JP6641825B2 - Negative resist composition, method for producing resist pattern, and electronic component - Google Patents

Description

  The present invention relates to a negative resist composition for forming a chemically amplified resist useful for microfabrication, a method for producing a resist pattern using the negative resist composition, and an electronic component.

In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, patterns have been rapidly miniaturized due to advances in lithography technology, and, for example, high resolution with a dimension width of 50 nm or less has been required.
As a method of miniaturization, the wavelength of an exposure light source is generally shortened. In addition to the currently used KrF excimer laser light, ArF, F2, EUV, X-ray, electron beam, and other charged particle beams are used. Lithography using such as exposure light has been proposed.

  Particularly, pattern formation by electron beam and EUV exposure is regarded as a next-generation or next-next-generation lithography technology, and has high sensitivity and high sensitivity for forming a gate layer of a semiconductor integrated circuit and processing a mask pattern formed on a glass substrate. There is a demand for development of a resist that satisfies resolution requirements. As a resist material for these, a chemically amplified photosensitive composition utilizing a catalytic reaction of an acid is used for the purpose of improving sensitivity. The negative chemically amplified photosensitive composition usually contains an alkali-soluble resin, an acid generator component that generates an acid upon irradiation with light, a crosslinkable compound, a basic compound, and the like. In the photosensitive composition, crosslinking occurs between the resin and the crosslinking compound due to the action of an acid generated from the acid generator component upon exposure, and the composition changes from alkali-soluble to alkali-insoluble. Further, the acid generated at the time of the cross-linking reaction catalytically repeats the reaction, thereby enabling pattern exposure with a smaller exposure amount. On the other hand, a positive chemically amplified photosensitive composition has an increased solubility in a developer due to, for example, elimination of an acid dissociable protecting group due to the action of an acid generated from an acid generator component upon exposure. I do.

Conventionally, a resist material based on a polymer having a weight average molecular weight of about 5,000 or more has been used for lithography of a semiconductor.
However, since such a polymer material has a large molecular weight and a wide molecular weight distribution, there is a limit in reducing the resolving power and the line edge roughness (LER).

  Therefore, a low molecular weight material having a low molecular weight and a small molecular size is being developed, and the low molecular weight material is superior in resolution as compared with a high molecular weight material, and can be expected to reduce LER. Examples of negative resists based on such low molecular weight materials include resists using calixresorcinarenes and derivatives thereof (Patent Document 1 and Non-Patent Document 1), resists using low molecular weight polyphenolic compound derivatives ( Non-Patent Document 2) and a resist using a cyclic polyphenolic compound derivative (Patent Document 2).

  On the other hand, as a chemical amplification type resist material in which a basic compound is used, Patent Document 3 discloses an alkali-soluble novolak resin, a quinonediazide group-containing compound, and a vinyl group, a benzyl group, and an alkyl group substituted. A positive photoresist composition comprising an imidazole compound is disclosed. Patent Literature 3 is a technique aimed at obtaining a resist pattern having excellent adhesion to a substrate without impairing the storage stability of the resist.

Patent Document 4 discloses a specific benzimidazole skeleton and an ester group, an acetal group, or a cyano group for the purpose of obtaining a resist material having a high effect of preventing the film from being reduced in the resist and having a high resolution and a focus margin expanding effect. The resist composition described above contains a basic compound having a polar functional group.
However, Patent Literature 4 which has a problem of resolution only forms a 160 nm line and space, and the photoresists of Patent Literatures 1 to 4 and Non-Patent Literatures 1 and 2 have insufficient resolution. Therefore, a resist capable of forming a further miniaturized pattern has been demanded.

  In view of this, the present inventors have disclosed in Patent Document 5 a phenolic compound (A) as a negative resist composition having excellent resolution while maintaining high sensitivity peculiar to a chemically amplified resist in pattern formation by irradiation with active energy rays. And an acid generator (B) and a base having at least one aromatic ring in one molecule and having at least one phenolic hydroxyl group and / or oxy group (-O-) in one molecule and having a molecular weight of 400 or more. A resist composition containing a neutral nitrogen-containing compound (C) is disclosed.

JP-A-10-239843 JP-A-11-153863 JP-A-9-236923 JP-A-2004-337738 JP 2012-220850 A

Journal of Photopolymer Science and Technology Volume 21, Number 3 (2008) 443-449. Chemistry of Materials 2006, 18, 3404-3411

  In recent years, as the miniaturization of resist patterns has progressed further and the demand for high resolution has further increased, various lithography characteristics have been required to be improved. Above all, dimensional fidelity (also called linearity) for forming a resist pattern with dimensions faithful to the design dimensions and mask size of an electron beam is an important characteristic, and its improvement is required. It is also required that no resist residue is generated after development.

  The present invention has been made under such circumstances, and provides a resist composition having improved dimensional fidelity and suppression of resist residue, a method of manufacturing a resist pattern using the resist composition, and an electronic component. With the goal.

The present inventors have conducted intensive studies to achieve the above object, and as a result, combined a phenolic compound and an acid generator with a basic nitrogen-containing compound having a specific crosslinkable group and a phenolic hydroxyl group. It has been found that by using the resist composition, a resist composition having improved dimensional fidelity and resist residue suppression can be obtained without impairing sensitivity or other properties.
The present invention has been completed based on such findings.

  The present invention relates to a phenolic compound (A), an acid generator (B), an aromatic ring having at least one phenolic hydroxyl group in one molecule and having a phenolic hydroxyl group, a hydroxymethyl group and an alkoxymethyl group. A basic nitrogen-containing compound (C) having a molecular weight of 400 to 3,000 having at least one substituent selected from the group consisting of one or more substituents per molecule, and a crosslinkable compound (D); The present invention provides a negative resist composition wherein the reactive compound (A) and the crosslinkable compound (D) may be the same compound.

  In the resist composition according to the present invention, the phenolic compound (A) and the crosslinkable compound (D) are the same compound, and the same compound has two or more phenolic hydroxyl groups in one molecule. A phenolic compound having a molecular weight of 300 to 3000 and having one or more substituents per molecule selected from a group consisting of a hydroxymethyl group and an alkoxymethyl group on an aromatic ring having a phenolic hydroxyl group; A ′) is preferable because a pattern with high resolution and low line edge roughness can be obtained.

  In the resist composition according to the present invention, it is preferable that the basic nitrogen-containing compound (C) has a partial structure represented by the following formula (1) from the viewpoint of improving dimensional fidelity and resist residue suppression.

In (the above formula (1), R ^a represents a hydrocarbon group which may contain a hetero atom, Base is a group represented by the following formula (1-a), or, may have a substituent Represents a good basic nitrogen-containing heterocyclic group, R ^d is a substituent, and s is the number of substituents, and is 0 to 4.)

(In the formula (1-a), R ^b and R ^c each independently represent a hydrocarbon group which may contain a hetero atom, and R ^b and R ^c may be the same or different from each other. .)

The present invention provides (i) a step of applying the resist composition according to the present invention on a substrate and then performing a heat treatment to form a resist film; and (ii) exposing, heating and developing the resist film. And a method for manufacturing a relief pattern.
The present invention also provides an electronic component at least partially formed of the resist composition according to the present invention or a cured product thereof.

  According to the present invention, it is possible to provide a resist composition in which dimensional fidelity and resist residue suppression are improved, a method for producing a resist pattern using the resist composition, and an electronic component.

Hereinafter, the resist composition, the method for producing a resist pattern, and the electronic component according to the present invention will be described in order.
In the present invention, the active energy ray, KrF excimer laser, ArF excimer laser, and _{F 2} far infrared excimer laser, electron beam, means an ion beam, EUV, X-rays or the like.
In addition, in the notation of the group (atomic group) in the present invention, the notation that does not denote substituted or unsubstituted includes those having a substituent as well as those having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Divalent linking alkylene groups can optionally from different carbon atoms _(e.g., -CH 2 -CH ₂ -) Other, also divalent bonds from the same carbon atom (e.g., _-CH 2 -). The alkyl group and the cycloalkyl group include unsaturated hydrocarbons having a double bond, a triple bond, and the like, in addition to saturated hydrocarbons. The cycloalkyl group includes monocyclic and bicyclic, tricyclic, and other polycyclic hydrocarbons.

[Resist composition]
The resist composition according to the present invention comprises a phenolic compound (A), an acid generator (B), and an aromatic ring having at least one phenolic hydroxyl group in one molecule and having a phenolic hydroxyl group. A basic nitrogen-containing compound (C) having a molecular weight of 400 to 3,000 having one or more substituents per molecule selected from a group consisting of a group and an alkoxymethyl group, and a crosslinkable compound (D). The phenolic compound (A) and the crosslinkable compound (D) may be the same compound.

  The resist composition according to the present invention uses a combination of the phenolic compound (A), the acid generator (B), and the basic nitrogen-containing compound (C) having the specific crosslinkable group and the phenolic hydroxyl group. Accordingly, it is possible to form a resist composition having improved dimensional fidelity capable of forming a resist pattern with a dimension faithful to a design dimension or a mask size of an electron beam and suppression of resist residue.

By using the above-mentioned specific basic nitrogen-containing compound (C) in combination with the phenolic compound (A) and the acid generator (B), the effect of exhibiting the above-mentioned effects has not been elucidated yet, but is as follows. It is estimated as follows.
A chemically amplified resist composition usually contains an acid generator component that generates an acid by irradiation with active energy rays (hereinafter, sometimes referred to as exposure). When an acid is generated from the acid generator by exposure, the acid acts as a catalyst, and in the case of a negative resist composition, many crosslinks occur between the alkali-soluble resin and the crosslinkable compound, and the alkali-soluble to alkali-insoluble Changes to Therefore, in the formation of a resist pattern, when selectively exposing a resist film made of a chemically amplified resist composition, a difference in alkali solubility occurs between an exposed portion and an unexposed portion. A pattern can be formed.
Incidentally, for example, when a negative resist composition is used as a coating film, each component of the resist composition and the acid generated from the acid generator diffuse in the coating film when heated in PEB. Presumed. Above all, if the generated acid moves in the coating film and diffuses into the unexposed area, it is presumed that the pattern is formed in the unexposed area where the pattern should not be formed, which deteriorates the resolution of the resist pattern. Is done. Therefore, it has been conventionally known to use an organic basic compound or the like in order to suppress such acid diffusion. However, a negative resist composition using a conventional organic basic compound has insufficient dimensional fidelity. Further, when a pattern is formed using a negative resist composition using a conventional organic basic compound, a problem that a resist residue is present in a space portion on a substrate is likely to occur.

On the other hand, the basic nitrogen-containing compound (C) used in the present invention has one or more phenolic hydroxyl groups in one molecule, and the aromatic ring having a phenolic hydroxyl group has a hydroxymethyl group and an alkoxymethyl group. It has one or more substituents selected from the group consisting of one or more in one molecule.
Since the molecule has a phenolic hydroxyl group, the basic nitrogen-containing compound (C) used in the present invention has alkali solubility in the unexposed area. Therefore, when a pattern is formed using the negative resist composition using the basic nitrogen-containing compound (C) of the present invention, the unexposed portion has improved solubility in an alkali developing solution, and the unexposed portion has a resist. It is presumed that the residue hardly remains and the generation of the resist residue in the space on the substrate is suppressed.
Further, since the aromatic ring having a phenolic hydroxyl group has one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, the basic nitrogen-containing compound (C) used in the present invention is And crosslinkability in the exposed area. Therefore, when a pattern is formed using the negative resist composition using the basic nitrogen-containing compound (C) of the present invention, the cross-linking property is improved in the exposed area, the film loss is further suppressed in the exposed area, and the electron It is presumed that dimensional fidelity for forming a resist pattern with dimensions faithful to the line design dimensions and mask size is improved.

  Further, the basic nitrogen-containing compound (C) used in the present invention has at least one phenolic hydroxyl group in one molecule, and a group consisting of a hydroxymethyl group and an alkoxymethyl group in an aromatic ring having a phenolic hydroxyl group. The compound has at least one substituent selected from the group consisting of at least one in one molecule, and thus has a high compatibility with the phenolic compound (A) and a relatively large molecular weight of 400 or more. Therefore, in the present invention, it is presumed that the uniformity in the resist coating film is increased and the diffusivity of the basic nitrogen-containing compound (C) is reduced. As described above, in the present invention, by suppressing the organic basic compound that diffuses to the exposed portion, in the exposed portion, the generated acid is suppressed from being neutralized more than expected, and in the unexposed portion, In order to prevent the acid generated from the exposed part from diffusing, the acid is present at a high concentration in the exposed part and the acid is not present in the unexposed part, that is, the acid at the boundary between the exposed part and the unexposed part. The density difference becomes clear. Therefore, the negative resist composition containing the basic nitrogen-containing compound (C) of the present invention has excellent resolution while maintaining the high sensitivity characteristic of a chemically amplified resist.

The resist composition of the present invention contains at least a phenolic compound (A), an acid generator (B), a specific basic nitrogen-containing compound (C), and a crosslinkable compound (D). The phenolic compound (A) and the crosslinkable compound (D) may be the same compound, and may contain other components as needed.
Hereinafter, each component of the resist composition of the present invention will be described in order.

<Phenolic compound (A)>
The phenolic compound (A) used in the present invention is a compound having a phenolic hydroxyl group. In the present invention, the “phenolic hydroxyl group” means a hydroxyl group directly bonded to an aromatic ring such as a benzene ring.

In the phenolic compound (A) used in the present invention, the number of phenolic hydroxyl groups in one molecule is not particularly limited. Above all, it is preferable to have two or more phenolic hydroxyl groups in one molecule from the viewpoint of improving the resolution of the pattern, and the phenolic compound (A) has three or more phenolic hydroxyl groups in one molecule. It is more preferable that the compound has four or more phenolic hydroxyl groups in one molecule. When there are four or more phenolic hydroxyl groups in one molecule, three-dimensional cross-linking becomes possible and the pattern strength is improved, so that a decrease in resolution due to pattern collapse after development can be suppressed, and the resolution is further improved. In addition, since more polar groups are present in the molecule, the interaction between the polar groups and the substrate is improved and the adhesion is improved, and the adhesion to the substrate leads to an improvement in resolution.
Above all, it is even more preferable that four or more benzene rings having a phenolic hydroxyl group are contained in one molecule from the viewpoint of the above effects.

The molecular weight of the phenolic compound (A) used in the present invention is not particularly limited. Above all, a phenolic compound having a molecular weight of 300 to 3000 is preferred from the viewpoint of achieving high resolution of the pattern.
When the molecular weight is 300 or more, the ability to form a resist film and the ability to form a pattern are excellent. When the molecular weight is 3,000 or less, swelling due to the solvent used in the resist composition is less likely to occur, pattern collapse is less likely to occur, and a good pattern shape can be obtained. The molecular weight in the present invention refers to the sum of the atomic weights of the atoms constituting the molecule. In the case of an oligomer having a molecular weight distribution, it is represented by a weight average molecular weight using GPC (in terms of polystyrene).
The molecular weight of the phenolic compound (A) used in the present invention is preferably from 500 to 2500, and more preferably from 600 to 2,000 from the viewpoint of film-forming properties and resolution.

  From the above, the phenolic compound (A) used in the present invention is preferably a phenolic compound having a molecular weight of 300 to 3000 and having two or more phenolic hydroxyl groups in one molecule.

The phenolic compound (A) used in the present invention preferably has a glass transition temperature (Tg) of 60 ° C. or higher, more preferably 90 ° C. or higher. When the glass transition temperature is 60 ° C. or higher, a dewetting phenomenon is less likely to occur when forming a coating film, and a uniform film is easily obtained. Note that the dewetting phenomenon refers to a phenomenon in which a spread coating film is dissolved during prebaking, repelling occurs, and a uniform film is not formed.
Here, the glass transition temperature is measured by a differential scanning calorimeter (DSC).

  Further, the phenolic compound (A) used in the present invention preferably has a solubility of at least 0.5% by weight at 23 ° C in an organic solvent having a boiling point of 80 to 180 ° C. In such a case, rapid drying of the resist film during spin coating can be prevented, and there is an advantage that a uniform resist film can be obtained. Representative examples of the organic solvent having a boiling point of 80 to 180 ° C include cyclopentanone, propylene glycol monomethyl ether, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl lactate, 2-heptanone, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, and the like. Is mentioned.

  Among them, the phenolic compound (A) used in the present invention has three or more phenolic hydroxyl groups in one molecule, has a glass transition temperature (Tg) of 60 ° C. or more, and has a boiling point of 80 to 180 ° C. The organic solvent preferably has a solubility of 0.5% by weight or more at 23 ° C.

The phenolic compound (A) used in the present invention has a development rate of 10 to 80 nm in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) from the viewpoint of improving the pattern shape and increasing the sensitivity. / Sec is preferably selected and used, and more preferably 15 to 35 nm / sec.
The developing rate for a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) is, for example, a 30% by weight solution of the phenolic compound (A), and the film thickness after drying on a silicon wafer is 1 μm. After forming the coating film so as to obtain, the film was immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) (aqueous solution temperature: 23 ° C.), and the time until the coating film was completely dissolved was measured. Can be calculated.

  Examples of the phenolic compound (A) include compounds represented by the following chemical formulas (2) and (4). The compound represented by the following chemical formula (2) is preferable from the viewpoint of obtaining a pattern having a high sensitivity, a high resolution and a good shape.

[In the chemical formula (2), R ¹ is each independently a group selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, and a group represented by the following chemical formula (3).

(In the chemical formula (3), R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q is an aryl group or a cycloalkyl group, and m is 1 or 2. Represents.)
R ² is independently a hydrogen atom or an organic group, and at least two of a plurality of R ² in one molecule are hydrogen atoms. R ³ is a halogen atom or a group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, and a nitro group. The alkyl group, cycloalkyl group, and aryl group each may have a substituent.
n1 represents an integer of 1 to 3, and n2 represents an integer of 0 to 2. However, a combination that satisfies n1 + n2 ≦ 4 is selected from the numerical range of n1 and n2. x1 represents an integer of 3 to 12. In addition, the groups represented by the same symbol included in the chemical formula (2) may be the same or different from each other. ]

(In the chemical formula (4), R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a hydroxymethyl group, or an alkoxymethyl group, or a combination thereof. A plurality of R ⁷ may combine to form a ring, a plurality of R ⁸ may combine to form a ring, and a plurality of R ⁹ may combine to form a ring The plurality of R ⁷ , R ⁸ and R ⁹ may be the same or different from each other.
R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a monovalent organic group, and a plurality of R ¹⁰ and R ¹¹ may be the same or different. Further, at least two of the plurality of R ¹⁰ and R ¹¹ are hydrogen atoms. Further, R ⁷ and / or R ⁹ may have at least one substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group.
W represents a single bond, an ether bond, a thioether bond, or an alkylene group, a cycloalkylene group, or an arylene group which may contain a hetero atom, or a group composed of any combination thereof. A plurality of W may be the same or different from each other.
x2 represents a positive integer.
When x2 is 1, R ⁶ may be the same as R ^7, and when x2 is 2 or more, R ⁶ is a (X2) -valent group, and has an ether bond, a thioether bond, or a hetero atom. Represents an alkylene group, a cycloalkylene group, or an arylene group, or a group composed of any combination of these;
y1 represents an integer of 0 or more, and when W is a single bond, y1 is 0.
y2 represents an integer of 0 or more, and y3 represents a positive integer.
z represents an integer of 0 or more.
v represents an integer of 0 or more.
k1 and k4 represent a positive integer.
k2, k3, and k5 each independently represent an integer of 0 or more. However, k1 + k2 + z = 5, k3 + v = 3, k4 + k5 = 5, and k2 + k5 ≧ 2 are satisfied. )

In the compound represented by the chemical formula (2), the alkyl group for R ¹ is not particularly limited, but is preferably an alkyl group having 1 to 18 carbon atoms. The alkyl group may be linear or branched. Examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, an i-butyl group, a t-butyl group, an i-pentyl group, a t-pentyl group, and a hexadecyl group. Further, it may have an unsaturated bond such as a double bond or a triple bond.

  Examples of the substituent of the alkyl group include a hydroxyl group, an alkoxy group, and a halogen atom.

The cycloalkyl group for R ¹ is not particularly limited, and includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like. Further, it may have an unsaturated bond such as a double bond or a triple bond, and may be monocyclic or polycyclic. As the cycloalkyl group, a cyclohexyl group is preferable.

  The substituent of the cycloalkyl group is not particularly limited, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, and a halogenoalkyl group.

  The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a 2-ethylhexyloxy group.

  The alkoxyalkyl group is not particularly limited, but is preferably an alkoxyalkyl group having 1 to 8 carbon atoms, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and a methoxypropyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The halogenoalkyl group is not particularly limited, but is preferably a halogenoalkyl group having 1 to 8 carbon atoms, for example, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, Fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-chloroethyl group, 1-bromoethyl group, 1-fluoroethyl group, 1,2-dichloroethyl group, 1,1,2,2-tetrachloroethyl group and the like. No.

The aryl group represented by R ¹ is not particularly limited, but preferably has 6 to 14 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms. For example, a phenyl group, a naphthyl group , Biphenyl, anthryl group and the like.

Examples of the substituent of the aryl group include a cycloalkyl group, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, and a halogenoalkyl group.
Examples of the cycloalkyl group as a substituent of the aryl group include the same as the above-described cycloalkyl group. Further, the cycloalkyl group may have a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, and an alkoxy group.
The alkyl group having 1 to 5 carbon atoms, the alkoxy group, the alkoxyalkyl group, the halogen atom, and the halogenoalkyl group as the substituents of the aryl group are as described above for the cycloalkyl group.

In the above chemical formula (3), R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms may be linear or branched, and among them, a methyl group and an ethyl group are preferred from the viewpoint of achieving both high sensitivity and solvent solubility. When m is 2, two R ⁴ and R ⁵ may be the same or different.
In the above chemical formula (3), the case where both R ⁴ and R ⁵ are hydrogen atoms is preferably used.

  As the aryl group for Q in the above chemical formula (3), the same as the above aryl group can be mentioned. The substituent which the aryl group of Q has is the same as the substituent which the aryl group has. In addition, as the cycloalkyl group of Q in the above chemical formula (3), the same as the above cycloalkyl group can be mentioned. The substituent which the cycloalkyl group of Q has is the same as the substituent which the above-mentioned cycloalkyl group has.

The organic group for R ² is not particularly limited, and includes an alkyl group, a cycloalkyl group, and an aryl group.

As the alkyl group for R ² , those similar to the aforementioned R ¹ can be mentioned. As the substituent of the alkyl group for R ^2, the same substituents as those described above for R ¹ can be mentioned.

The cycloalkyl group of R ² and the substituent of the cycloalkyl group may be the same as those of R ¹ described above. The aryl group for R ^{2 and} the substituents on the aryl group can be the same as those for R ¹ above.

As the halogen atom and the alkyl group for R ³ , those similar to the aforementioned R ¹ can be mentioned.
The substituent of the alkyl group as R ³ is a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxy group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group. , An alkoxycarbonyl group, a cyano group, a nitro group and the like.

The cycloalkyl group of R ³ and the substituents of the cycloalkyl group can be the same as those of R ¹ described above. The aryl group of R ^{3 and} the substitution of the aryl group can be the same as those of the above R ¹ .
As the alkoxy group for R ³ , those similar to the aforementioned R ¹ can be mentioned.

The acyl group for R ³ is not particularly limited, but is preferably an acyl group having 1 to 8 carbon atoms, such as a formyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a pivaloyl group, and a benzoyl group. Can be

  x1 is an integer of 3 to 12, preferably an integer of 4 to 12, and more preferably an integer of 4 to 8.

As long as the compound represented by the chemical formula (2) has two or more phenolic hydroxyl groups, the substituents represented by the same symbol in each repeating unit may be the same or different. The positions of OR ² and R ³ in each repeating unit may be the same or different. Further, the numbers of n1 and n2 in each repeating unit may be the same or different. For example, in the compound represented by the chemical formula (2), when x1 is 4, all the repeating units may be the same as in the following chemical formula (5), or all the repeating units as in the following chemical formula (6). The repeating units may be different.

In the compound represented by the chemical formula (2), x1 is preferably 4, and n1 is preferably 2 or 3, from the viewpoint of obtaining a pattern having high sensitivity, high resolution, and good shape. x1 is 4, n1 is 2, it is preferable hydrogen atom of the eight R ² is a 2-8 calix resorcin arene derivatives. Further, it is preferable that the Rx is a Cax resorcinol allene derivative having 2 to 4 hydrogen atoms out of 8 R ² , and in particular, one of ² R ² in the repeating unit of the chemical formula (2) is a hydrogen atom. The other is an organic group, preferably a calixresorcinalene derivative having four hydrogen atoms in one molecule, from the viewpoint of achieving high sensitivity while using a high-concentration developer.

On the other hand, in the compound represented by the chemical formula (4), the alkyl group in R ⁷ , R ⁸ and R ⁹ may be linear or branched, and is preferably a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group. And a hexyl group, an octyl group and the like having 1 to 10 carbon atoms.
The cycloalkyl group for R ⁷ , R ⁸ and R ⁹ may be either monocyclic or polycyclic. For example, a group having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms can be mentioned. The number of carbon atoms is preferably from 6 to 30, particularly preferably from 7 to 25. For example, adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol Group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, cyclododecanyl group and the like. These alicyclic hydrocarbon groups may have a substituent.
The aryl group in R ⁷ , R ⁸ and R ⁹ may be the same as R ¹ described above.
When (x2) is 1 in the compound represented by the chemical formula (4), R ⁶ may be the same as R ⁷ . When (x2) is 2 or more, R ⁶ is a (x2) -valent group, which may contain an ether bond, a thioether bond, or a hetero atom, an alkylene group, a cycloalkylene group, or an arylene group; Alternatively, it represents a group consisting of any combination of these. An alkylene group, a cycloalkylene group, or an arylene group, which may contain an ether bond, a thioether bond, or a hetero atom in R ⁶ , or a group composed of any combination thereof is the same as W described later. good.

Examples of the substituent which the alkyl group, cycloalkyl group and aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom and an alkoxy group. These may be similar to those described above R ^1.

The organic group in R ¹⁰ and R ¹¹ is a group containing one or more carbon atoms, and examples thereof include an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an amide group, and a cyano group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl Group, cyclopropyl group, cyclobutyl group, cyclohexyl group, adamantyl group and the like. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. The aralkyl group is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a cumyl group. The alkoxy group in the alkoxy group and the alkoxycarbonyl group is preferably an alkoxy group having 1 to 5 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, and an isobutoxy group.

The alkylene group for W may be linear or branched and preferably has 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and an isobutylene group.
The cycloalkylene group for W may be either monocyclic or polycyclic, and examples of the alkylene group forming a ring include cycloalkylene groups having 3 to 8 carbon atoms (for example, cyclopentylene group, cyclohexylene group). be able to.
The alkylene group, cycloalkylene group, and arylene group in W may further have a substituent. As the substituent, an alkyl group (preferably having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc.), alkoxy group (preferably having 1 to 1 carbon atoms) 4, for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), fluorine atom, chlorine atom, bromine atom, iodine atom and the like.

Further, the alkylene chain and the cycloalkylene chain are represented by -O-, -OC (= O)-, -OC (= O) O-, -N (R) -C (= O)-, -N (R) -C (= O) O -, - S -, - SO -, - SO 2 - may contain. Here, R is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl) Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc.).
As the cyclic arylene group for W, those having 6 to 15 carbon atoms such as a phenylene group, a tolylene group and a naphthylene group are preferred.

When the phenolic compound (A) has two or more phenolic hydroxyl groups in one molecule, the phenolic hydroxyl group of a compound (mother nucleus compound) serving as a mother nucleus such as a polyhydric phenolic compound is protected with an organic group. You may.
Specific examples of the mother nucleus compound of the phenolic compound (A) are shown below, but the invention is not limited thereto. The phenolic hydroxyl group in the following specific examples may be protected by an organic group as long as two or more phenolic hydroxyl groups exist in one molecule.

  The nucleus compound of the phenolic compound (A) is commercially available from, for example, Honshu Chemical Industry Co., Ltd., Asahi Organic Material Industry Co., Ltd., and can be used. It can also be synthesized by condensation of various phenolic compounds with various aldehydes and ketones.

  Furthermore, the phenolic compound (A) used in the present invention may have a crosslinkable group. When the phenolic compound (A) has a crosslinkable group, the phenolic compound (A) can have both a function as a resist substrate and a function as a crosslinkable compound (D) described later. The compound (A) and the later-described crosslinkable compound (D) are used as the same compound.

  The crosslinkable group of the phenolic compound (A) is not particularly limited as long as the phenolic compound (A) can be crosslinked by the action of an acid. Among them, it is preferable to have a hydroxymethyl group or an alkoxymethyl group as a crosslinkable group, since the uniformity of the resist film is improved and a pattern with low line edge roughness can be obtained.

When the phenolic compound (A) having a crosslinkable group used in the present invention, that is, the phenolic compound (A) and the later-described crosslinkable compound (D) are the same compound, the phenolic hydroxyl group is contained in one molecule. Having at least one substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on the aromatic ring having a phenolic hydroxyl group, and having at least one substituent per molecule having a molecular weight of 400 to 3,000. It is preferably a phenolic compound (A '). By using such a phenolic compound (A ′), the phenolic compound (A) and the crosslinkable compound (D) become the same compound, and the number of components in the resist composition can be substantially reduced. A uniform resist film can be formed, and a pattern with high resolution and low line edge roughness can be obtained.
Hereinafter, such a phenolic compound (A ′) will be described in detail.

(Phenolic compound (A '))
The phenolic compound (A ') used in the present invention has two or more phenolic hydroxyl groups in one molecule, and is selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on an aromatic ring having a phenolic hydroxyl group. It is a phenolic compound having a molecular weight of 400 to 3000 and having at least one substituent in one molecule.

The phenolic compound (A ′) used in the present invention is characterized in that one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group are added to an aromatic ring having a phenolic hydroxyl group in one molecule. You only need to have more than one. At least one substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group functions as a crosslinkable group of the phenolic compound.
The phenolic compound (A ′) used in the present invention includes, in one molecule, one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on an aromatic ring having a phenolic hydroxyl group. It preferably has two or more, more preferably three or more in one molecule, and more preferably four or more in one molecule from the viewpoint of increasing the crosslinkability.

  Further, the substitution position of the hydroxymethyl group and the alkoxymethyl group on the aromatic ring having a phenolic hydroxyl group is not particularly limited, and may be any one of the ortho position, the meta position, and the para position, based on the position of the phenolic hydroxyl group. Is also good. Among them, from the viewpoint of easy synthesis, it is preferably substituted at the ortho or para position, more preferably at the ortho position, based on the phenolic hydroxyl group.

  As the alkoxymethyl group, those having 1 to 6 carbon atoms in the alkoxy group are preferable. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group , Sec-butoxymethyl group, t-butoxymethyl group, various pentyloxymethyl groups and the like. As the alkoxymethyl group, among them, a methoxymethyl group and an ethoxymethyl group are preferable from the viewpoint of improving sensitivity.

  Among the crosslinkable groups, among them, at least one substituent selected from the group consisting of a hydroxymethyl group, a methoxymethyl group, and an ethoxymethyl group at the ortho position of the phenolic hydroxyl group has high reactivity, It is preferable because the sensitivity is improved.

Since the phenolic compound (A ′) has the properties of the phenolic compound (A), the preferred embodiment of the phenolic compound (A) also applies to the phenolic compound (A ′).
Specific examples of the phenolic compound (A ′) include, for example, a nucleus compound such as the chemical formulas (A-1) to (A-36) exemplified in the phenolic compound (A) and having a phenolic hydroxyl group. Compounds having one or more substituents per molecule in the aromatic ring, which include at least one substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, may be mentioned.

Hereinafter, specific examples of the phenolic compound (A ′) are shown, but the present invention is not limited thereto. Two or more phenolic hydroxyl groups are present in one molecule, and one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group are added to the aromatic ring having a phenolic hydroxyl group in one molecule. If there are more than one, the phenolic hydroxyl group in the following specific examples may be protected by an organic group.
In the following formula, L is each independently a hydrogen atom or one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, and at least one L in one molecule is , One or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group existing at the ortho position of the phenolic hydroxyl group.

  The phenolic compound (A ') used in the present invention is obtained by substituting at least one kind selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on an aromatic ring having a phenolic hydroxyl group in a phenolic compound core compound. Can be obtained by introducing groups. As a method for introducing a substituent functioning as a crosslinkable group into a core compound of a phenolic compound, for example, a method of reacting a phenol compound having no corresponding hydroxymethyl group with formaldehyde in the presence of a base catalyst. Can be. At this time, in order to prevent a side reaction such as gelation, the reaction is preferably performed at a temperature of 50 ° C. or lower. Various bisphenol derivatives having an alkoxymethyl group can be obtained by reacting a corresponding bisphenol derivative having a hydroxymethyl group with an alcohol under an acid catalyst. At this time, in order to prevent side reactions such as gelation, the reaction is preferably performed at a temperature of 100 ° C. or lower.

In the resist composition according to the present invention, the phenolic compound (A) may be used alone or as a mixture of two or more of the above compounds. Among the phenolic compounds (A), those belonging to the phenolic compound (A ′) and those not belonging to the phenolic compound (A ′) may be used in combination.
However, in the resist composition according to the present invention, it is preferred that the phenolic compound (A) having the same structural formula has a purity of 90% by weight or more from the viewpoint of improving low line edge roughness. In the phenolic compound (A), the compounds having the same structural formula preferably have a purity of 90% by weight or more, more preferably 95% by weight or more.
It is presumed that when a phenolic compound (A) having a high purity of a compound having the same structural formula is used, development progresses uniformly, so that line edge roughness is reduced.
However, even if the phenolic compound (A) has the same structural formula but the purity of the compound is less than 90% by weight, the structure of the impurities is similar to the phenolic compound (A) and the compatibility is good. Can be suitably used.

  From the viewpoint of improving low line edge roughness, the phenolic compound used in the present invention preferably has no molecular weight distribution. The phenolic compound used in the present invention preferably has a small molecular weight distribution, even if it has a molecular weight distribution, and has a low molecular weight distribution (ratio <Mw> between weight average molecular weight <Mw> and number average molecular weight <Mn>). / <Mn> is preferably from 1.0 to 1.1.

The content of the phenolic compound (A) is preferably from 30 to 95% by weight, more preferably from 50 to 93% by weight, based on the total solids of the resist composition.
When the compound belongs to the phenolic compound (A '), its content is preferably from 70 to 98% by weight, and more preferably from 80 to 96% by weight, based on the total solids of the resist composition. Is more preferable.
In the present invention, the solid content means components other than the organic solvent among the components contained in the resist composition.

<Acid generator (B)>
In the present invention, the acid generator (B) can be used without particular limitation from known acid generators used in conventional chemically amplified resist compositions. Among them, an acid generator that generates an acid directly or indirectly by irradiation with an active energy ray having a wavelength of 248 nm or less is preferable.

  The acid generator (B) is preferably at least one selected from the group consisting of compounds represented by the following chemical formulas (7) to (12).

(In the chemical formula (7), R ¹² may be the same or different, and each is independently a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, 12 cyclic alkyl groups, a linear alkoxy group having 1 to 12 carbon atoms, a branched alkoxy group having 3 to 12 carbon atoms, a cyclic alkoxy group having 3 to 12 carbon atoms, a branched alkoxycarbonyl alkoxy having 5 to 10 carbon atoms group, a hydroxyl group, or a halogen atom, X ^- represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, or 6 to 12 carbon atoms A sulfonate ion having a halogen-substituted aryl group or a halide ion, and n is an integer of 0 to 5.)

(In the chemical formula (8), X ⁻ , R ¹³ and n are the same as X ⁻ , R ¹² and n in the chemical formula (7).)

(In the chemical formula (9), A is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an alkyleneoxy group having 1 to 12 carbon atoms (-R'-O-, wherein R 'is R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, or 6 to 12 carbon atoms. Is a halogen-substituted aryl group.)

(In the chemical formula (10), R ¹⁵ may be the same or different, and each is independently a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, A cyclic alkyl group having 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. A hydroxyl group, a halogen atom, or a haloalkyl group having 1 to 12 carbon atoms.)

(In the chemical formula (11), R ¹⁶ may be the same or different and are each independently a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, A cyclic alkyl group having 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Group, a halogen atom, or an alkoxy group having 1 to 12 carbon atoms.)

(In the chemical formula (12), R ¹⁷ may be the same or different, and each is independently a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms.)
The halogenated alkyl group preferably has 1 to 5 carbon atoms.

  The compound represented by the chemical formula (7), the compound represented by the chemical formula (8), the compound represented by the chemical formula (9), the compound represented by the chemical formula (10), and the compound represented by the chemical formula (11) Specific examples of the compound represented, the compound represented by the chemical formula (12), and other acid generators are described in paragraphs 0114, 0117, 0120, 0123, 0126, 0129, and 0130 of JP-A-2012-220850. Compounds that have been used.

One of these acid generators (B) may be used alone, or two or more thereof may be used in combination.
In the resist composition of the present invention, the content of the acid generator (B) is preferably 1 to 30 parts by weight, more preferably 1 to 25 parts by weight, based on 100 parts by weight of the phenolic compound (A). More preferably, it is 5 to 20 parts by weight. When the amount is less than this range, image formation cannot be performed. When the amount is too large, a uniform solution is not obtained, and a uniform coating film may not be obtained.
Therefore, the content of the acid generator (B) is preferably from 2 to 30% by weight, and more preferably from 4 to 20% by weight, based on the total solid content of the resist composition.

<Basic nitrogen-containing compound (C)>
The basic nitrogen-containing compound (C) used in the present invention has at least one phenolic hydroxyl group in one molecule, and is selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on an aromatic ring having a phenolic hydroxyl group. It is an organic basic compound having a molecular weight of 300 to 3000 and having one or more substituents in one molecule.
The basic nitrogen-containing compound (C) has a function of suppressing the acid generated from the acid generator (B) from diffusing and changing the composition before and after exposure, and has a resist pattern shape and stable with time in a storage state. Improve the properties. In the present invention, the use of the specific basic nitrogen-containing compound (C) can suppress the diffusion of the basic compound, so that the resolution can be improved without deteriorating the sensitivity. .
Further, since the basic nitrogen-containing compound (C) has a phenolic hydroxyl group, it has an alkali developing property in an unexposed portion and plays a role of reducing a resist residue in an unexposed portion.
Furthermore, since the basic nitrogen-containing compound (C) has at least one substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on the aromatic ring having a phenolic hydroxyl group, the substituent is It functions as a crosslinkable group in the exposed part. The basic nitrogen-containing compound (C) is also crosslinked at the exposed portion, whereby components eluted from the exposed portion at the time of development are further reduced, and the film loss at the exposed portion is suppressed, and dimensional fidelity is improved.

  The phenolic hydroxyl group may have one or more in one molecule of the basic nitrogen-containing compound (C). Above all, the basic nitrogen-containing compound (C) is preferred because the compatibility with the phenolic compound (A) is improved, the uneven distribution in the resist coating is suppressed, and the alkali solubility is improved. More preferably, one molecule has two or more phenolic hydroxyl groups.

The aromatic ring in the basic nitrogen-containing compound (C) is not particularly limited. For example, in addition to aromatic hydrocarbons such as benzene, naphthalene, and anthracene, heteroaromatic rings such as pyridine, pyrrole, and thiophene are exemplified. Among them, from the viewpoint of compatibility with the phenolic compound (A), the aromatic ring is preferably an aromatic hydrocarbon, and more preferably benzene.
The aromatic ring may be one or more in one molecule of the basic nitrogen-containing compound (C). Among them, from the viewpoint that the compatibility with the phenolic compound (A) is improved and uneven distribution in the resist coating film is suppressed, two aromatic rings are contained in one molecule of the basic nitrogen-containing compound (C). It is preferable to have at least three aromatic rings in one molecule.

  The basic nitrogen-containing compound (C) used in the present invention has a hydroxymethyl group on the aromatic ring having a phenolic hydroxyl group in order that a crosslinkable group reacts after exposure and suppresses elution from an exposed portion during alkali development. And one or more substituents selected from the group consisting of an alkoxymethyl group and an alkoxymethyl group. When one or more substituents selected from the group consisting of the hydroxymethyl group and the alkoxymethyl group have two or more substituents in one molecule, it is preferable because they can be a crosslinking agent with other molecules.

  Further, the substitution position of the hydroxymethyl group and the alkoxymethyl group on the aromatic ring having the phenolic hydroxyl group is not particularly limited, but, as in the case of the phenolic compound (A ′), based on the phenolic hydroxyl group, It is preferably substituted at the ortho or para position, more preferably at the ortho position.

The basic nitrogen-containing compound (C) used in the present invention contains a nitrogen-containing basic group. In order to make the compound as a whole basic, it usually has no acidic group.
Examples of the nitrogen-containing basic group include an amino group and a basic nitrogen-containing heterocyclic group. Examples of the nitrogen-containing heterocyclic ring constituting the basic nitrogen-containing heterocyclic group include imidazole, pyridine, piperidine, pyrrolidine, morpholine, piperazine, benzimidazole, phenothiazine, phenoxazine, phenazine and the like.
In the present invention, it preferably has at least one of an amino group and a basic nitrogen-containing heterocyclic group, and particularly preferably has at least one of a tertiary amino group and a basic nitrogen-containing heterocyclic group. It preferably has a tertiary amino group.

  The basic nitrogen-containing compound (C) used in the present invention has at least one nitrogen-containing basic group in one molecule, but may have two or more nitrogen-containing basic groups in one molecule.

  The basic nitrogen-containing compound (C) used in the present invention has a developing rate of 5.38% by weight of a tetramethylammonium hydroxide (TMAH) aqueous solution of 5 to 5% in view of dimensional fidelity and suppression of resist residue. It is preferable that the number of phenolic hydroxyl groups, the number of nitrogen-containing basic groups, and the structure such as a skeleton containing an aromatic ring be appropriately adjusted and used so as to be 150 nm / sec.

  The molecular weight of the basic nitrogen-containing compound (C) used in the present invention is from 400 to 3,000. When the molecular weight is 400 or more and 3000 or less, a resist composition using the basic nitrogen-containing compound (C) can have excellent resolution while maintaining high sensitivity. If the molecular weight is too small, the basic nitrogen-containing compound (C) may easily diffuse in the coating film. On the other hand, if the molecular weight is too small, the basic nitrogen-containing compound (C) tends to volatilize, which may contaminate the inside of the apparatus or change the sensitivity over time, so that a predetermined line width may not be maintained. On the other hand, when the molecular weight is too large, the molecular weight of the basic nitrogen-containing compound (C) is preferably 2,000 or less, more preferably 1,500 or less, since swelling is likely to occur.

  In the present invention, the basic nitrogen-containing compound (C) has at least two phenolic hydroxyl groups in one molecule and is selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on an aromatic ring having a phenolic hydroxyl group. A tertiary amino group to at least one of the phenolic hydroxyl groups of the phenolic compound (A ′) having one or more substituents in one molecule by using a Williamson synthesis reaction, an ester synthesis reaction or the like. It is preferable to obtain at least one of the basic nitrogen-containing heterocyclic groups by introducing at least one phenolic hydroxyl group in one molecule.

More specifically, as shown below, the phenolic hydroxyl group of the phenolic compound (A ′) is reacted with an alkyl halide having a basic group represented by the following formula (A) by a Williamson synthesis reaction. The following formula (1) wherein at least one hydrogen atom of the phenolic hydroxyl group of the phenolic compound (A ') is substituted with -R ^a -Base of the following formula (A) Is preferably a basic nitrogen-containing compound (C) having a partial structure represented by In such a case, the basic nitrogen-containing compound (C) can be selected from various structures having high compatibility with the phenolic compound (A) and can be combined with the phenolic compound (A). The uniformity of the composition is improved, and the resolution can be improved without lowering the sensitivity.

(In the above formulas, R ^a represents a hydrocarbon group which may contain a hetero atom, Base is a group represented by the following formula (1-a), or, better basic may have a substituent Represents a nitrogen-containing heterocyclic group, R ^d is a substituent, s represents the number of substituents, and is 0 to 4. X is a halogen atom.

(In the above formula, R ^b and R ^c each independently represent a hydrocarbon group which may contain a hetero atom, and R ^b and R ^c may be the same or different.)

Examples of the hydrocarbon group which may contain ^a hetero atom in ^Ra include an alkylene group, a cycloalkylene group, an arylene group and a combination thereof which may contain a hetero atom, and W in the above formula (4) And an alkylene group, a cycloalkylene group, an arylene group, and a combination thereof, which may contain a hetero atom.
^Ra is preferably an alkylene group, a cycloalkylene group, an arylene group, or a combination thereof, and more preferably an alkylene group, in view of flexibility and solubility in a resist solvent.

Examples of the hydrocarbon group which may include a hetero atom in R ^b and R ^c include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, and a combination thereof (such as an aralkyl group and an alkylaryl group). ). These hydrocarbon groups may contain a bond of a hetero atom or a substituent in the hydrocarbon group, and they may be linear or branched. The bond other than the hydrocarbon group such as a hetero atom in the hydrocarbon group may be the same as the bond of the hetero atom contained in the alkylene group or the cycloalkylene group in W in the formula (4).

Examples of the cyclic structure of the basic nitrogen-containing heterocyclic group which may have a substituent include the aforementioned basic nitrogen-containing heterocyclic ring. The substituent that may be the cyclic structure has, may be similar to the following R ^d.

The alkyl group in R ^b and R ^c is preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, -Ethylhexyl, octyl, cyclopropyl, cyclobutyl, cyclohexyl, adamantyl and the like. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, a biphenyl group, and an anthracenyl group. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a cumyl group. The alkylaryl group is preferably an alkylaryl group having 7 to 20 carbon atoms, and examples thereof include various alkylphenyl groups and various alkylnaphthyl groups.

The hydrocarbon group for R ^a , R ^b and R ^c may have a substituent, and the substituent is not particularly limited, and may be a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a silyl group, an alkoxy group. , A nitro group, an acyl group, an acyloxy group, an amino group and the like.

R ^d is a substituent, and is composed of an alkyl group, a cycloalkyl group, an aryl group, a hydroxymethyl group, an alkoxymethyl group, a halogen atom, an alkoxy group, an acyl group, a cyano group, a nitro group, a hydroxyl group, or a combination thereof. Groups.
R ^d is preferably an alkyl group, a cycloalkyl group, an aryl group, a hydroxymethyl group, an alkoxymethyl group, or a group composed of a combination thereof.
Specific examples of R ^d may be the same as those of R ³ and R ⁷ .

In the present invention, the base having a partial structure represented by the following formula (1 ′), wherein at least one of R ^d is one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group. The nitrogen-containing compound (C) is a preferred structure.

(In the above formula, R ^a , Base and R ^d are the same as in formula (1). S ′ represents the number of substituents and is 0 to 3. L ′ is a hydroxymethyl group and an alkoxymethyl group. One or more substituents selected from the group consisting of :)

  Examples of the basic nitrogen-containing compound (C) used in the present invention include compounds represented by the following (1-1).

(In the formula (1-1), R ^a and Base are the same as those in the formula (1). Ar is an n-valent organic group having an aromatic ring, and n is an integer of 1 or more.) However, one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group are contained in one molecule of the aromatic ring having a phenolic hydroxyl group and one or more phenolic hydroxyl groups in one molecule. It has one or more.)

The n-valent organic group having an aromatic ring of Ar has at least one phenolic hydroxyl group in one molecule, and is selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group in the aromatic ring having a phenolic hydroxyl group. The substituent is not particularly limited as long as it has one or more substituents in one molecule, and may further have a substituent on the aromatic ring. Or it may be a combination with an unsaturated cycloalkyl group. The substituent of the aromatic ring may be the same as ^Rd described above.

Examples of the combination of an aromatic ring with a saturated or unsaturated alkyl group or a saturated or unsaturated cycloalkyl group include the chemical formulas (A-1) to (A-36) and the chemical formulas described in the examples of the phenolic compound (A). Various carbon skeletons such as (a-1) to (a-47) are exemplified.
Examples of the basic nitrogen-containing compound (C) used in the present invention include at least one phenolic hydroxyl group represented by any one of the chemical formulas (a-1) to (a-47) described in the example of the phenolic compound (A ′). And the above-mentioned —R ^a —Base is substituted.
The -R ^a -base, for example, there may be mentioned groups represented by the following formula, but is not limited thereto. Among them, it is preferable that at least one of R ^b and R ^c is an aralkyl group from the viewpoint of structural similarity with the phenolic compound.
In the following formula, X represents a part that bonds to an oxygen atom.

  The basic nitrogen-containing compound (C) used in the present invention preferably has the same carbon skeleton as the phenolic compound (A) used in combination from the viewpoint of improving compatibility. Here, the same carbon skeleton as the phenolic compound refers to a portion of the phenolic compound from which a hydroxyl group and other substituents have been removed.

  These basic nitrogen-containing compounds (C) can be used alone or in combination of two or more. The compounding amount of the basic nitrogen-containing compound (C) is 0.01 to 15 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the phenolic compound (A). If the amount is less than 0.01 part by weight, the effect of the addition may not be obtained. On the other hand, if it exceeds 15 parts by weight, the sensitivity tends to decrease.

<Crosslinkable compound (D)>
The crosslinkable compound (D) used in the present invention is a compound which crosslinks the phenolic compound (A) by the action of an acid to make it hardly soluble in alkali. Therefore, a resist composition using the crosslinkable compound (D) can be used as a negative resist composition.
When the phenolic compound (A ′) is used, it is not necessary to separately include a crosslinkable compound. However, also in this case, a small amount may be added to improve the sensitivity and the resolving power accompanying the improvement in the pattern strength.
The crosslinkable compound (D) used in the present invention is not particularly limited. It can be arbitrarily selected from known cross-linkable compounds used in conventional chemically amplified resist compositions.
Specific examples include compounds described in paragraphs 0151 to 0156 of JP-A-2012-220850.

In the present invention, the crosslinkable compound (D) can be used alone or in combination of two or more.
When the crosslinkable phenolic compound (A ′) is not used, the compounding amount of the crosslinkable compound (D) is 3 to 40 parts by weight, preferably 3 to 30 parts by weight based on 100 parts by weight of the phenolic compound (A). Department. If the compounding amount of the crosslinkable compound (D) is less than 3 parts by weight, the crosslinking may not proceed sufficiently, and a good resist pattern may not be obtained. On the other hand, when the amount exceeds 40 parts by weight, the storage stability of the resist solution is reduced, and the sensitivity may be deteriorated with time.

<A resin (E) having a repeating unit represented by the chemical formula (13) and having solubility in an alkali developing solution>
The resist composition of the present invention further comprises a resin (E) having a repeating unit represented by the following chemical formula (13) and having solubility in an alkali developing solution (hereinafter, also referred to as an alkali-soluble polymer (E)). May be contained.

(In the chemical formula (13), Z is a halogen atom, a cyano group, a nitro group, an alkyl group, an acyl group, an acyloxy group, an alkylsulfonyl group, or an alkoxy group. When there are a plurality of Zs, even if the Zs are the same, R ¹⁸ is a hydrogen atom, a methyl group, a halogen atom, a cyano group, or a trifluoro group, p represents an integer of 2 to 4, q represents an integer of 1 to 3, and p + q = 5. Is.)

Specific examples of Z and R ¹⁸ in the chemical formula (13) may be the same as those described in paragraph 0160 of JP-A-2012-220850.
Further, as a specific example of the repeating unit represented by the chemical formula (13), a repeating unit described in Paragraph 0162 of JP-A-2012-220850 can be mentioned.

  The alkali-soluble polymer (E) has, in addition to the above-mentioned repeating units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are generally required characteristics of resist. Various recurring units can be included for control purposes.

Examples of such a repeating unit include repeating structural units corresponding to the following monomers, but are not limited thereto. Examples include compounds having one addition-polymerizable unsaturated bond selected from acrylic acid and esters, methacrylic acid and esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Specific examples thereof include monomers described in paragraphs 0165 to 172 of JP-A-2012-220850.
In addition, as long as it is an addition-polymerizable unsaturated compound copolymerizable with the monomer corresponding to the above various repeating units, it may be copolymerized. Further, the monomer to be copolymerized may further have a substituent.

  The content of the repeating unit represented by the chemical formula (13) in the alkali-soluble polymer (E) is preferably from 40 to 100 mol%, more preferably from 70 to 100 mol%.

  Further, the weight average molecular weight of the alkali-soluble polymer (E) is preferably from 2,000 to 80,000, and more preferably from 2,500 to 8,000.

  The content of the alkali-soluble polymer (E) is preferably from 0.5 to 70% by weight, more preferably from 1 to 50% by weight, based on the total solid content.

<Other ingredients>
The resist composition of the present invention may further contain additives that are optionally miscible, such as an additional resin for improving the performance of the resist film, a surfactant for improving coating properties, a dissolution inhibitor, and a plasticizer. , A stabilizer, a coloring agent, an antihalation agent and the like can be appropriately added and contained.

<Preparation of negative resist composition>
The negative resist composition according to the present invention is usually prepared by adding the above-mentioned phenolic compound (A), acid generator (B), basic nitrogen-containing compound (C) and crosslinkable compound (D) to an organic solvent (F). And, if necessary, by uniformly mixing other additives.

As the organic solvent (F), those generally used as a solvent for a chemically amplified resist can be used. Specific examples include an organic solvent described in paragraph 0179 of JP-A-2012-220850. In the present invention, among these organic solvents (F), in addition to diethylene glycol dimethyl ether, cyclohexanone, cyclopentanone, 1-ethoxy-2-propanol, and ethyl lactate, which have the highest solubility of the acid generator in the resist component, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and their mixed solvents, which are safe solvents, are preferably used.
The amount of the solvent in the resist composition is not particularly limited, and is appropriately set at a concentration that can be applied to a substrate or the like and according to the applied film thickness. Generally, the solvent is used so that the solid content concentration of the resist composition is preferably in the range of 0.5 to 20% by weight, more preferably 0.5 to 15% by weight.

  The resist composition of the present invention can be suitably used in a microlithography process for manufacturing a miniaturized electronic component such as for forming a gate layer of a semiconductor integrated circuit and for processing a mask pattern formed on a glass substrate. Can be.

[Electronic components]
The present invention also provides an electronic component at least partially formed of the resist composition according to the present invention or a cured product thereof. The electronic component according to the present invention includes a resist composition or a cured product thereof in any of the configurations including the resist composition or the cured product thereof, and the other configurations are the same as those of the conventionally known configuration. Things. Examples of the electronic component according to the present invention include a MEMS (micro electro mechanical device) component, a micro mechanical component, a micro fluid engineering component, a μ-TAS (micro total analyzer) component, an inkjet printer component, a micro reactor component, Electrically conductive layers, metal bump connections, LIGA (lithographic electroforming) parts, molds and dies for microinjection and micro stamping, screens or stencils for precision printing, parts for MEMS and semiconductor packages, and UV ( (UV) Printed wiring boards that can be processed by lithography.

[Method of manufacturing resist pattern]
The method of manufacturing a resist pattern according to the present invention,
(I) a step of applying a negative resist composition according to the present invention on a substrate and then performing a heat treatment to form a resist film; and (ii) exposing, heating and developing the resist film. It is characterized by including.

  According to the method for manufacturing a resist pattern according to the present invention, a pattern having a good shape can be formed with high sensitivity and high resolution.

Hereinafter, each of the steps will be described.
(I) A step of applying a resist composition according to the present invention onto a substrate and then performing a heat treatment to form a resist film In this step, first, the above-described resist composition is applied onto the substrate.
The application method is not particularly limited as long as the method can uniformly apply the resist composition on the substrate surface, and various methods such as a spray method, a roll coating method, a slit coating method, and a spin coating method are used. be able to.

Next, the resist composition applied on the substrate is subjected to pre-baking (PAB) to remove the organic solvent (F) to form a resist film.
The temperature of prebaking may be appropriately determined depending on the components of the composition, the proportion used, the type of the organic solvent (F), and the like, and is usually 70 to 160 ° C, preferably 90 to 130 ° C. The pre-bake time is usually about 30 seconds to 15 minutes.

(Ii) Step of Exposing, Heating, and Developing the Resist Film In this step, first, the resist film is exposed to, for example, an active energy ray having a wavelength of 248 nm or less. For example, by using an exposure apparatus such as an electron beam lithography apparatus or an EUV exposure apparatus, the resist film is exposed through a mask having a predetermined pattern shape, or drawn by direct irradiation of an electron beam without passing through the mask. And selectively exposing.
The exposure light source is not particularly limited, ArF excimer laser, KrF excimer laser, _{F 2} excimer laser, EUV (Extreme Ultraviolet: extreme ultraviolet), electron beam, can be performed using X-rays.
Next, after exposure, post-exposure bake (Post Exposure Bake, PEB) is performed. The conditions of the PEB treatment are usually 70 to 160 ° C., preferably 90 to 130 ° C., for about 0.1 to 15 minutes.
Next, the substrate that has been subjected to the PEB processing is developed using an alkaline developer to remove unexposed portions.
Examples of the developing method include a spray method, a slit method, a liquid filling method, a dipping method, and a shaking dipping method.
As the alkali developer of the resist composition of the present invention, a conventionally known alkali developer can be used. For example, an aqueous solution of an alkali described in paragraph 0186 of JP-A-2012-220850 is used. be able to. Further, an appropriate amount of an alcohol such as isopropyl alcohol or a surfactant such as a nonionic surfactant may be added to an aqueous solution of the above alkalis. Among these alkali developing solutions, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are preferable.

  When an aqueous solution of tetramethylammonium hydroxide (TMAH) is used as the alkali developer, the concentration of the aqueous solution of tetramethylammonium hydroxide is preferably 0.1% to 5%, more preferably 0.5%. ３3%, particularly preferably 1.19% to 2.38%. A 2.38% strength aqueous tetramethylammonium hydroxide solution is generally the most readily available in the semiconductor industry. Further, when the concentration of the tetramethylammonium hydroxide aqueous solution is less than 0.1%, the developer is neutralized by carbon dioxide in the air, and the sensitivity fluctuates, and it is difficult to obtain a stable product. Become.

  After the development treatment, a rinsing treatment is performed, and the alkali developing solution on the substrate and the resist composition dissolved by the alkali developing solution are washed away and dried to obtain a resist pattern.

  Note that the present invention is not limited to the above embodiment. The above embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and has the same effect. Within the technical scope of

Hereinafter, the present invention will be described specifically with reference to examples. The description is not intended to limit the invention.
The structure and physical properties in the following production examples were confirmed using the following apparatus.
-MALDI-TOF MS: The measurement was performed using REFLEX II 1,8,9-trihydroxyanthracene as a matrix, manufactured by BRUKER.
· ¹ H-NMR: BRUKER Co., AVANCE 400
・ High performance liquid chromatography (HPLC): LC-10ADvp, manufactured by Shimadzu Corporation
Temperature: 40 ° C., flow rate: 0.5 mL / min, column: VP-ODS (4.7 mm × 150 mm), detector SPD-M10Avp, mobile phase: acetonitrile / water = 8/2. .

(Preparation of phenolic compounds and basic nitrogen-containing compounds)
<Phenolic compound (A-1)>
A phenolic compound (A-1) (trade name TekOC-4HBPA: Honshu Chemical Industry Co., Ltd.) represented by the following chemical formula (14) was obtained.

<Production Example 1: Synthesis of phenolic compound (A-2)>
The phenolic compound (A-2) represented by the following chemical formula (15) was synthesized with reference to paragraphs 0210 to 0211 of JP-A-2012-22050.

<Production Example 2: Synthesis of phenolic compound (A-3)>
To a solution consisting of 20 mL of a 10% by weight aqueous potassium hydroxide solution and 20 mL of ethanol, 4.5 g (10 mmol) of a phenolic compound (TEOC-DF: Asahi Organic Materials Co., Ltd.) represented by the following chemical formula (16) was added, and the mixture was stirred at room temperature. To dissolve. To this solution, 14.0 mL (160 mmol) of a 37% formalin aqueous solution was slowly added at room temperature. Furthermore, after stirring at 40 ° C. for 24 hours under a nitrogen atmosphere, the mixture was poured into 200 mL of water in a beaker. While cooling in an ice bath, a 2.0 wt% acetic acid aqueous solution was slowly added until the pH reached 5.0. The precipitate was separated by filtration, sufficiently washed with water, and then dried to obtain a mixture of phenolic compounds into which 1 to 4 hydroxymethyl groups had been introduced. Purification was performed by high performance liquid chromatography to obtain a phenolic compound (A-3) represented by the following chemical formula (17).

<Production Example 3: Synthesis of phenolic compound (A-4)>
In the synthesis of the phenolic compound (A-3), instead of using the phenolic compound represented by the chemical formula (16), the phenolic compound (A-1) (TekOC-4HBPA: Honshu Chemical Industry Co., Ltd.) 6 0.3 g (10 mmol) and the addition amount of the 37% formalin aqueous solution was changed to 7.0 mL (80 mmol) in the same manner as in the synthesis of the phenolic compound (A-3). The phenolic compound (A-4) represented was synthesized.

<Production Example 4: Synthesis of phenolic compound (A-5)>
In a 300 mL three-necked flask, 16.6 g (0.1 mol) of 1,3-diethoxybenzene was dissolved in 400 mL of ethanol under a nitrogen atmosphere. While cooling this in an ice bath, 12.2 g (0.1 mol) of 4-hydroxybenzaldehyde was added, and then 20 mL of concentrated hydrochloric acid was slowly added dropwise, followed by reaction at 75 ° C. for 12 hours. After the reaction, the reaction solution was cooled in an ice bath, and the precipitated crystals were separated by filtration, washed with distilled water until neutral, and dried. Purification was performed by recrystallization using N, N-dimethylformamide as a solvent to obtain 9.6 g of a pale yellow phenolic compound represented by the following chemical formula (19).
In the synthesis of the phenolic compound (A-3), 1.1 g (1 mmol) of a phenolic compound represented by the following chemical formula (19) was used instead of using the phenolic compound represented by the chemical formula (16). Except for the above, a phenolic compound (A-5) represented by the following chemical formula (20) was synthesized in the same manner as in the synthesis of the phenolic compound (A-3).

<Production Example 5: Synthesis of basic nitrogen-containing compound (C-1)>
The phenolic compound (A-3) represented by the chemical formula (17) (2.3 g; 4.0 mmol), N- (2-chloroethyl) dibenzylamine hydrochloride (0.6 g; 2.2 mmol), carbonic acid The reaction was carried out by heating and refluxing potassium (1.5 g; 10.1 mmol) in acetone (30 ml) under an argon atmosphere for 24 hours. The mixture was extracted with ethyl acetate (50 ml) -water (150 ml), and the obtained organic layer was washed with water (150 ml), dried over anhydrous magnesium sulfate, and filtered, and the obtained filtrate was concentrated. Subsequently, preliminary purification was performed by silica gel column chromatography (developing solution: chloroform-methanol (85:15 (v / v)).
As a result of HPLC analysis, the obtained compound (mixture) was found to be a mixture (C-1m) of monosubstituted (C-1a) and disubstituted (C-1b) amino groups. The ratio of the mixture was 72% for 1-substituted product and 28% for 2-substituted product.
The resulting mixture; the basic nitrogen-containing compound (C-1m) was subsequently purified by high performance liquid chromatography (HPLC) to obtain a monosubstituted amino group represented by the chemical formula (21); A nitrogen compound (C-1a) and a disubstituted compound represented by the chemical formula (22); a basic nitrogen-containing compound (C-1b) were obtained.
The structures of the basic nitrogen-containing compound (C-1a) and the basic nitrogen-containing compound (C-1b) were confirmed by MALDI-TOF MS and ¹ H-NMR spectrum. Table 1 shows the results.

(In the above formula, two of the three A's are hydrogen atoms, and one is a substituent represented by the chemical formula (23).)

<Production Example 6: Synthesis of basic nitrogen-containing compound (C-2)>
In Preparation Example 5, N- (2-chloroethyl) dibenzylamine hydrochloride (0.6 g; 2.2 mmol) was used instead of N- (2-chloroethyl) diethylamine hydrochloride (0.3 g; 2.2 mmol). ) Was used in the same manner as in Production Example 5 to synthesize a basic nitrogen-containing compound (C-2) represented by the chemical formula (24). The structure of the basic nitrogen-containing compound (C-2b) was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum. Table 1 shows the results.

<Production Example 7: Synthesis of basic nitrogen-containing compound (C-3)>
Instead of using N- (2-chloroethyl) dibenzylamine hydrochloride (0.6 g; 2.2 mmol) in Production Example 5, N- (chloromethyl) piperidine hydrochloride (0.3 g; 2.2 mmol) In the same manner as in Production Example 5 except that was used, a basic nitrogen-containing compound (C-3) represented by the chemical formula (25) was synthesized. The structure of the basic nitrogen-containing compound (C-3) was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum. Table 1 shows the results.

<Production Example 8: Synthesis of basic nitrogen-containing compound (C-4)>
In Preparation Example 5, instead of using the phenolic compound (A-3) represented by the chemical formula (17) (2.3 g; 4.0 mmol), a phenolic compound represented by the chemical formula (18) ( A-4) (3.1 g; 4.0 mmol) was used in the same manner as in Production Example 5 to synthesize a basic nitrogen-containing compound (C-4) represented by the chemical formula (26). The structure of the basic nitrogen-containing compound (C-4) was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum. Table 1 shows the results.

<Production Example 9: Synthesis of basic nitrogen-containing compound (C-5)>
In Preparation Example 5, instead of using the phenolic compound (A-3) represented by the chemical formula (17) (2.3 g; 4.0 mmol), a phenolic compound represented by the chemical formula (20) ( A-5) (5.3 g; 4.0 mmol) was used in the same manner as in Production Example 5 to synthesize a basic nitrogen-containing compound (C-5) represented by the chemical formula (27). The structure of the basic nitrogen-containing compound (C-5) was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum. Table 1 shows the results.

<Comparative basic compound (RC-1)>
As the comparative basic compound (RC-1) (molecular weight: 353.7) represented by the following chemical formula (28), (product name: trioctylamine) was obtained from Tokyo Chemical Industry Co., Ltd.

<Comparative basic compound (RC-2)>
As a comparative basic compound (RC-2) (molecular weight: 287, 4) represented by the following chemical formula (29), (product name: tribenzylamine) was obtained from Tokyo Chemical Industry Co., Ltd.

<Comparative basic compound (RC-3)>
As the comparative basic compound (RC-3) (molecular weight: 191.3) represented by the following chemical formula (30), (product name 1- (3-hydroxybenzyl) piperidine) was obtained from Tokyo Chemical Industry Co., Ltd.

<Comparative basic compound (RC-4)>
In Preparation Example 5, instead of using the phenolic compound (A-3) represented by the chemical formula (17) (2.3 g; 4.0 mmol), a phenolic compound represented by the chemical formula (14) ( A-1) A basic compound represented by a chemical formula (31) in the same manner as in Production Example 5 except that TekOC-4HBPA (trade name: Honshu Chemical Industry Co., Ltd.) (2.5 g; 4.0 mmol) was used. A nitrogen-containing compound (RC-4) was synthesized.

<Acid generator>
The acid generator diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate (B-1) represented by the following chemical formula was obtained from Wako Pure Chemical Industries, Ltd.

<Crosslinkable compound>
As the crosslinkable compound (D-1) represented by the following chemical formula, (product name TM-BIP-A) was obtained from Asahi Organic Materials Industry Co., Ltd.

(Examples 1 to 11, Comparative Examples 1 to 6: Preparation of negative resist composition)
Each component was dissolved in propylene glycol monomethyl ether (F-1) in a blending amount as shown in Table 2, stirred for 12 hours, and then filtered through a 0.2 μm PTFE filter, to obtain Examples 1 to 11 and Comparative Examples 1 to 6. A negative resist composition was prepared.
The reason for the difference in parts by weight of the basic nitrogen-containing compound is that the number of moles of the basic compound used in Examples and Comparative Examples was adjusted.

<Evaluation: Formation of resist pattern>
Using the resist compositions of Examples 1 to 11 and Comparative Examples 1 to 6, resist patterns were formed by the following method and evaluated. Table 3 shows the results.

(1) Application of Resist Each of the resist compositions of Examples and Comparative Examples was uniformly applied on a 6-inch silicon substrate using a spinner, and prebaked (PAB) at 100 ° C. for 60 seconds to obtain a film thickness of 70 nm. Was formed.

(2) Formation of resist pattern The above resist-coated substrate was drawn using an electron beam drawing apparatus (acceleration voltage: 100 KV). After the drawing, baking (PEB) is performed at 100 ° C. or 110 ° C. for 60 seconds, development is performed with a 2.38% TMAH aqueous solution (23 ° C.) for 60 seconds, and rinsing is performed with pure water for 60 seconds. A line and space (L / S) pattern was formed.

<Evaluation>
(1) Sensitivity and Resolution The sensitivity was measured in μC / cm ² with the minimum irradiation dose at which a 100 nm L / S pattern was formed at a ratio of 1: 1. In addition, the limiting resolving power (line and space are separated and resolving) at the irradiation dose was defined as the resolving power. Confirmation of the resolution was determined by a length measuring SEM manufactured by Holon.

(2) Dimensional fidelity A line-and-space (L / S) pattern having a designed line width (50 nm and 30 nm) was formed at the above-mentioned dose measured as the sensitivity. The ratio of the line width of the actual line pattern to the design line width (50 nm and 30 nm) of the electron beam (actual line width / design line width of the electron beam) was calculated and evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: The ratio of the line width of the actual line pattern is 97% or more B: The ratio of the line width of the actual line pattern is 95% or more and less than 97% C: The ratio of the line width of the actual line pattern is less than 95%

(3) Resist Residue Evaluation was made based on the presence or absence of a residue on the substrate surface of a space pattern having a designed line width of 50 nm, which was measured as the sensitivity used in the dimensional fidelity evaluation.
[Evaluation criteria]
A: No residue
C: There is a residue

<Summary of results>
From the results shown in Table 3, in Examples 1 to 11, the desired fine patterns excellent in resolution, excellent in dimensional fidelity to the designed line width of the electron beam, and in which the resist residue was suppressed were obtained without impairing the sensitivity. Could be formed.
On the other hand, Comparative Examples 1 to 6 were inferior in dimensional fidelity, and Comparative Examples 1 to 3 were also inferior in resist residue.

Claims (5)

A phenolic compound (A), an acid generator (B), an aromatic ring having at least one phenolic hydroxyl group in one molecule and having a phenolic hydroxyl group, and a hydroxymethyl group and an alkoxymethyl group. one or more substituents selected possess one or more in one molecule, a basic nitrogen-containing compound having a molecular weight of 400 to 3000 which have a tertiary amino group (C), and the crosslinkable compound (D) And the phenolic compound (A) and the crosslinkable compound (D) may be the same compound. A phenolic compound (A), an acid generator (B), an aromatic ring having at least one phenolic hydroxyl group in one molecule and having a phenolic hydroxyl group, and a hydroxymethyl group and an alkoxymethyl group. A phenolic compound (A) containing a basic nitrogen-containing compound (C) having a molecular weight of 400 to 3,000 having at least one selected substituent in one molecule and a crosslinkable compound (D); ) and the crosslinkable compound (D) is rather good even with the same compound, the basic nitrogen-containing compound (C) having a partial structure represented by the following formula (1), the negative resist composition.
In (the above formula (1), R ^a represents a hydrocarbon group which may contain a hetero atom, Base is a group represented by the following formula (1-a), or, may have a substituent Represents a good basic nitrogen-containing heterocyclic group, R ^d is a substituent, and s is the number of substituents, and is 0 to 4.)
(In the formula (1-a), R ^b and R ^c each independently represent a hydrocarbon group which may contain a hetero atom, and R ^b and R ^c may be the same or different from each other. .) The phenolic compound (A) and the crosslinkable compound (D) are the same compound, and the same compound has two or more phenolic hydroxyl groups in one molecule and has an aromatic ring having a phenolic hydroxyl group. to a phenolic compound having a molecular weight of 300 to 3000 with one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group 1 or more in one molecule (a '), according to claim 1 or 3. The negative resist composition according to item 2. (I) a step of applying the negative resist composition according to any one of claims 1 to 3 on a substrate, followed by heat treatment to form a resist film, and (ii) exposing the resist film to light. And a step of heating and developing the resist pattern.   An electronic component, at least a part of which is formed from the negative resist composition according to any one of claims 1 to 3 or a cured product thereof.