group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Having a plurality of alicyclic hydrocarbon groups has a plurality of these groups. The structure having a plurality of monocyclic alicyclic hydrocarbon groups preferably has 2 to 4 monocyclic alicyclic hydrocarbon groups, and particularly preferably has 2 monocyclic alicyclic hydrocarbon groups.

Examples of the polycyclic alicyclic hydrocarbon structure include a bicyclo, tricyclo, and tetracyclo structure having 5 or more carbon atoms, and a polycyclic cyclo structure having 6 to 30 carbon atoms is preferable. Examples thereof include an adamantane structure, a decalin structure, A norbornene structure, a norbornene structure, a heptal roll structure, an isobornane structure, a Bonne structure, a dicyclopentane structure, an alpha -pinene structure, a tricyclodecane structure, a tetracyclododecane structure, . In addition, a part of carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.

Preferable examples of the polycyclic alicyclic hydrocarbon structure include an adamantane structure, a decalin structure, a norbornene structure, a norbornene structure, a heptal structure, a structure having a plurality of cyclohexyl groups, a structure having a plurality of cycloheptyl groups, A structure having a plurality of groups, a structure having a plurality of cyclodecanyl groups, a structure having a plurality of cyclododecanyl groups, and a tricyclodecane structure, and an adamantane structure is most preferable in view of dry etching resistance (that is, It is most preferable that the group having a non-acid decomposable polycyclic alicyclic hydrocarbon structure is a group having a non-acid-decomposable adamantane structure).

For a structure having a plurality of monocyclic alicyclic hydrocarbon groups, a monocyclic alicyclic hydrocarbon structure corresponding to the above-mentioned monocyclic alicyclic hydrocarbon group (specifically, the following formulas (47) to (50) ))) Is shown below.

[Chemical Formula 22]

The polycyclic alicyclic hydrocarbon structure may further have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (Preferably having 1 to 6 carbon atoms), a carboxyl group, a carbonyl group, a thiocarbonyl group, an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), and a halogen atom, (Preferably 1 to 30 carbon atoms in total, more preferably 1 to 15 carbon atoms in total).

Examples of the polycyclic alicyclic hydrocarbon structure include a structure represented by any one of the formulas (7), (23), (40), (41), and (51) A structure having two bonded monovalent groups of atoms is preferable and a structure represented by any one of the formulas (23), (40) and (51) A structure having two monovalent groups bonded by hydrogen atoms is more preferable, and the structure represented by the formula (40) is most preferable.

The group having a polycyclic alicyclic hydrocarbon structure is preferably a monovalent group formed by bonding any one hydrogen atom of the polycyclic alicyclic hydrocarbon structure.

The compound (D) may contain a repeating unit represented by the following general formula (IV) or the following general formula (V).

(23)

Wherein,

R ₆ represents a hydroxyl group, a linear, branched or cyclic alkyl group of 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, COOR: R represents an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group.

n ₃ represents an integer of 0 to 6;

&Lt; EMI ID =

Wherein,

R ₇ represents a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, COOR: R represents an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group.

and n ₄ represents an integer of 0 to 4.

X ₄ is a methylene group, an oxygen atom or a sulfur atom.

Specific examples of the repeating unit represented by the formula (IV) or the following formula (V) are shown below, but are not limited thereto.

(25)

Specific examples of the compound having a phenolic hydroxyl group in addition to the compound (D) composed of only the repeating unit having a phenolic hydroxyl group as described above are shown below, but the present invention is not limited thereto.

(26)

(27)

(28)

[Chemical Formula 29]

When the compound (D) having a phenolic hydroxyl group is a polymer compound, the weight average molecular weight is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 2,000 to 15,000. The dispersion degree (molecular weight distribution) (Mw / Mn) is preferably 2.0 or less, more preferably 1.0 to 1.60, most preferably 1.0 to 1.20.

The radiation-sensitive or light-sensitive radiation sensitive composition of the present invention may or may not contain the compound (D) having a phenolic hydroxyl group, but if contained, the content of the compound (D) Is preferably from 1 to 50% by mass, more preferably from 2 to 40% by mass, and still more preferably from 3 to 30% by mass, based on the total solid content of the active radiation-

&Lt; Basic compound or ammonium salt compound >

The radiation-sensitive or light-sensitive radiation-sensitive composition of the present invention preferably contains, in addition to the above components, a basic compound or an ammonium salt compound, and is preferably a basic compound or an ammonium salt compound Decomposable basic compound). The photodegradable basic compound means a basic compound having a basic atom and an organic acid moiety generated by irradiation with an actinic ray or radiation although a basic atom (for example, nitrogen atom) acts as a base and shows basicity And a basic compound or an ammonium salt compound in which the basicity is reduced or eliminated by neutralization in the molecule. Examples of the photo-decomposable basic compound include compounds disclosed in JP-A-3577743, JP-A-2001-215689, JP-A-2001-166476, JP-A-2008-102383, WO2014 / 109337A1 And the like. Among these basic compounds, the photodegradable basic compounds described in WO2014 / 109337A1 are preferable from the viewpoint of improving the resolution.

The basic compound may also contain an amine compound or amine oxide compound which has a carboxyl group and does not contain hydrogen which is covalently bonded to nitrogen as a basic center. As such basic compounds, compounds represented by the following general formulas (12) to (14) are preferable.

(30)

Of the general formulas (12) and (13)

R ₂₁ and R ₂₂ each independently represent an alkyl group, a cycloalkyl group or an aryl group.

R ₂₁ and R ₂₂ may be bonded to form a ring structure together with the nitrogen atom to which they are bonded.

R ₂₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a halogen atom.

R ₂₄ represents a single bond, an alkylene group, a cycloalkylene group or an arylene group.

In the general formula (14)

R ₂₅ represents an alkylene group, and one or more carbonyl group (-CO-), ether group (-O-), ester group (-COO-), and sulfide (-S-) May be included.

R ₂₆ represents an alkylene group, a cycloalkylene group or an arylene group.

R ₂₁ and R ₂₂ may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an acyloxy group and an alkylthio group.

R ₂₁ and R ₂₂ are preferably a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, , An alkoxyalkyl group having 2 to 10 carbon atoms, an acyloxyalkyl group having 2 to 10 carbon atoms, or an alkylthioalkyl group having 1 to 10 carbon atoms.

R ₂₃ may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an acyloxy group and an alkylthio group.

R ₂₃ is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, A hydroxyalkyl group, an alkoxyalkyl group having 2 to 10 carbon atoms, an acyloxyalkyl group having 2 to 10 carbon atoms, an alkylthioalkyl group having 1 to 10 carbon atoms, or a halogen atom.

R ₂₄ is preferably a single bond, a straight chain, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.

R &lt; ₂₅ &gt; is preferably an alkylene group which may have a substituent group of straight chain or branched chain having 2 to 20 carbon atoms.

R ₂₆ is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.

Specific examples of the amine compound having a carboxyl group represented by the general formula (12) and containing no hydrogen atom covalently bonded to nitrogen as a basic center are shown below, but are not limited thereto.

That is, there can be mentioned, for example, o-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid, m-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, p-dipropylaminobenzoic acid, p-dibutylaminobenzoic acid, , p-diethanolaminobenzoic acid, p-diethanolaminobenzoic acid, p-diethanolaminobenzoic acid, p-diisopropanolaminobenzoic acid, p-dimethanolaminobenzoic acid, 2- 2-naphthalenic acid, 3-dimethylamino-2-naphthalenic acid, 2-dimethylamino-5-bromobenzoic acid, 2- - chlorobenzoic acid, 2-dimethylamino-5-iodobenzoic acid, 2-dimethylamino-5-hydroxybenzoic acid, 4-dimethylaminophenylacetic acid, 4-dimethylaminophenylpropionic acid, Butyric acid, 4-dimethylaminophenylmalonic acid, 4-dimethylaminophe 2- (4-dimethylaminophenyl) benzoic acid, 2- (4- (dibutylamino) -2-hydroxybenzoyl) benzoic acid, and the like.

The amine compound having a carboxyl group represented by the general formula (13) and containing no hydrogen atom covalently bonded to the nitrogen as the basic center is obtained by oxidizing the above-exemplified amine compound, but is not limited thereto.

Specific examples of the amine compound having a carboxyl group represented by the general formula (14) and containing no hydrogen atom covalently bonded to nitrogen as a basic center are shown below, but are not limited thereto.

That is, 1-piperidine propionic acid, 1-piperidine butyric acid, 1-piperidine malic acid, 1-piperidine pyruvic acid, 1-piperidine lactic acid and the like can be given.

The radiation-sensitive or light-sensitive radiation-sensitive composition of the present invention may or may not contain a basic compound or an ammonium salt compound, but if contained, the content of the basic compound or the ammonium salt compound is not particularly limited so long as the radiation- Is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass, and particularly preferably from 0.05 to 3% by mass, based on the total solid content of the resin composition.

〔Surfactants〕

The radiation-sensitive or actinic ray-sensitive composition of the present invention may further contain a surfactant to improve the coating property. Examples of the surfactant include, but are not limited to, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters (Manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC430 (manufactured by Sumitomo 3M), Surfinol E1004 (manufactured by Asahi Glass Co., Ltd.) and PF656 and PF6320 (manufactured by OMNOVA, etc.) Fluorine-based surfactants, and organosiloxane polymers.

The radiation-sensitive or actinic ray-sensitive composition of the present invention may or may not contain a surfactant. When the surfactant is contained, the content of the surfactant is preferably such that the total amount of the composition (excluding the solvent) Is 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass.

[Organic carboxylic acid]

The radiation-sensitive or light-sensitive radiation sensitive composition of the present invention preferably contains, in addition to the above components, an organic carboxylic acid. Examples of the organic carboxylic acid include aliphatic carboxylic acids, alicyclic carboxylic acids, unsaturated aliphatic carboxylic acids, oxycarboxylic acids, alkoxycarboxylic acids, ketocarboxylic acids, benzoic acid derivatives, phthalic acid, terephthalic acid, isophthalic acid, 2- -Hydroxy-3-naphthoic acid. However, when the electron beam exposure is carried out under vacuum, there is a risk of volatilization from the surface of the resist film and contamination of the inside of the painting chamber. As preferable compounds, aromatic organic carboxylic acids, For example, benzoic acid, 1-hydroxy-2-naphthoic acid and 2-hydroxy-3-naphthoic acid are suitable.

The radiation-sensitive or actinic ray-sensitive composition of the present invention may or may not contain an organic carboxylic acid, but if contained, the compounding ratio of the organic carboxylic acid is preferably from 0.01 to 10 parts by mass per 100 parts by mass of the compound (A) More preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 3 parts by mass.

The radiation-sensitive or light-sensitive radiation-sensitive composition of the present invention may contain, if necessary, a dye, a plasticizer, an acid propagating agent (WO 95/29968, WO 98/24000, JP- -305262, JP-A-9-34106, JP-A-8-248561, JP-A-8-503082, U.S. Patent No. 5,445,917, JP-A-8-503081 U.S. Patent No. 5,534,393, U.S. Patent No. 5,395,736, U.S. Patent No. 5,741,630, U.S. Patent No. 5,334,489, U.S. Patent No. 5,582,956, U.S. Patent No. 5,578,424, U.S. Patent No. 5,453,345, US Patent No. 5,445,917, European Patent Publication No. 665,960, European Patent Publication No. 757,628, European Patent Publication No. 665,961, US Patent No. 5,667,943, Japanese Patent Application Laid-Open No. 10-1508, 10-282642, JP-A-9-512498 JP-A-2000-62337, JP-A-2005-17730, JP-A-2008-209889, etc.). As for these compounds, all of the compounds described in JP-A-2008-268935 can be mentioned.

[Carboxylic acid onium salt]

The radiation-sensitive or light-sensitive radiation sensitive composition of the present invention may contain a carboxylic acid onium salt. Examples of the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt. Particularly, as the carboxylic acid onium salt, a carboxylic acid sulfonium salt or a carboxylic acid iodonium salt is preferable. Further, in the present invention, it is preferable that the carboxylate residue of the onium carboxylate does not contain an aromatic group or a carbon-carbon double bond. As a particularly preferable anion moiety, a linear, branched, monocyclic or polycyclic cyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. More preferably, an anion of a carboxylic acid in which a part or all of these alkyl groups are fluorine-substituted is preferable. The alkyl chain may contain an oxygen atom. As a result, transparency to light of 220 nm or less is ensured, sensitivity and resolving power are improved, density dependency and exposure margin are improved.

The radiation-sensitive or actinic-ray-sensitive composition of the present invention may or may not contain a carboxylic acid onium salt, but if contained, the content of the onium salt of the carboxylic acid is not more than the total solid content of the radiation- , Preferably 0.5 to 20 mass%, more preferably 0.7 to 15 mass%, and still more preferably 1.0 to 10 mass%.

〔solvent〕

The radiation-sensitive or light-sensitive radiation-sensitive composition of the present invention preferably contains a solvent.

Examples of the solvent that can be used in preparing the radiation-sensitive or actinic-ray-sensitive composition include alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, lactic acid alkyl esters, alkyl alkoxypropionates, Organic solvents such as cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonates, alkyl alkoxyacetates and alkyl pyruvic acids.

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

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

As the solvent containing a hydroxyl group and the solvent containing no hydroxyl group, the above-mentioned exemplified compounds can be appropriately selected. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, alkyl butyrate and the like are preferable, Propylene glycol monomethyl ether (PGME, alias 1-methoxy-2-propanol), ethyl lactate, and methyl 2-hydroxyisobutyrate are more preferable. As the solvent containing no hydroxyl group, an alkylene glycol monoalkyl ether acetate, an alkyl alkoxy propionate, a monoketone compound which may contain a ring, a cyclic lactone, and an alkyl acetate are preferable. Of these, propylene glycol Particularly preferred is colmonomethylether acetate (PGMEA, 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone,? -Butyrolactone, cyclohexanone and butyl acetate And propylene glycol monomethyl ether acetate, ethyl ethoxypropionate and 2-heptanone are most preferable.

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

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

The solid concentration of the radiation-sensitive or light-sensitive radiation sensitive composition of the present invention is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and still more preferably 3 to 20% by mass.

<Sensitizing Radiation or Sensitive Actinic Ray Film>

The present invention also relates to a radiation-sensitive or actinic radiation-sensitive film (preferably a resist film) formed by the radiation-sensitive or light-sensitive radiation-sensitive composition of the present invention, On a support such as a substrate. The thickness of this film is preferably 0.02 to 0.1 mu m. As a method of coating on a substrate, it is coated on a substrate by a suitable coating method such as spin coating, roll coating, float coating, dip coating, spray coating, doctor coat, etc., but spin coating is preferable, 3000 rpm is preferable. The coated film is prebaked at 60 to 150 DEG C for 1 to 20 minutes, preferably at 80 to 120 DEG C for 1 to 10 minutes to form a thin film.

The material constituting the a processed substrate and the uppermost layer is, for example, in the case of a semiconductor wafer, it is possible to use a silicon wafer, examples of which the outermost surface layer material, Si, SiO _2, SiN, SiON, TiN, WSi, BPSG (Boron Phosphorus Silicon Glass), SOG (spin on glass), organic antireflection film, and the like.

Before forming the resist film, an antireflection film may be formed on the substrate in advance.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon and the like and an organic film type comprising a light absorber and a polymer material can be used. As the organic antireflection film, a commercially available organic antireflection film such as DUV30 series manufactured by Brewer Science, DUV-40 series, AR-2, AR-3, AR-5 manufactured by Shipley may be used.

<Mask blank>

The present invention also relates to a mask blank provided with a resist film formed by a radiation-sensitive or light-sensitive radiation-sensitive composition. When a pattern is formed on a photomask blank for producing a photomask in order to obtain a mask blank having such a resist film, a transparent substrate such as quartz or calcium fluoride may be used as the transparent substrate to be used. In general, necessary functional films such as a light-shielding film, an antireflection film, a phase shift film, an etching stopper film, and an etching mask film are laminated on the substrate. As a material of the functional film, a film containing silicon or a transition metal such as chromium, molybdenum, zirconium, tantalum, tungsten, titanium or niobium is laminated. As the material used for the outermost layer, a material containing silicon and / or silicon as a main constituent material and a silicon compound material containing a transition metal as a main constituent material At least one element selected from the group consisting of oxygen, nitrogen and carbon, and a transition metal, particularly at least one element selected from the group consisting of chromium, molybdenum, zirconium, tantalum, tungsten, titanium and niobium, Further, transition metal compound materials made of constituent materials are further exemplified.

The light-shielding film may be a single layer, but is more preferably a multi-layer structure in which a plurality of materials are overlaid. In the case of the multilayer structure, the thickness of the film per one layer is not particularly limited, but is preferably 5 to 100 nm, more preferably 10 to 80 nm. The thickness of the entire light-shielding film is not particularly limited, but is preferably 5 to 200 nm, more preferably 10 to 150 nm.

Among these materials, in general, when a pattern is formed on a photomask blank having the outermost layer of a material containing oxygen or nitrogen in chromium, a so-called undercut shape is likely to be formed in the vicinity of the substrate. However, The undercut problem can be improved as compared with the conventional one.

This resist film is irradiated with an actinic ray or radiation (electron beam or the like), preferably baked (usually at 80 to 150 캜, more preferably 90 to 130 캜), and then developed. As a result, a good pattern can be obtained. Then, the semiconductor fine circuit and the mold structure for imprint are manufactured by appropriately performing the etching process and the ion implantation using the pattern as a mask.

The process for producing the imprint mold using the radiation sensitive or light sensitive active ray sensitive composition of the present invention is described in, for example, Japanese Patent Publication No. 4109085, Japanese Patent Application Laid-Open No. 2008-162101, and Japanese Patent Application Laid- "Fundamentals and technology development and application of nanoimprint - Nanoimprint technology and latest technology development - Editing: Hirai Yoshihiko (Frontier Shotpan)" is described.

The composition of the present invention is obtained by dissolving the above components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering the solution, and applying the solution on a predetermined substrate. The pore size of the filter used for filter filtration is preferably polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 탆 or less, more preferably 0.05 탆 or less, and even more preferably 0.03 탆 or less. In filter filtration, for example, as in Japanese Laid-Open Patent Publication No. 2002-62667, cyclic filtration may be performed, or a plurality of types of filters may be connected in series or in parallel to conduct filtration. In addition, the composition may be filtered a plurality of times. The composition may be degassed before or after the filtration of the filter.

<Method of Forming a Resist Pattern Using a Sensitizing Radiation or Sensitive Actinic Rayleigh Composition>

The present invention provides a process for producing a resist pattern, comprising the steps of: forming a film by applying the radiation sensitive or photoactive composition on a substrate; exposing the film; and developing the exposed film to form a negative resist pattern And a method of forming a resist pattern. The present invention also relates to a resist pattern forming method comprising a step of exposing a mask blank having the radiation-sensitive or actinic ray-sensitive film and a step of developing the exposed mask blank. In the present invention, it is preferable that the exposure is performed using an electron beam or an extreme ultraviolet ray.

In the exposure (pattern forming step) on the resist film in the production of a precision integrated circuit device, it is preferable that the resist film of the present invention is first subjected to electron beam or extreme ultraviolet (EUV) irradiation in the form of a pattern. The exposure dose is about 0.1 to 20 μC / cm ² , preferably about 3 to 10 μC / cm ^{2 for} electron beam and about 0.1 to 20 mJ / cm ² , preferably about 3 to 15 mJ / cm ^{2 for} extreme ultraviolet light . Subsequently, post exposure baking (postexposure baking) is performed on a hot plate at 60 to 150 ° C for 1 to 20 minutes, preferably at 80 to 120 ° C for 1 to 10 minutes, and then development, rinsing and drying are performed to form a pattern do. The developing solution is appropriately selected, but it is preferable to use a developing solution (also referred to as an organic developing solution) containing an alkaline developing solution (typically, an aqueous alkali solution) or an organic solvent. When the developer is an aqueous alkaline solution, it is preferable to use 0.1 to 5 mass%, preferably 2 to 3 mass%, of an aqueous alkaline solution such as tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide (TBAH) For example, a dip method, a puddle method, or a spray method for 3 minutes, preferably 0.5 to 2 minutes. To the alkali developing solution, an appropriate amount of an alcohol and / or a surfactant may be added. In this way, the film of the unexposed portion is dissolved, and the exposed portion is hardly dissolved in the developer, and a desired pattern is formed on the substrate.

When the resist pattern forming method of the present invention has a step of developing using an alkaline developer, examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, , Primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, tertiary amines such as dimethylethanolamine, Alcohol amines such as ethanolamine and the like, aliphatic amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetra Octylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium &lt; RTI ID = 0.0 &gt; Tetramethylammonium hydroxide, tetramethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammoniumhydroxide, tetraethylammonium hydroxide, tetraethylammonium hydroxide, tetraethylammonium hydroxide, tetraethylammonium hydroxide, And alkaline aqueous solutions such as quaternary ammonium salts such as sodium hydroxide, potassium hydroxide, and the like, and cyclic amines such as pyrrole and piperidine.

Alcohols and surfactants may be added to the alkaline aqueous solution in an appropriate amount.

The alkali concentration of the alkali developing solution is usually 0.1 to 20 mass%.

The pH of the alkali developing solution is usually from 10.0 to 15.0.

Particularly, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is preferable.

As the rinse solution in the rinse treatment performed after the alkali development, pure water may be used and an appropriate amount of a surfactant may be used.

After the developing treatment or the rinsing treatment, the developer or rinsing liquid adhering to the pattern can be removed by supercritical fluid.

When the resist pattern forming method of the present invention has a step of developing using a developer containing an organic solvent, the developer (hereinafter also referred to as an organic developer) in the above step may be a ketone solvent, an ester solvent, Polar solvents such as alcohol solvents, amide solvents and ether solvents, and hydrocarbon solvents can be used.

In the present invention, the ester type solvent is a solvent having an ester group in the molecule, and the ketone type solvent is a solvent having a ketone group in the molecule, and the alcohol type solvent is a solvent having an alcoholic hydroxyl group in the molecule, and the amide type solvent means an amide group And the ether-based solvent is a solvent having an ether bond in the molecule. Among these solvents, there is a solvent having a plurality of the above-mentioned functional groups in one molecule, but in this case, any solvent type including the functional group of the solvent is also considered. For example, the diethylene glycol monomethyl ether corresponds to any of alcohol-based solvents and ether-based solvents in the above-mentioned classification. The hydrocarbon hydrocarbon solvent is a hydrocarbon solvent having no substituent.

In particular, it is preferably a developer containing at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent and an ether solvent.

The developer preferably has a number of carbon atoms of 7 or more (preferably 7 to 14, more preferably 7 to 12, and more preferably 7 to 10) in view of suppressing swelling of the resist film, It is preferable to use an ester-based solvent.

The hetero atom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms is preferably 2 or less.

Preferable examples of the ester type solvent having 7 or more carbon atoms and 2 or less hetero atoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, Butyl carbonate, and the like, and it is particularly preferable to use isoamyl acetate.

The developing solution may be prepared by mixing a solvent mixture of the ester solvent and the hydrocarbon solvent or a mixed solvent of the ketone solvent and the hydrocarbon solvent in place of the ester solvent having the number of carbon atoms of 7 or more and the number of heteroatoms of 2 or less, May be used. Even in this case, it is effective for suppressing the swelling of the resist film.

When an ester solvent and a hydrocarbon hydrocarbon solvent are used in combination, it is preferable to use isoamyl acetate as the ester solvent. As the hydrocarbon hydrocarbon solvent, it is preferable to use a saturated hydrocarbon solvent (e.g., octane, nonene, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint of preparing solubility of the resist film Do.

Examples of the ketone-based solvent include aliphatic ketones such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylamyl ketone) But are not limited to, alcohols such as 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone diacetone, Acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, and the like.

Examples of the ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , Methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate and methyl 2-hydroxyisobutyrate.

Examples of the alcoholic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, , n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, Propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol And glycol ether solvents such as monoethyl ether and methoxymethyl butanol.

As the ether-based solvent, for example, there can be mentioned anisole, dioxane, tetrahydrofuran and the like in addition to the above glycol ether type solvent.

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

Examples of the hydrocarbon hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane and undecane.

A plurality of the above-mentioned solvents may be mixed, or they may be mixed with a solvent or water other than the above. However, in order to sufficiently exhibit the effect of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, more preferably substantially water-free.

That is, the amount of the organic solvent to be used for the organic developing solution is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less based on the total amount of the developing solution.

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

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

Specific examples having a vapor pressure of not more than 5 kPa include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methylamyl ketone), 4-heptanone, Ketone solvents such as isobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone and methyl isobutyl ketone, acetyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene Glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3- Ethyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isopropyl alcohol, isopropyl alcohol, isopropyl alcohol, Butylalcoh , Alcohol solvents such as isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and n-decanol, glycols such as ethylene glycol, diethylene glycol and triethylene glycol Based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethylether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, Glycol ether solvents such as triethylene glycol monoethyl ether and methoxymethylbutanol, ether solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylacetate Amide, N, N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as octane and decane.

Specific examples having a vapor pressure of not more than 2 kPa, which is a particularly preferable range, are 1-octanone, 2-octanone, 1-nonanone, 2- Ketone solvents such as acetone, methyl ethyl ketone, butyl ketone, cyclohexanone, methylcyclohexanone, and phenylacetone, acetyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, lactic acid Butyl alcohol, isobutyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol and the like Alcohol solvent, ethylene glycol, da Glycol solvents such as ethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol mono Glycol ether solvents such as ethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and methoxymethyl butanol, N-methyl-2-pyrrolidone, N, N- Amide solvents of N, N-dimethylformamide, aromatic hydrocarbon solvents such as xylene, aliphatic hydrocarbon solvents such as octane, decane and undecane, and the like.

The organic developer may contain a basic compound. Specific examples and preferable examples of the basic compound that can be contained in the developer used in the present invention are the same as those in the above-described basic compound that can contain the actinic ray-sensitive or radiation-sensitive composition.

To the organic developing solution, an appropriate amount of a surfactant may be added, if necessary.

The surfactant is not particularly limited and, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. As such fluorine- and / or silicon-based surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP- Japanese Unexamined Patent Application Publication No. Hei 8-62834, Japanese Unexamined Patent Application, First Publication No. Hei 9-54432, Japanese Unexamined Patent Application, First Publication No. Hei 9- And surfactants described in U.S. Patent Nos. 5,605,792, 5,605,720, 5,560,892, 5,296,330, 5,453,143, 5,576,143, 5,295,451, and 5,824,451, It is an ionic surfactant. The nonionic surfactant is not particularly limited, but a fluorinated surfactant or a silicone surfactant is more preferably used.

The amount of the surfactant to be used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and particularly preferably 0.0005 to 1% by mass, based on the total amount of the developer.

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

The various types of the developing methods, in the case of a step of discharging the developer nozzle of the developing device toward the resist film with a developing solution, the ejection of the developing solution which is a discharge pressure (per unit flow rate of the discharged developer) is preferably 2mL / sec / mm ² More preferably not more than 1.5 mL / sec / mm ² , even more preferably not more than 1 mL / sec / mm ² . Although the lower limit of the flow velocity is not particularly specified, it is preferably 0.2 mL / sec / mm ² or more in consideration of the throughput.

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

Although details of this mechanism are not clear, it is presumably because the pressure applied to the resist film by the developer is reduced by prescribing the discharge pressure within the above-mentioned range, whereby the resist film and the resist pattern are inadvertently suppressed from being scraped or collapsed.

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

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

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

After the step of developing using a developing solution containing an organic solvent, the step of cleaning may be performed using a rinsing liquid. However, from the viewpoints of throughput (productivity) and amount of rinsing solution used, .

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

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

After the step of developing using a developing solution containing an organic solvent, it is more preferable to use a rinsing solution containing at least one organic solvent selected from the group consisting of an ester solvent, an alcohol solvent and a hydrocarbon hydrocarbon solvent It is preferable to carry out a step of cleaning, and more preferably, a step of cleaning by using a rinsing liquid containing an alcoholic solvent or a hydrocarbon hydrocarbon solvent.

As the organic solvent contained in the rinsing liquid, it is also preferable to use a hydrocarbon hydrocarbon solvent among organic solvents, more preferably an aliphatic hydrocarbon hydrocarbon solvent. As the aliphatic hydrocarbon solvents for use in the rinsing liquid, aliphatic hydrocarbon solvents having 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane, dodecane, Ketene, hexadecane, etc.), and aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferable, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferable.

The upper limit value of the number of carbon atoms of the aliphatic hydrocarbon group-containing solvent is not particularly limited, but may be, for example, 16 or less, preferably 14 or less, and more preferably 12 or less.

Among the above-mentioned fat-soluble hydrocarbon solvents, particularly preferred are decane, undecane and dodecane, and most preferably undecane.

By using a hydrocarbon hydrocarbon solvent (particularly, an aliphatic hydrocarbon solvent solvent) as the organic solvent contained in the rinse liquid, the developer that has been slightly impregnated into the resist film after washing is washed away, the swelling is further suppressed, and the pattern collapse is suppressed The effect is further exerted.

A plurality of these components may be mixed, or they may be mixed with other organic solvents.

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

The vapor pressure of the rinsing liquid used after the developing process using an organic solvent is preferably 0.05 kPa or more and 5 kPa or less at 20 캜, more preferably 0.1 kPa or more and 5 kPa or less, more preferably 0.12 kPa or more, Or less. By adjusting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, temperature uniformity in the wafer surface is improved, swelling due to infiltration of the rinsing liquid is suppressed, and dimensional uniformity within the wafer surface is improved.

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

In the rinsing process, the wafer having undergone development using a developer containing an organic solvent is subjected to a cleaning treatment using a rinsing liquid containing the organic solvent. There is no particular limitation on the method of the cleaning treatment, but a method of continuously discharging the rinsing liquid onto the substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in the tank filled with the rinsing liquid for a predetermined time ), A method of spraying a rinsing liquid onto the surface of the substrate (spraying method), etc. Among them, a cleaning treatment is carried out by a rotation coating method, and after cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm, It is preferable to remove it from the substrate. It is also preferable to include a post-baking process after the rinsing process. The developer and rinsing liquid remaining in the patterns and in the patterns are removed by baking. The heating step after the rinsing step is usually carried out at 40 to 160 ° C, preferably 70 to 95 ° C, for 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The present invention also relates to a photomask obtained by exposing and developing a resist-coated mask blank. As the exposure and development, the processes described above are applied. The photomask is suitably used for semiconductor manufacturing.

The photomask in the present invention may be a light transmission type mask used in an ArF excimer laser or the like, or a light reflection type mask used in reflection type lithography using EUV light as a light source.

Further, the mold for imprinting may be produced using the composition of the present invention. For details, reference may be made to, for example, Japanese Patent Publication No. 4109085 or Japanese Patent Application Laid-Open No. 2008-162101.

The method of forming a resist pattern of the present invention is also applicable to formation of a guide pattern in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8, page 4815-4823) have.

The resist pattern formed by the above method can be used as a core (core) of a spacer process disclosed in, for example, Japanese Unexamined Patent Application Publication No. 3-270227 and Japanese Unexamined Patent Publication No. 2013-164509.

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

The electronic device (preferably a semiconductor device) of the present invention is suitably mounted in electric and electronic devices (home appliances, office appliances, media-related devices, optical devices, communication devices, etc.).

&Lt; a compound represented by the general formula (I) and having a molecular weight of not less than 450 but not more than 2000>

The present invention also relates to a compound represented by the above general formula (I) and having a molecular weight of 450 or more and 2000 or less.

A detailed description of the compound is the same as the compound (A) contained in the radiation-sensitive or light-sensitive radiation-sensitive composition of the present invention, and the compound of the present invention can be used as a crosslinking agent or the like in a radiation- Can be suitably used.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

The structural formulas and molecular weights of the compounds (A1) to (A16) are shown in Tables 1, 2 and 3 and the structural formulas and molecular weights of the compounds (R1) to (R5) (Mw), weight average molecular weight (Mw), and degree of dispersion (Mw / Mn) of the repeating units are shown in Table 4 below.

The compound (A) constitutional formula Molecular Weight compound
(A1)

550.64 compound
(A2)

578.78 compound
(A3)

566.68 compound
(A4)

596.71 compound
(A5)

622.75 compound
(A6)

786.36

The compound (A) constitutional formula Molecular Weight compound
(A7)

580.67 compound
(A8)

538.78 compound
(A9)

620.77 compound
(A10)

562.73 compound
(A11)

550.64 compound
(A12)

458.50

The compound (A) constitutional formula Molecular Weight compound
(A13)

568.76 compound
(A14)

654.79 compound
(A15)

530.65 compound
(A16)

1342.72

The Molecular Weight The comparative polymer compound (R1)

조성비는 몰비

The mole ratio 4500
(Weight average molecular weight)

Dispersion degree: 1.52 Comparative compound
(R2)

252.35 Comparative compound
(R3)

442.37 Comparative compound
(R4)

318.33 Comparative compound
(R5)

462.62

[Example 1E]

(1) Preparation of Support

A 6-inch silicon wafer (subjected to a shielding film treatment used for a normal photomask blank) with Cr oxide deposition was prepared. One inch is 25.4 mm.

(2) Preparation of resist coating liquid

(Coating composition of negative resist composition N1)

The polymer compound (P1) 4.21 g

The compound (A1) represented by the general formula (I) 0.89 g

Photoacid generator (z42) 0.47 g

Tetrabutylammonium hydroxide (B1) 0.04 g

The organic carboxylic acid (D1) 0.11 g

Surfactant PF6320 (manufactured by Omnova) (W-1) 0.005 g

Propylene glycol monomethyl ether acetate (S1) (solvent) 75.0 g

Propylene glycol monomethyl ether (S2) (solvent) 18.8g

The composition solution was microfiltered with a polytetrafluoroethylene filter having a pore diameter of 0.04 mu m to obtain a resist coating solution.

(3) Preparation of resist film

A resist coating solution was coated on the 6-inch silicon wafer using a spin coater Mark 8 manufactured by Tokyo Electron and dried on a hot plate at 110 캜 for 90 seconds to obtain a resist film having a thickness of 50 nm. That is, a resist-coated mask blank was obtained.

(4) Fabrication of negative resist pattern

The resist film was subjected to pattern irradiation using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Co., Ltd., acceleration voltage: 50 KeV). After the irradiation, the substrate was heated on a hot plate at 120 DEG C for 90 seconds, immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and rinsed with water for 30 seconds.

(5) Evaluation of resist pattern

The obtained patterns were evaluated for sensitivity, resolution, pattern shape, line edge roughness (LER) performance, dry etching resistance, PEB time dependency, PED stability, and in-plane uniformity (CDU) of line width in the following manner.

〔Sensitivity〕

The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). And the exposure amount (electron beam irradiation amount) at the time of resolving a 1: 1 line-and-space resist pattern having a line width of 50 nm was taken as sensitivity. The smaller the value, the higher the sensitivity.

〔definition〕

The minimum resolution (the minimum line width at which lines and spaces are separated and resolved) in the exposure amount (electron beam irradiation amount) indicating the above sensitivity is defined as the LS resolution (nm).

[Pattern shape]

Sectional shape of a 1: 1 line-and-space pattern having a line width of 50 nm in the exposure amount (electron beam irradiation amount) indicating the above sensitivity was observed using a scanning electron microscope (S-4300, Hitachi Seisakusho Co., Ltd.). (The line width in the top portion of the line pattern / the line width in the middle portion of the line pattern (the height position of half the height of the line pattern)] is 1.2 or more, Quot; reverse taper ", and those having a ratio of 1.05 or more and less than 1.2 were called "slightly inverse taper ", and those having a ratio of less than 1.05 were referred to as " rectangle ".

[Line edge roughness (LER) performance]

A 1: 1 line-and-space pattern having a line width of 50 nm was formed by the irradiation amount (electron beam irradiation amount) indicating the above sensitivity. Then, the distance from the reference line on which an edge is to be present was measured using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) for arbitrary 30 points included in the longitudinal direction of 10 mu m. Then, the standard deviation (?) Of this distance was calculated, and 3σ of this value was calculated. The smaller the value, the better the performance.

[Dry etching resistance]

The resist film formed by irradiating the entire surface with the irradiation amount (electron beam irradiation amount) indicating the above sensitivity was irradiated with Ar / C ₄ F ₆ / O ₂ gas (volume ratio 100/4/2 mixed with HITACHI U-621) Gas) was used for dry etching for 30 seconds. Thereafter, the resist residual film ratio was measured and used as an index of dry etching resistance.

Very good: Remaining film ratio 95% or more

Good: Less than 95% Less than 90%

Poor: Less than 90%

[PEB time dependency]

(PEB) at 120 DEG C for 90 seconds, the exposure amount for reproducing the 1: 1 line and space of 50 nm is set to the optimum exposure amount, and then the exposure is performed at the optimum exposure amount. Sec and -10 sec (100 sec, 80 sec), and line widths of the obtained line and space were measured, and their line widths L1 and L2 were obtained. The PEB time dependency (PEBS) was defined as the variation of the line width per one second of PEB time variation, and was calculated by the following equation.

PEB time dependency (nm / sec) = | L1-L2 | / 20

The smaller the value, the smaller the performance change over time and the better the performance.

[Post Exposure time Delay (PED) stability]

The line line width dimension (0h) obtained by PEB treatment after the exposure and the line line width dimension (5.0) on the wafer subjected to the PEB treatment after 5 hours were measured at the exposure amount at which the line width dimension of the 1: 1 line- h) was measured, and the line width change ratio was calculated by the following equation.

Line width change rate (%) = | DELTA CD (5.0h-0h) | nm / 50nm

The smaller the value, the better the performance and was the index of PED stability.

[In-plane uniformity of line width (CDU)]

100 line widths of each line pattern were measured at the exposure amount at which the line width of the 1: 1 line and space pattern was 50 nm, and the line width (3σ) of the standard deviation (?) Of the average value calculated from the measurement results was obtained, Plane uniformity (CDU) (nm). The 3 sigma obtained from the above means that the smaller the value, the higher the in-plane uniformity (CDU) of each line CD formed in the resist film.

[Examples 2E to 21E and Comparative Example 1ER to Comparative Example 5ER]

(Negative type resist compositions N2 to N21, negative type resist comparative compositions NR1 to NR5) were prepared in the same manner as in Example 1E except that the components listed in Tables 5 and 6 were used in the resist solution prescription, Pattern formation and evaluation thereof were carried out.

Composition Compounds having a phenolic hydroxyl group The compound (A) Photoacid generator Basic compound or ammonium salt compound Organic carboxylic acid Surfactants solvent N1 P1 A1 z42 B1 D1 W-1 S1 / S2 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) N2 P1 A2 z5 B2 D1 W-1 S1 / S3 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) N3 P1 A3 z49 B4 D3 W-2 S2 / S3 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) N4 P1 A4 z61 B5 D2 W-1 S2 / S7 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) N5 P1 A5 z63 B6 D1 none S2 / S1 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (75.0 g / 18.8 g) N6 P1 A6 z65 B7 D3 W-1 S2 / S1 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) N7 P1 A7 z67 B8 D1 W-1 S2 / S1 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) N8 P1 A8 z37 B2 D2 W-1 S2 / S1 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) N9 P1 A9 z68 B1 D1 W-1 S2 / S1 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) N10 P1 A10 z42 B1 D1 W-1 S2 / S1 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) N11 P1 A11 z45 B2 D2 none S2 / S1 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (75.0 g / 18.8 g) N12 P1 A12 z49 B3 D1 W-2 S1 / S2 / S6 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (50.0 g / 25.0 g / 18.8 g) N13 P1 A13 z61 B4 none W-2 S1 / S2 / S5 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.005 g) (50.0 g / 25.0 g / 18.8 g) N14 P1 A14 z68 B5 D1 W-3 S1 / S2 / S4 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (50.0 g / 25.0 g / 18.8 g) N15 P1 A15 z66 B1 D2 none S2 / S1 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (75.0 g / 18.8 g) N16 P2 A1 z42 B8 D3 W-1 S2 / S1 (4.21 g) (0.40 g)
A2 (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) (0.49 g) N17 P3 A1 z48 B7 D1 W-1 S2 / S1 (4.21 g) (0.49 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) R4 (0.40 g) N18 P4 A1 z42 B8 D3 none S2 / S1 (2.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (75.0 g / 18.8 g) P3 (2.0 g) N19 P5 A1 z42
(0.20 g) B8 D1 none S2 / S1 (3.21 g) (1.89 g) z42
(0.27 g) (0.04 g) (0.11 g) (75.0 g / 18.8 g) N20 P6 A1 z42 B8 D2 none S2 / S1 (2.21 g) (2.89 g) (0.47 g) (0.04 g) (0.11 g) (75.0 g / 18.8 g) N21 P1 A16 z42 B1 D1 W-1 S1 / S2 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g)

Composition Compounds having a phenolic hydroxyl group compound
(Crosslinking agent) Photoacid generator Basic compound or ammonium salt compound Organic carboxylic acid Surfactants solvent NR1 P1 R1 z42 B1 D1 W-1 S2 / S1 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) NR2 P1 R2 z42 B1 D1 W-1 S1 / S3 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) NR3 P1 R3 z42 B1 D1 W-1 S2 / S3 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) NR4 P1 R4 z42 B1 D1 W-1 S2 / S3 (4.21 g) (0.89 g) (0.47 g) (0.04 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g) NR5 P1 R5 z42 B1 D1 W-1 S2 / S3 (4.21 g) (0.89 g) (0.47 g) (0.005 g) (0.11 g) (0.005 g) (75.0 g / 18.8 g)

The abbreviations of the materials other than the above-mentioned materials used in the above-mentioned Examples or Comparative Examples are described below.

[Compound having a phenolic hydroxyl group]

(31)

[Basic compound or ammonium salt compound]

B1: tetrabutylammonium hydroxide

B2: tri (n-octyl) amine

B3: 2,4,5-Triphenylimidazole

(32)

[Organic carboxylic acid]

D1: 2-Hydroxy-3-naphthoic acid

D2: 2-Naphthoic acid

D3: benzoic acid

〔Surfactants〕

W-1: PF6320 (manufactured by Omnova)

W-2: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc., fluorine)

W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co.,

〔solvent〕

S1: Propylene glycol monomethyl ether acetate (1-methoxy-2-acetoxypropane)

S2: Propylene glycol monomethyl ether (1-methoxy-2-propanol)

S3: 2-heptanone

S4: Ethyl lactate

S5: cyclohexanone

S6:? -Butyrolactone

S7: Propylene carbonate

[Photo acid generator]

(33)

The evaluation results are shown in Table 7.

sample A radiation-sensitive or actinic ray-sensitive composition Sensitivity
(μC / cm ² ) definition
(nm) Pattern shape LER
(nm) Dry etching resistance PEB time dependency
(nm / sec) PED stability
(%) CDU
(nm) 1E N1 11.2 25 Rectangle 4.5 Very good 0.4 0.4 3.5 2E N2 11.0 25 Rectangle 4.5 Very good 0.4 0.4 3.6 3E N3 11.2 24 Rectangle 4.5 Very good 0.4 0.4 3.5 4E N4 11.2 25 Rectangle 4.5 Very good 0.4 0.4 3.5 5E N5 11.3 26 Rectangle 4.0 Very good 0.4 0.4 3.7 6E N6 11.3 25 Rectangle 4.5 Very good 0.4 0.4 3.6 7E N7 11.3 25 Rectangle 4.5 Very good 0.8 0.8 3.5 8E N8 15.2 25 Rectangle 4.5 Very good 0.4 0.4 3.7 9E N9 11.8 30 Rectangle 4.5 Very good 0.4 0.4 3.5 10E N10 11.2 24 Rectangle 4.5 Very good 0.4 0.4 3.6 11E N11 14.6 30 Rectangle 4.5 Very good 0.4 0.4 3.5 12E N12 11.2 25 Rectangle 4.5 Very good 0.8 0.8 3.5 13E N13 11.3 25 Rectangle 4.5 Very good 0.4 0.4 3.5 14E N14 11.3 25 Rectangle 4.5 Very good 0.4 0.4 3.6 15E N15 11.3 30 Rectangle 4.5 Good 0.4 0.4 3.5 16E N16 11.3 25 Rectangle 4.0 Very good 0.4 0.4 3.6 17E N17 11.3 30 Rectangle 4.5 Very good 0.4 0.4 3.5 18E N18 11.3 25 Rectangle 4.0 Very good 0.4 0.4 3.0 19E N19 11.3 25 Rectangle 4.0 Very good 0.4 0.4 3.5 20E N20 11.3 25 Rectangle 4.0 Very good 0.4 0.4 3.5 21E N21 11.3 25 Taper slightly 4.5 Very good 0.4 0.4 4.0 1ER NR1 11.8 40 Taper slightly 5.0 Good 0.4 0.4 4.3 2ER NR2 14.8 50 Reverse taper 5.5 Good 2.0 1.9 4.3 3ER NR3 13.8 40 Taper slightly 5.0 Good 1.9 1.8 4.2 4ER NR4 20.8 50 Reverse taper 5.0 Bad 2.0 2.0 4.5 5ER NR5 13.8 30 Reverse taper 5.5 Good 0.5 0.4 4.5

From the results shown in Table 7, it can be seen that Examples 1E to 20E using the radiation sensitive or photoactive ray sensitive composition of the present invention are superior in sensitivity, resolution, pattern shape, LER It can be seen that it is superior in both performance and dry etching resistance, has lower PEB time dependency, and has better PED stability.

Further, in the above examples, the same performance is exhibited even when the compound having a phenolic hydroxyl group, the photoacid generator, and the basic compound are changed within the preferable ranges described above.

[Examples 1F to 6F and Comparative Examples 1FR to 5FR]

The negative resist compositions shown in Table 8 below were microfiltered with a polytetrafluoroethylene filter having a pore diameter of 0.04 mu m to obtain a resist coating solution.

(Preparation of resist film)

A resist coating solution was coated on the 6-inch silicon wafer using a spin coater Mark 8 manufactured by Tokyo Electron and dried on a hot plate at 110 캜 for 90 seconds to obtain a resist film having a thickness of 50 nm. That is, a resist-coated mask blank was obtained.

(Resist evaluation)

The obtained resist film was evaluated for sensitivity, resolution, pattern shape, line edge roughness (LER), PED stability, in-plane uniformity of line width (CDU) and dry etching resistance in the following manner.

〔Sensitivity〕

The exposed resist film was exposed to light using an EUV exposure apparatus (Micro Exposure Tool manufactured by Exitec, NA0.3, Quadrupole, Outer Sigma 0.68, Inner Sigma 0.36) while changes in the range of 20.0mJ / cm ² by 0.1mJ / cm ^2, the line width of 50nm 1: through the reflective mask in the first line and space pattern was subjected to the exposure, and was baked at 110 ℃ 90 seconds. Thereafter, development was performed using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH).

The exposure dose for reproducing a mask pattern of 1: 1 line-and-space with a line width of 50 nm was set to sensitivity. The smaller the value, the higher the sensitivity.

〔definition〕

(Minimum line width at which lines and spaces (line: space = 1: 1) are separated and resolved) in the exposure amount indicating the above sensitivity is defined as resolution (nm).

[Pattern shape]

The cross-sectional shape of the 1: 1 line-and-space pattern having a line width of 50 nm in the exposure amount indicating the above sensitivity was observed using a scanning electron microscope (S-4300, Hitachi Seisakusho Co., Ltd.). (The line width in the top portion of the line pattern / the line width in the middle portion of the line pattern (the height position of half the height of the line pattern)] of not less than 1.5 is referred to as " Quot; reverse taper ", and those having a ratio of 1.2 or more and less than 1.5 were called "slightly inverse taper"

[Line edge roughness (LER)]

A 1: 1 line-and-space pattern having a line width of 50 nm was formed at an exposure amount representing the above sensitivity. Then, the distance from the reference line on which the edge should be measured was measured using a scanning electron microscope (S-9220, manufactured by Hitachi Seisakusho Co., Ltd.) for arbitrary 30 points in the longitudinal direction of 50 m. Then, the standard deviation (?) Of this distance was calculated, and 3σ of this value was calculated. The smaller the value, the better the performance.

[Post Exposure time Delay (PED) stability]

The line line width dimension (0h) obtained by PEB treatment after the exposure and the line line width dimension (5.0h) on the wafer subjected to the PEB treatment after 5 hours were measured at the exposure amount at which the line width dimension of the 50: 1 nm line- ) Was measured, and the line width change ratio was calculated by the following formula.

Line width change rate (%) = | DELTA CD (5.0h-0h) | nm / 50nm

The smaller the value, the better the performance and was the index of PED stability.

[Dry etching resistance]

The resist film formed by performing the entire surface exposure with an exposure amount (extreme ultraviolet ray exposure amount) indicating the sensitivity described above was irradiated with Ar / C ₄ F ₆ / O ₂ gas (mixed gas of volume ratio 100/4/2) with Hitachi U- To perform dry etching for 30 seconds. Thereafter, the resist residual film ratio was measured and used as an index of dry etching resistance.

Very good: Remaining film ratio 95% or more

Good: Less than 95% Less than 90%

Poor: Less than 90%

[In-plane uniformity of line width (CDU)]

100 line widths of each line pattern were measured at the exposure amount at which the line width of the 1: 1 line and space pattern was 50 nm, and the line width (3σ) of the standard deviation (?) Of the average value calculated from the measurement results was obtained, Plane uniformity (CDU) (nm). The 3 sigma obtained from the above means that the smaller the value, the higher the in-plane uniformity (CDU) of each line CD formed in the resist film.

Table 8 shows the above evaluation results.

sample A radiation-sensitive or actinic ray-sensitive composition Sensitivity
(mJ / cm ² ) definition
(nm) Pattern shape LER
(nm) PED stability
(%) Dry etching resistance CDU
(nm) 1F N1 12.8 25 Rectangle 4.5 0.4 Very good 3.5 2F N2 12.7 25 Rectangle 4.5 0.4 Very good 3.6 3F N3 12.8 25 Rectangle 4.5 0.4 Very good 3.5 4F N5 12.8 24 Rectangle 4.0 0.4 Very good 3.5 5F N8 14.2 26 Rectangle 4.5 0.4 Very good 3.7 6F N18 12.7 25 Rectangle 4.0 0.4 Very good 3.0 1FR NR1 12.8 50 Taper slightly 5.0 0.4 Good 4.3 2FR NR2 15.8 50 Reverse taper 5.5 2.0 Good 4.4 3FR NR3 15.5 40 Taper slightly 5.0 2.0 Good 4.3 4FR NR4 20.5 35 Reverse taper 5.0 2.0 Bad 4.6 5FR NR5 15.5 35 Reverse taper 5.5 0.6 Good 4.6

From the results shown in Table 8, it is understood that Examples 1F to 6F using the radiation sensitive or photoactive ray sensitive composition of the present invention are superior in sensitivity, resolution, pattern shape and LER It can be seen that it is superior in both of the performance and the PED stability.

[Examples 1C to 6C and Comparative Examples 1CR to 5CR]

(1) Preparation of resist composition and preparation of resist film

The composition shown in Table 9 described below was microfiltered with a membrane filter having a pore size of 0.1 mu m to obtain a resist composition.

This resist composition was coated on a 6-inch Si wafer previously subjected to hexamethyldisilazane (HMDS) treatment using a spin coater Mark 8 manufactured by Tokyo Electron and dried on a hot plate at 100 캜 for 90 seconds to form a resist film having a thickness of 50 nm Thereby obtaining a resist film.

(2) EB exposure and development

The wafer coated with the resist film obtained in the above (1) was subjected to pattern irradiation using an electron beam drawing apparatus (HL750, Hitachi, Ltd., acceleration voltage: 50 KeV). At this time, drawing was performed so that a line-and-space of 1: 1 was formed. After the electron beam lithography, the substrate was heated on a hot plate at 110 DEG C for 60 seconds, and the organic developer described in Table 9 was purged and developed for 30 seconds. After rinsing using the rinse solution shown in the table, rinsing was performed at 4000 rpm The wafer was rotated for 30 seconds and then heated at 90 DEG C for 90 seconds to obtain a resist pattern of 1: 1 line and space pattern having a line width of 50 nm.

The obtained resist film was evaluated for sensitivity, resolution, pattern shape, line edge roughness (LER), PEB time dependency, in-plane uniformity of line width (CDU) and PED stability in the same manner as in Example 1E. The results are shown in Table 9 below.

The abbreviations of the components other than those described above used in the above examples / comparative examples are described below.

&Lt; Developer / rinse liquid >

S8: Acetic acid butyl

S9: pentyl acetate

S10: Anisole

S11: 1-hexanol

S12: Deccan

From the results shown in Table 9, it can be seen that Examples 1C to 6C using the radiation sensitive or photoactive ray sensitive composition of the present invention are superior in sensitivity, resolution, pattern shape, LER Performance, and dry etching resistance, lower PEB time dependency, and better PED stability.

Industrial availability

According to the present invention, it is possible to improve the sensitivity, resolution, pattern shape, line edge roughness performance, PEB time dependency, PED stability, dry etching resistance, and linewidth in the pattern formation of a very fine (for example, a line width of 50 nm or less) A mask blank, a pattern forming method, an electronic device manufacturing method, and an electronic device can be provided, which are excellent radiation-sensitive or actinic ray-sensitive compositions at a very high level in all of the uniformity (CDU) .

While the invention has been described in detail and with reference to specific embodiments thereof, it is evident to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

This application is based on Japanese Patent Application No. 2015-013351 filed on January 27, 2015, the content of which is incorporated herein by reference.

Claims (12)

A compound represented by the general formula (I) and having a molecular weight of 450 or more and 2000 or less,
A radiation-sensitive or light-sensitive radiation-sensitive composition containing an acid generator which generates an acid upon irradiation with an actinic ray or radiation.
[Chemical Formula 1]

Wherein,
X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an acyl group.
A represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or an alicyclic group.
R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Provided that not all R ₁ and all R ₂ are hydrogen atoms at the same time.
m and n each independently represent an integer of 1 or more.
When at least one of m and n represents an integer of 2 or more, a plurality of R ₁ , a plurality of R _2, and a plurality of X may be the same or different.
When m represents an integer of 2 or more, a plurality of A may be the same or different.
Y represents an m-valent group having a hetero atom.
At least one of A and R ₁ and R ₂ may be bonded to form a ring.
R ₁ and R ₂ may bond together to form a ring together with the carbon atom to which they are bonded. The method according to claim 1,
Wherein Y is an m-valent group having a heteroatom and a cyclic structure. The method according to claim 1 or 2,
A radiation-sensitive or light-sensitive radiation-sensitive composition further comprising a polymer compound having a structural unit represented by formula (II).
(2)

Wherein,
R ₄ represents a hydrogen atom, an organic group, or a halogen atom.
D ₁ represents a single bond or a divalent linking group.
Ar ₂ represents aromatic ring.
m ₁ represents an integer of 1 or more. The method according to any one of claims 1 to 3,
Wherein the acid generator is a sulfonium salt. The method according to any one of claims 1 to 4,
A radiation-sensitive or light-sensitive radiation-sensitive composition further having a basic compound or an ammonium salt compound, the basicity of which is lowered by irradiation with an actinic ray or radiation. The method according to any one of claims 1 to 5,
A radiation-sensitive or light-sensitive radiation-sensitive composition which is a chemically amplified negative resist composition for electron beam or extreme ultraviolet exposure. A radiation-sensitive or actinic ray-forming film formed using the radiation-sensitive or light-sensitive radiation-sensitive composition according to any one of claims 1 to 6. A mask blank provided with the radiation sensitive or actinic radiation film according to claim 7. A process for forming a film by applying the radiation-sensitive or light-sensitive radiation-sensitive composition according to any one of claims 1 to 6 onto a substrate,
A step of exposing the film, and
And developing the exposed film to form a negative resist pattern. A step of exposing the mask blank having the radiation sensitive or light sensitive active film according to claim 7, and
And developing the exposed mask blank. The method according to claim 9 or 10,
Wherein the exposure is performed using an electron beam or an extreme ultraviolet ray. A method of manufacturing an electronic device comprising the resist pattern forming method according to claim 9.