Non-chemical amplification type negative resist composition, and manufacturing method of resist pattern using the resist composition, and mold

Abstract

To provide a non-chemical amplification type negative resist composition useful for fine processing, and a manufacturing method of a resist pattern using the resist composition, and a mold.SOLUTION: A negative resist composition is a non-chemical amplification type and includes: a phenolic compound (A) with a molecular weight of 400 to 2500, having two or more phenolic hydroxyl groups in one molecule, and two or more substituent groups of one or more kinds selected from a group composed of a hydroxymethyl group and an alkoxymethyl group at an ortho position of a phenolic hydroxyl group, in one molecule; and a nitrogen-containing basic compound (B) with a molecular weight of 400 to 3000, having one or more aromatic rings in one molecule and one or more phenolic hydroxyl groups and / or phenoxy groups in one molecule. A content of the phenolic compound (A) is 70 mass% or more in a total solid of the negative resist composition. The negative resist composition includes substantially no acid generator.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a non-chemically amplified negative resist composition useful for microfabrication, and a method for manufacturing a resist pattern and a mold using the resist composition.

Background Art

[0002] In recent years, in the manufacture of semiconductor devices and display devices, pattern miniaturization has been rapidly progressing due to the advancement of lithography technology, and high resolution has been demanded. As a miniaturization technique, generally, the wavelength of the exposure light source is shortened. In addition to the currently used KrF excimer laser light, lithography using ArF, F2, EUV, X-rays, electron beams, and other charged particle beams as exposure light has been proposed.

[0003] In particular, pattern formation by electron beam and EUV exposure is regarded as a next-generation or next-next-generation lithography technology, and the development of a negative resist that satisfies the requirements of high sensitivity and high resolution for forming a gate layer of a semiconductor integrated circuit and for processing a mask pattern formed on a glass substrate is desired. In addition, the development of a resist having high resolution is also desired for the manufacture of an imprint mold that is an original plate for imprint lithography.

[0004] As a resist material for these, a chemically amplified photosensitive composition using an acid-catalyzed reaction has been used for the purpose of improving sensitivity. A negative chemically amplified photosensitive composition usually contains an acid generator that generates an acid upon irradiation with light, a crosslinking agent, a basic compound, etc. in an alkali-soluble resin that serves as a resist substrate. Such a photosensitive composition undergoes crosslinking between the resin and the crosslinking agent by the action of the acid generated from the acid generator upon exposure, changing from alkali-soluble to alkali-insoluble. In addition, the acid generated during the crosslinking reaction catalyzes the reaction to repeat, enabling pattern exposure with a smaller exposure amount.

[0005] Conventionally, in semiconductor lithography, a resist material using a polymer having a mass average molecular weight of about 5000 or more as an alkali-soluble resin serving as a resist substrate has been used. However, since such a polymer material has a large molecular weight and a wide molecular weight distribution, there is a limit to the reduction of resolution. Therefore, development of low molecular weight materials has been carried out as an alkali-soluble resin serving as a resist substrate. As an example of a negative resist using such a low molecular weight material as a resist substrate, a resist using calixresorcinolaren and its derivatives (Patent Document 1) can be mentioned.

[0006] In addition, the present applicant has proposed a chemically amplified or non-chemically amplified negative resist composition that has high line width stability after exposure in vacuum, high resolution, and can obtain a pattern with low line edge roughness. The composition contains a phenolic compound (A) having two or more phenolic hydroxyl groups in one molecule, and one or more substituents selected from the group consisting of hydroxymethyl groups and alkoxymethyl groups at the ortho position of the phenolic hydroxyl group, with a molecular weight of 400 to 2500. The content of the phenolic compound (A) in the total solid content of the negative resist composition is 70% by mass or more. (Patent Document 2) However, in Patent Document 2, the non-chemically amplified negative resist composition uses only the phenolic compound (A) as the solid content. The basic compound described in Patent Document 2 is only described as a quencher for suppressing the diffusion of the acid generated from the acid generator in the chemically amplified negative resist composition. There is no description at all about combining a basic compound with the phenolic compound (A) without using an acid generator in the non-chemically amplified negative resist composition.

[0007] In addition, the applicant of the present application aims to provide a resist composition that is excellent in resolution while maintaining the high sensitivity peculiar to chemically amplified resists, and includes a phenolic compound (A), an acid generator (B), and a nitrogen-containing basic compound (B) having a molecular weight of 400 or more and 3000 or less, which has one or more aromatic rings in one molecule and one or more phenolic hydroxyl groups and / or oxy groups (-O-) in one molecule. However, the basic compound described in Patent Document 3 is merely described as a quencher for suppressing the diffusion of the acid generated from the acid generator in a chemically amplified negative resist composition.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0009] Although conventional chemically amplified negative resist compositions are highly sensitized by acid generators, they are not suitable for, for example, tone exposure, and non-chemically amplified negative resist compositions are required. Conventional non-chemically amplified negative resist compositions still have insufficient sensitivity, and a non-chemically amplified negative resist composition capable of forming a pattern with high sensitivity and excellent resolution is required.

[0010] [[ID=…]] In view of the above circumstances, an object of the present disclosure is to provide a non-chemically amplified negative resist composition capable of forming a pattern that can be developed with alkali, has high sensitivity, and is excellent in resolution in pattern formation by irradiation with an electron beam, an ion beam, or EUV, and a method for manufacturing a resist pattern and a mold using the negative resist composition.

Means for Solving the Problems

[0011] One embodiment of the present disclosure is a phenolic compound (A) having two or more phenolic hydroxyl groups in one molecule, having two or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group in one molecule, and having a molecular weight of 400 to 2500, and a negative resist composition containing a nitrogen-containing basic compound (B) having one or more aromatic rings in one molecule and having one or more phenolic hydroxyl groups and / or phenoxy groups in one molecule, wherein the content of the phenolic compound (A) in the total solid content of the negative resist composition is 70% by mass or more, and substantially does not contain an acid generator, and provides a non-chemically amplified negative resist composition.

[0012] In the non-chemically amplified negative resist composition of the present disclosure, it is preferable that the nitrogen-containing basic compound (B) is a compound represented by the following formula (I) from the viewpoint of being able to form a pattern with high sensitivity and excellent resolution.

[0013]

Chemical formula

[0014] In the non-chemically amplified negative resist composition of the present disclosure, the nitrogen-containing basic compound (B) may not have one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group.

[0015] Another embodiment of the present disclosure includes a step of applying the non-chemically amplified negative resist composition according to the present disclosure onto a substrate, followed by heat treatment to form a resist film, and a step of exposing and developing the resist film with an electron beam, an ion beam, EUV, or X-ray, and provides a method for manufacturing a resist pattern.

[0016] Further, another embodiment of the present disclosure provides a mold having a concavo-convex pattern, wherein at least the convex portion contains a cured product of the non-chemically amplified negative resist composition according to the present disclosure.

Advantages of the Invention

[0017] According to the present disclosure, in pattern formation by irradiation with an electron beam, an ion beam, or EUV, an alkali-developable, highly sensitive, and excellent-resolution pattern can be formed, and a non-chemically amplified negative resist composition, a method for manufacturing a resist pattern using the negative resist composition, and a mold are provided.

Brief Description of the Drawings

[0018]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0019] Hereinafter, embodiments, examples, etc. of the present disclosure will be described with reference to the drawings and the like. However, the present disclosure can be implemented in many different modes and is not to be construed as being limited to the description of the embodiments, examples, etc. exemplified below. Also, for the purpose of making the description clearer, the drawings may schematically represent the width, thickness, shape, etc. of each part compared to the actual mode, but this is merely an example and does not limit the interpretation of the present disclosure. Further, in this specification and each drawing, elements similar to those described above with respect to the previously shown drawings may be denoted by the same reference numerals, and detailed descriptions may be omitted as appropriate. Also, for convenience of explanation, the terms "above" or "below" may be used in the description, but the up and down directions may be reversed. In this specification, when a certain configuration of a certain member or a certain region, etc. is said to be "above (or below)" another configuration of another member or another region, etc., unless otherwise specifically limited, this includes not only the case where it is directly above (or directly below) the other configuration, but also the case where it is above (or below) the other configuration, that is, the case where another component is included between them above (or below) the other configuration.

[0020] In the present disclosure, the "active energy ray" means far ultraviolet rays such as KrF excimer laser, ArF excimer laser, and F2 excimer laser, electron beam, ion beam, EUV, X-ray, etc. In the notation of a group (atomic group) in the present disclosure, a notation that does not indicate substitution and non-substitution includes both those having no substituent and those having a 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). The divalent bond of the alkylene group includes not only the case from different carbon atoms (for example, -CH2CH2-), but also the divalent bond from the same carbon atom (for example, -CH2-). Also, the alkyl group and cycloalkyl group include not only saturated hydrocarbons but also unsaturated hydrocarbons having double bonds, triple bonds, etc. The cycloalkyl group includes not only monocyclic but also polycyclic hydrocarbons such as bicyclic and tricyclic. In the present disclosure, the "phenolic hydroxyl group" means a hydroxyl group directly bonded to an aromatic ring such as benzene, and the "phenoxy group" means an oxy group (-O-) directly bonded to an aromatic ring such as benzene. In the present disclosure, the phrase "X and / or Y" means "(X), (Y), or (X and Y)". Further, in the present disclosure, the "~" indicating a numerical range is used to mean including the numerical values described before and after it as the lower limit value and the upper limit value. Hereinafter, the non-chemically amplified negative resist composition, the method for producing a resist pattern, and the mold of the present disclosure will be described in detail in order.

[0021] I. Non-chemically amplified negative resist composition The non-chemically amplified negative resist composition according to one embodiment of the present disclosure has two or more phenolic hydroxyl groups in one molecule, and two or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group in one molecule, and has a molecular weight of 400 to 2,500 phenolic compound (A), A negative resist composition containing a nitrogen-containing basic compound (B) having one or more aromatic rings in one molecule and one or more phenolic hydroxyl groups and / or phenoxy groups in one molecule, wherein the content of the phenolic compound (A) in the total solid content of the negative resist composition is 70% by mass or more, and substantially does not contain an acid generator. It is a non-chemically amplified negative resist composition.

[0022] The non-chemically amplified negative resist composition according to one embodiment of the present disclosure contains the specific phenolic compound (A) and the specific nitrogen-containing basic compound (B), so that in pattern formation by irradiation with an electron beam, an ion beam, or EUV, alkali development is possible, and a pattern with high sensitivity and excellent resolution can be formed. The action of exerting the above effects by combining and using the specific phenolic compound (A) and the specific nitrogen-containing basic compound (B) is not yet clarified, but is presumed as follows. The specific phenolic compound (A) is a relatively low-molecular-weight specific phenolic compound serving as a resist substrate, and one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group are introduced at the ortho position of the phenolic hydroxyl group as crosslinkable groups. That is, the specific phenolic compound (A) is a resist substrate that also functions as a crosslinking agent. The specific phenolic compound (A) has a high ratio of crosslinkable groups to hydroxyl groups, and the content of the phenolic compound (A) in the total solid content in the resist composition is high. Therefore, in the non-chemically amplified resist composition of the present disclosure, by irradiating active energy rays, the crosslinking reaction of the specific phenolic compound (A) by the crosslinkable groups proceeds without going through an acid. The hydroxymethyl group and the alkoxymethyl group introduced as crosslinkable groups have excellent chemical stability, but when the specific nitrogen-containing basic compound (B) is introduced therein, the reactivity is improved, and the crosslinking reaction can proceed even with lower active energy, so it is presumed that the sensitivity is improved. Since the above negative resist composition has a phenolic hydroxyl group, it is alkali-soluble. However, during resist pattern formation, upon exposure (irradiation with light) such as an electron beam, crosslinking bonds are formed between the above phenolic compounds (A) due to the presence of one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group present at the ortho position of the phenolic hydroxyl group, resulting in alkali-insolubility. Therefore, in resist pattern formation, when a resist film made of the negative resist composition is selectively exposed, the exposed portion becomes alkali-insoluble while the unexposed portion remains alkali-soluble and does not change, so a negative resist pattern can be formed by alkali development. In addition, the non-chemically amplified negative resist composition of the present disclosure uses the specific phenolic compound (A) having a relatively low molecular weight in a state where the solid content of the resist composition is high, and the specific nitrogen-containing basic compound (B) has a structure highly compatible with the specific phenolic compound (A). Therefore, the uniformity of the resist composition in the coating film is improved. Furthermore, since acid diffusion is not utilized during image formation, it is presumed that the resolution is excellent.

[0023] Hereinafter, each component of such a negative resist composition of the present disclosure will be described in detail in order. <Phenolic compound (A)> The phenolic compound (A) used in the present disclosure has two or more phenolic hydroxyl groups in one molecule, and has two or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group in one molecule, and is a compound having a molecular weight of 400 to 2500. By setting the molecular weight of the phenolic compound (A) within the above range, excellent resolution can be obtained.

[0024] The phenolic compound (A) used in the present disclosure only needs to have two or more phenolic hydroxyl groups in one molecule, and the number of phenolic hydroxyl groups in one molecule is not particularly limited. The phenolic compound (A) used in the present disclosure is preferably appropriately selected so as to have alkali solubility based on the following. It is preferable to select and use the phenolic compound (A) having a development rate of 0.5 nm / sec or more with respect to an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 25% by mass (23 ° C), and more preferably to select and use the one having a development rate of 1.0 nm / sec or more. By setting the alkali development rate of the alkali-soluble resin within the above range, the pattern shape can be improved.

[0025] For example, the development rate with respect to an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 25% by mass (23 ° C) can be measured and calculated by, for example, using the above phenolic compound (A) alone as a solution of 5% by mass, forming a coating film on a silicon wafer so that the film thickness after drying becomes 300 nm, immersing it in an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 25% by mass (23 ° C), and measuring the time until the coating film is completely dissolved.

[0026] The phenolic compound (A) used in the present disclosure may have two or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group in one molecule. One or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group function as a crosslinkable group of the phenolic compound. It is preferable that the phenolic compound (A) used in the present disclosure has three or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group in one molecule, and more preferably four or more in one molecule, from the viewpoint of enhancing crosslinkability.

[0027] 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, etc. can be mentioned. Among them, as the alkoxymethyl group, methoxymethyl group and ethoxymethyl group are preferable from the viewpoint of good sensitivity.

[0028] Among the crosslinkable groups, one or more substituents 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 are preferable from the viewpoint of high reactivity and good sensitivity.

[0029] As the phenolic compound (A) used in the present disclosure, a compound having a molecular weight of 400 to 2500 is selected and used. If the molecular weight is less than the lower limit value, the ability to form a resist film and the ability to form a pattern may be inferior. On the other hand, if the molecular weight exceeds the upper limit value, it is likely to swell by the solvent used in the resist composition, pattern collapse is likely to occur, and the shape of the pattern may deteriorate. The molecular weight here 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 the mass average molecular weight using GPC (polystyrene conversion). Among others, the molecular weight of the phenolic compound (A) used in the present disclosure is preferably from 500 to 2500, more preferably from 600 to 2000 from the viewpoints of film-forming property and resolution.

[0030] The phenolic compound (A) used in the present disclosure 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, dewetting is less likely to occur during film formation, and a uniform film is more easily obtained. The dewetting phenomenon refers to a phenomenon in which a spread coating film dissolves during pre-baking, repulsion occurs, and a uniform film is not formed. Generally, when a low-boiling solvent is used as the solvent for a resist composition, the resist film dries rapidly and a uniform film cannot be obtained. Therefore, in order to obtain a uniform resist film when applying by a spin coating method or the like, a solvent having a boiling point of 90 to 180°C is used. Since the resist film formed by the spin coating method contains a large amount of residual solvent, in order to remove this solvent and form a stable resist film, the resist substrate is heated on a hot plate at a temperature of 90°C or higher (pre-baking). However, when a phenolic compound having a glass transition temperature of less than 60°C is used, dewetting of the resist film may occur in the pre-baking step, and a uniform film may not be obtained. On the other hand, when a phenolic compound having a glass transition temperature of 60°C or higher is used, pre-baking at a high temperature becomes possible, and a uniform film can be obtained. In addition, a resist film excellent in environmental resistance (post-coating delay: PCD) can be obtained. Furthermore, the density dependence of the pattern generated during pattern formation by an electron beam can be suppressed. Also, in the dry etching step after resist pattern formation, a pattern excellent in etching resistance (capable of preventing melting of the pattern due to high temperature during etching) can be obtained. Here, the glass transition temperature is measured by a differential scanning calorimeter (DSC).

[0031] In addition, the phenolic compound (A) used in the present disclosure preferably has a solubility of 5% by mass or more at 23°C in an organic solvent having a boiling point of 80 to 180°C. In such a case, it is possible to prevent rapid drying of the resist film during spin coating, 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.

[0032] Among them, the phenolic compound (A) used in the present disclosure preferably has a glass transition temperature (Tg) of 60°C or higher and a solubility of 5% by mass or more at 23°C in an organic solvent having a boiling point of 80 to 180°C.

[0033] The phenolic compound (A) is not particularly limited and can be appropriately selected and used. For example, compounds represented by the following chemical formula (1) and chemical formula (3) can be mentioned.

[0034]

Chemical formula

[0035]

Chemical formula

[0036]

Chemical Formula

[0037] In the compound represented by the above chemical formula (1), the alkyl group of R 1 is not particularly limited, but an alkyl group having 1 to 18 carbon atoms is preferred. The alkyl group may be linear or branched. For example, 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, a hexadecyl group, etc. may be mentioned. Also, it may have an unsaturated bond such as a double bond or a triple bond.

[0038] Examples of the substituent of the alkyl group include a hydroxyl group, an alkoxy group, a halogen atom, a halogenoalkyl group, etc.

[0039] R 1 The cycloalkyl group of has no particular limitation, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc. Further, it may have an unsaturated bond such as a double bond or a triple bond, and may be either monocyclic or polycyclic. As the cycloalkyl group, a cyclohexyl group is preferable.

[0040] The substituent of the cycloalkyl group has no particular limitation, 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, a halogenoalkyl group, etc.

[0041] The alkyl group having 1 to 5 carbon atoms may be either linear or branched. Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc. Examples of the branched alkyl group include an i-propyl group, an i-butyl group, a t-butyl group, an i-pentyl group, a t-pentyl group, etc.

[0042] Further, the alkoxy group has no particular limitation, but an alkoxy group having 1 to 8 carbon atoms is preferable, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a 2-ethylhexyloxy group, etc.

[0043] The alkoxyalkyl group has no particular limitation, but an alkoxyalkyl group having 1 to 8 carbon atoms is preferable, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group, etc.

[0044] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0045] The halogenoalkyl group is not particularly limited, but a halogenoalkyl group having 1 to 8 carbon atoms is preferred. Examples thereof include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-chloroethyl group, a 1-bromoethyl group, a 1-fluoroethyl group, a 1,2-dichloroethyl group, a 1,1,2,2-tetrachloroethyl group, and the like.

[0046] R 1 The aryl group of R is not particularly limited, but preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. Examples thereof include a phenyl group, a naphthyl group, an anthryl group, and the like.

[0047] In addition, examples of the substituent of the aryl group include a hydroxymethyl group, an alkoxymethyl group, a cycloalkyl group, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, a halogenoalkyl group, and the like. Examples of the cycloalkyl group as the substituent of the aryl group are the same as those of the above 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, an alkoxy group, and the like. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an i-propyl group, and the like. The alkoxy group is not particularly limited, but an alkoxy group having 1 to 8 carbon atoms is preferred. Examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a 2-ethylhexyloxy group, and the like. The alkyl group having 1 to 5 carbon atoms, the alkoxy group, the alkoxyalkyl group, the halogen atom, the halogenoalkyl group, and the alkoxymethyl group as the substituent of the aryl group are as described above.

[0048] In the above chemical formula (2), R 4 and R 5are 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 either linear or branched, and among these, a methyl group and an ethyl group are preferred from the viewpoint of etching resistance. When m is 2, two R 4 and R 5 may be the same or different. In the above chemical formula (2), R 4 and R 5 and R 1 and R 2 are preferably hydrogen atoms.

[0049] The aryl group of Q in the above chemical formula (2) includes the same as the aryl group described above. The substituents of the aryl group of Q include the same as the substituents of the aryl group described above, and may include one or more substituents selected from the group consisting of a hydroxyl group, a hydroxymethyl group, and an alkoxymethyl group. Furthermore, the cycloalkyl group of Q in the above chemical formula (2) includes the same as the cycloalkyl group described above. The substituents of the cycloalkyl group of Q include the same as the substituents of the cycloalkyl group described above.

[0050] R 2 The monovalent organic group is not particularly limited, but examples thereof include an alkyl group, a cycloalkyl group, and an aryl group. R 2 The alkyl group of the above R 1 Similar examples include R 2 The substituents of the alkyl group in the above R 1 Examples include those similar to those in the above. Also, R 2 The cycloalkyl group and the substituents of the cycloalkyl group include the above R 1 Furthermore, R 2 The aryl group and the substituents of the aryl group include the above-mentioned R 1 The same can be used.

[0051] R 3 The alkoxymethyl group is as defined above. R 3 The halogen atom and alkyl group of the above R 1 The same can be mentioned. R 3 Examples of the substituent that the alkyl group has as the substituent include a cycloalkyl group, an aryl group, an amino group, an amido 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, and a nitro group.

[0052] R 3 The cycloalkyl group and the substituents of the cycloalkyl group include the above R 1 It can be similar to that of R 3 The aryl group and the substituents of the aryl group include the above-mentioned R 1 The same can be used. Also, R 3 The alkoxy group in the above R 1 The same can be mentioned.

[0053] R 3 The acyl group is not particularly limited, but is preferably an acyl group having 1 to 8 carbon atoms, and examples thereof include a formyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a pivaloyl group, and a benzoyl group.

[0054] x1 is an integer of 3 to 12, preferably an integer of 4 to 12, and more preferably an integer of 4 to 8.

[0055] The compound represented by the chemical formula (1) has two or more phenolic hydroxyl groups in one molecule, and one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho-position of the phenolic hydroxyl group, and the substituents represented by the same symbol in each repeating unit may be the same or different. 2 and R 3 The positions may be the same or different.

[0056] In the compound represented by the above chemical formula (1), from the viewpoint of obtaining a pattern with high sensitivity, high resolution, and good shape, among others, it is preferable that x1 is 4 and n1 is 2. Further, among the eight Rs where x1 is 4 and n1 is 2 2 is a calixresorcinaren derivative having 4 to 8 hydrogen atoms among the eight Rs, and 2 it is preferable to have at least one substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position where R is a hydrogen atom in one molecule. Also, in the compound represented by the above chemical formula (1), from the viewpoint of obtaining a pattern with high sensitivity, high resolution, and good shape, among others, it is preferable that x1 is 4 and n1 is 2. Further, among the eight Rs where x1 is 4 and n1 is 2 2 is a calixresorcinaren derivative having 0 to 8 hydrogen atoms among the eight Rs, and 1 it is preferable that R has an aryl group containing a phenolic hydroxyl group and 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.

[0057] On the other hand, in the compound represented by the above chemical formula (3), the alkyl groups in R 6 , R 7 , R 8 and R 9 may be linear or branched, and preferably include those having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group. R 6 , R 7 , R 8 and R 9The cycloalkyl group in may be either monocyclic or polycyclic. Examples include groups having a monocyclo, bicyclo, tricyclo, or tetracyclo structure having 5 or more carbon atoms. The number of carbon atoms is preferably 6 to 30, and particularly preferably 7 to 25, and examples thereof include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group. These alicyclic hydrocarbon groups may have a substituent. R 6 , R 7 , R 8 and R 9 The aryl group in the above R 1 It may be the same as: Also, R 6 , R 7 , R 8 and R 9 The hydroxymethyl group or alkoxymethyl group in may be the same as above. In the compound represented by the above chemical formula (3), R 6 If (x2) is an integer greater than or equal to 2, the group is (x2)-valent. R 6 When (x2) is an integer of 2 or more, R may be an (x2)-valent aliphatic hydrocarbon group, an (x2)-valent cyclic aliphatic hydrocarbon group, an (x2)-valent aromatic hydrocarbon group, or a group consisting of a combination thereof, for example, R 6 When (x2) is 2, it may be an alkylene group, a cycloalkylene group, an arylene group, or a group consisting of a combination thereof.

[0058] Examples of the substituent that the alkyl group, cycloalkyl group, and aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), a hydroxymethyl group, and an alkoxymethyl group.

[0059] R 10 and R11 The monovalent organic group in [reference] refers to an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an amide group, a cyano group, etc. The alkyl group is preferably an alkyl group or a cycloalkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, an adamantyl group, etc. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, etc. The aralkyl group is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a cumyl group, etc. 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, an isobutoxy group, etc.

[0060] The alkylene group in W may be linear or branched, and is preferably one having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, etc. The cycloalkylene group in W may be either a monocyclic or polycyclic group, and examples of the alkylene group forming the ring include a cycloalkylene group having 3 to 8 carbon atoms (for example, a cyclopentylene group, a cyclohexylene group). The alkylene group and the cycloalkylene group in W may further have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc.), an alkoxy group (preferably having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0061] In addition, the alkylene chain or cycloalkylene chain may contain -O-, -OC(=O)-, -OC(=O)O-, -N(R)-C(=O)-, -N(R)-C(=O)O-, -S-, -SO-, -SO2- in the alkylene chain. Here, R is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc.). As the cyclic arylene group in W, preferably those having 6 to 15 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, etc. can be mentioned.

[0062] Specific examples of the phenolic compound (A) are shown below, but the present disclosure is not limited thereto. If there are two or more phenolic hydroxyl groups in one molecule and two or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group are present at the ortho position of the phenolic hydroxyl group in one molecule, the phenolic hydroxyl groups in the following specific examples may be protected with an organic group. In addition, in the following formula, each L is 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 two Ls in one molecule are one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group present at the ortho position of the phenolic hydroxyl group. Also, the molecular weight should satisfy 400 to 2500.

[0063]

Chemical formula

[0064]

Chemical formula

[0065]

Chemical formula

[0066] [Chemistry]

[0067] [Chemistry]

[0068] The phenolic compound (A) used in the present disclosure can be obtained by introducing 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 in the parent compound of the phenolic compound. As a method for introducing a substituent that functions as the above crosslinkable group into the parent compound of the phenolic compound, for example, it can be obtained by reacting a phenolic compound having no corresponding hydroxymethyl group with formaldehyde under a base catalyst. At this time, in order to prevent side reactions such as gelation, it is preferable to carry out the reaction at a reaction temperature of 50°C or lower. In addition, various bisphenol derivatives having an alkoxymethyl group can be obtained by reacting a bisphenol derivative having a corresponding hydroxymethyl group with an alcohol under an acid catalyst. At this time, in order to prevent side reactions such as gelation, it is preferable to carry out the reaction at a reaction temperature of 100°C or lower.

[0069] The parent compound of the phenolic compound (A) is commercially available from, for example, Honshu Chemical Industry Co., Ltd., Asahi Organic Materials Industry Co., Ltd., etc., and these can be used. It can also be synthesized by condensation of various phenolic compounds with various aldehydes and ketones.

[0070] In the negative resist composition according to the present disclosure, the phenolic compound (A) may be used alone or in combination of two or more of the above-described compounds. However, in the negative resist composition according to the present disclosure, it is preferable that the purity of the phenolic compound (A) having the same structural formula is 70% by mass or more from the viewpoint of forming a good pattern. More preferably, the purity of the phenolic compound (A) having the same structural formula is 80% by mass or more, and still more preferably 90% by mass or more. When a phenolic compound (A) having a high purity of a compound having the same structural formula is used, it is presumed that the progress of development becomes uniform. However, even if the purity of the phenolic compound (A) having the same structural formula is less than the above value, the phenolic compound (A) can be preferably used when the structure of the impurity is similar to that of the phenolic compound (A) and the compatibility is good.

[0071] The phenolic compound used in the present disclosure preferably has no molecular weight distribution. Even if the phenolic compound used in the present disclosure has a molecular weight distribution, those having a small molecular weight distribution are preferable, and the molecular weight distribution (weight average molecular weight <mw>and number average molecular weight Ratio <mw> / It is preferably 1.0 to 1.1.

[0072] The content of the phenolic compound (A) is 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total solid content of the resist composition. The content of the phenolic compound (A) may be 95% by mass or more, 98% by mass or more, 99% by mass or more, or 99.1% by mass or more, and on the other hand, may be 99.9% by mass or less or 99.1% by mass or less. In the present disclosure, the solid content means components other than the organic solvent among the components contained in the negative resist composition.

[0073] <Basic nitrogen-containing compound (B)> The basic nitrogen-containing compound (B) used in the present invention is an organic basic compound having one or more aromatic rings in one molecule and one or more phenolic hydroxyl groups and / or phenoxy groups in one molecule, with a molecular weight of 400 or more and 3000 or less. When the basic nitrogen-containing compound (B) is used in combination with the phenolic compound (A), the sensitivity can be improved.

[0074] The aromatic ring in the basic nitrogen-containing compound (B) 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 can be mentioned. Among them, from the viewpoint of compatibility with the phenolic compound (A), the aromatic ring is preferably an aromatic hydrocarbon, and more preferably benzene. [[ID=A]] The aromatic ring may have one or more in one molecule of the basic nitrogen-containing compound (B). Among them, from the viewpoint of improving the compatibility with the phenolic compound (A) and suppressing the non-uniform distribution in the resist coating film, it is preferable that the basic nitrogen-containing compound (B) has two or more aromatic rings in one molecule, and more preferably three or more aromatic rings in one molecule.

[0075] In the nitrogen-containing basic compound (B), the phenoxy group (Ar-O-, where Ar represents an aromatic ring) may be included as an ester bond (Ar-OCO-) and a carbonate bond (Ar-O-COO-) as long as the oxygen of the oxy group is directly bonded to the aromatic ring.

[0076] The nitrogen-containing basic compound (B) used in the present invention may have one or more phenolic hydroxyl groups and / or phenoxy groups in one molecule. That is, the nitrogen-containing basic compound (B) used in the present invention may have one or more phenolic hydroxyl groups, phenoxy groups, or both phenolic hydroxyl groups and phenoxy groups in one molecule. Among them, from the viewpoint of improving the compatibility with the phenolic compound (A), it is preferable that the nitrogen-containing basic compound (B) has two or more phenolic hydroxyl groups and / or phenoxy groups in one molecule, and more preferably three or more phenolic hydroxyl groups and / or phenoxy groups in one molecule.

[0077] The molecular weight of the nitrogen-containing basic compound (B) used in the present invention is 400 or more and 3000 or less. By having a molecular weight of 400 or more and 3000 or less, the resist composition using the nitrogen-containing basic compound (B) can achieve high sensitivity and excellent resolution. The molecular weight of the nitrogen-containing basic compound (B) is more preferably 2000 or less, and even more preferably 1000 or less, from the viewpoint of resolution.

[0078] In the present invention, it is preferable that the nitrogen-containing basic compound (B) is a compound represented by the following formula (I) from the viewpoints of improving sensitivity and resolution.

[0079]

Chemical formula

[0080] R a The alkylene group in R is not particularly limited and may be linear or branched. Among them, those having 1 to 10 carbon atoms are preferable, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group and the like. Further, the carbon chain constituting the alkylene group may have an oxy group (-O-) in the middle or at the end of the carbon chain.

[0081] R b and R c Examples of the monovalent organic group in R include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, and combinations thereof (an aralkyl group, an alkylaryl group, etc.). These organic groups may contain bonds or substituents other than hydrocarbon groups such as heteroatoms containing an oxy group (-O-) in the organic group, and these may be linear or branched. Further, R b and R c may be bonded to form a cyclic structure. The cyclic structure may be a saturated or unsaturated alicyclic hydrocarbon, a heterocyclic ring, a condensed ring, or a structure formed by combining two or more selected from the group consisting of the alicyclic hydrocarbon, the heterocyclic ring, and the condensed ring.

[0082] The alkyl group is preferably an alkyl group or cycloalkyl group having 1 to 10 carbon atoms, and examples thereof include a 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, naphthyl group, biphenyl group, anthracenyl group, and the like. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, phenethyl group, cumyl group, and the like. 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. Examples of the bond other than the hydrocarbon group in the organic group include an ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond (-N=C(-R)-, -C(=NR)-, where R is a hydrogen atom or a monovalent organic group), carbonate bond, and the like. The substituent other than the hydrocarbon group in the organic group is not particularly limited, and examples thereof include a halogen atom, hydroxyl group, mercapto group, cyano group, silyl group, alkoxy group, nitro group, acyl group, acyloxy group, amino group, and the like. When having an aryl group or aralkyl group, it is preferably further provided with a hydroxyl group.

[0083] R b and R c The monovalent organic group in is R b and / or R c is preferably an aralkyl group, but R b is an aralkyl group, and R c may be a monovalent organic group which may have an oxy group (-O-).

[0084] Ar, which is a monovalent organic group having an aromatic ring, is not particularly limited and may be the aromatic ring itself, may further have a substituent on the aromatic ring, or may be a combination of the aromatic ring and a saturated or unsaturated alkyl group or a saturated or unsaturated cycloalkyl group. Examples of those having a further substituent on the aromatic ring include those having an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group, a hydroxyl group, etc. as a functional group on the aromatic ring. Among them, those having a hydroxyl group are preferred. As the combination of the aromatic ring and a saturated or unsaturated alkyl group or a saturated or unsaturated cycloalkyl group, it is preferably a phenolic compound. For example, various carbon skeletons such as a residue obtained by removing a hydrogen atom from one phenolic hydroxyl group in a phenolic compound in which all Ls in Chemical Formulas (a-1) to (a-53) exemplified as the phenolic compound (A) are hydrogen atoms can be mentioned. Examples of the aromatic ring include aromatic hydrocarbons such as benzene, naphthalene, and anthracene, and heteroaromatic rings such as pyridine, pyrrole, and thiophene. Among them, from the viewpoint of compatibility with the phenolic compound (A), the aromatic ring is preferably an aromatic hydrocarbon, and more preferably benzene.

[0085] In the present invention, the nitrogen-containing basic compound (B) used preferably has the same carbon skeleton as the phenolic compound (A) used in combination from the viewpoints of improving compatibility and improving resolution. Here, the same carbon skeleton as the phenolic compound means the part excluding the substituent in the phenolic compound. In addition, as the nitrogen-containing basic compound (B) of the present invention, a compound obtained by reacting a nitrogen-containing basic compound and a phenolic compound, such as a compound obtained by reacting a tertiary amine having a halogenated alkyl group with a phenolic compound, is preferred from the viewpoint of compatibility with the phenolic compound.

[0086] The nitrogen-containing basic compound (B) used in the present invention may have one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group, but it may not have one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group. This is because the sensitivity can be improved even without these crosslinkable groups.

[0087] Specific examples of the nitrogen-containing basic compound (B) used in the present invention are shown below, but the present invention is not limited thereto.

[0088]

Chemical formula

[0089]

Chemical formula

[0090]

Chemical formula

[0091]

Chemical formula

[0092]

Chemical formula

[0093] These nitrogen-containing basic compounds (B) can be used alone or in combination of two or more. The content of the nitrogen-containing basic compound (B) may be appropriately selected according to the improvement of sensitivity. For example, it is preferably 0.01 part by mass to 10 parts by mass, more preferably 0.1 part by mass to 5 parts by mass, based on 100 parts by mass of the phenolic compound (A). If it is less than 0.01 part by mass, the effect of its addition may not be obtained. On the other hand, if it exceeds 10 parts by mass, the developability of the unexposed part may deteriorate. The content of the nitrogen-containing basic compound (B) may be 0.01% by mass or more, may be 0.09% by mass or more, may be 10% by mass or less, may be 9.1% by mass or less, and may be 5% by mass or less, based on the total solid content of the resist composition.

[0094] <Other components> Since the non-chemically amplified negative resist composition of the present disclosure is non-chemically amplified, it does not substantially contain an acid generator. Here, not substantially containing means not containing to the extent that it substantially functions as a chemically amplified type. In the case of a non-chemically amplified resist composition, the content of the photoacid generator is less than 1 part by mass, may be 0 part by mass, based on 100 parts by mass of the phenolic compound (A), and is preferably less than 2% by mass, may be 0% by mass, based on the total solid content of the resist composition.

[0095] Since the non-chemically amplified negative resist composition of the present disclosure uses the above specific phenolic compound (A), it is not necessary to contain a phenolic compound having no hydroxymethyl group or alkoxymethyl group. Phenolic compounds that do not correspond to the above phenolic compound (A) of the present application, such as phenolic compounds having no hydroxymethyl group or alkoxymethyl group, may be contained within a range that does not impair the effects of the present disclosure, but it is preferably not contained from the viewpoint of low line edge roughness.

[0096] In addition, since the non-chemically amplified negative resist composition of the present disclosure uses the above-specified phenolic compound (A), it is not necessary to separately contain a conventionally used crosslinking agent. However, a small amount of a crosslinking agent may be added within the range where the effects of the present disclosure are not impaired to improve the resist sensitivity. The content of such a crosslinking agent can be set to 10% by mass or less, more preferably 5% by mass or less, based on the total solid content of the resist composition.

[0097] The crosslinking agent that does not correspond to the above-specified phenolic compound (A) is not particularly limited, and it can be arbitrarily selected from known crosslinking agents used in conventional chemically amplified negative resist compositions and used. For example, 4,4'-methylenebis[2,6-bis(hydroxymethyl)]phenol (MBHP), 4,4'-methylenebis[2,6-bis(methoxymethyl)]phenol (MBMP), 2,3-dihydroxy-5-hydroxymethylnorbornane, 2-hydroxy-5,6-bis(hydroxymethyl)norbornane, cyclohexanedimethanol, 3,4,8(or 9)-trihydroxytricyclodecane, 2-methyl-2-adamantanol, 1,4-dioxane-2,3-diol, 1,3,5-trihydroxycyclohexane, and other aliphatic cyclic hydrocarbons having a hydroxyl group or a hydroxyalkyl group or both, or oxygen-containing derivatives thereof can be mentioned. Also, a crosslinking agent using a melamine-based crosslinking agent, a urea-based crosslinking agent, an alkylene urea-based crosslinking agent, or glycoluril may be a glycoluril-based crosslinking agent.

[0098] In addition, an oligomer or polymer component for improving the performance of the resist film may be added to the non-chemically amplified negative resist composition of the present disclosure within the range where the effects of the present disclosure are not impaired. By adding an oligomer or polymer component and introducing a network structure into the resist film, it may be possible to improve the resolution by improving the pattern strength and improve the pattern shape (line edge roughness). The content of such an oligomer or polymer component is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total solid content of the resist composition. Examples of the oligomer or polymer component include novolak resins, polyhydroxystyrene derivatives, and acrylic copolymers derived from acrylic acid or methacrylic acid, which are alkali-developable resins conventionally used in negative resist compositions for i-line, KrF, and ArF. These oligomer or polymer components may have reactive functional groups. The mass average molecular weight of the oligomer or polymer component is preferably from 2,000 to 30,000, more preferably from 2,000 to 20,000. The mass average molecular weight herein refers to the polystyrene conversion value measured by GPC (gel permeation chromatography).

[0099] In the negative resist composition of the present disclosure, additives having miscibility as desired may be further added and contained as appropriate, such as additional resins for improving the performance of the resist film, surfactants for improving coatability, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, etc., as long as the effects of the present disclosure are not impaired. In the non-chemically amplified negative resist composition of the present disclosure, the total content of the specific phenolic compound (A) and the nitrogen-containing basic compound (B) may be 90% by mass or more, 95% by mass or more, 97% by mass or more, or even 100% by mass, based on the total solid content of the resist composition.

[0100] <Preparation of Non-Chemically Amplified Negative Resist Composition> The non-chemically amplified negative resist composition according to the present disclosure is usually prepared by uniformly mixing the specific phenolic compound (A), the nitrogen-containing basic compound (B), and, if necessary, other additives in an organic solvent.

[0101] As the organic solvent, those generally used as the solvent for the resist can be used. For example, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethylene glycol dimethyl ether, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc. are preferable, and these solvents can be used alone or in combination. Further, it may contain alcohols such as isopropyl alcohol, ethyl alcohol, methyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, isobutyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-methoxyethanol, 2-ethoxyethanol, 1-ethoxy-2-propanol, 1-methoxy-2-propanol, and aromatic solvents such as toluene and xylene. In the present disclosure, among these organic solvents, in addition to diethylene glycol dimethyl ether, cyclohexanone, cyclopentanone, 1-ethoxy-2-propanol, and ethyl lactate, 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 according to the coating film thickness at a concentration that can be applied to a substrate or the like. Generally, the solvent is used such that the solid content concentration of the resist composition is preferably in the range of 0.5 to 20% by mass, more preferably 0.5 to 15% by mass.

[0102] The non-chemically amplified negative resist composition according to the present disclosure preferably has a water content adjusted to 0.5 mass% or less, more preferably 0.01 to 0.5 mass%, and even more preferably 0.15 to 0.3 mass%. The water content can be adjusted, for example, by appropriately drying the materials used or by drying the preparation atmosphere (for example, a humidity of 50% or less).

[0103] Further, the non-chemically amplified negative resist composition according to the present disclosure has an acid component content of 1×10 -3 milliequivalent / g or less, more preferably 5×10 -4 milliequivalent / g or less. The acid component content can be adjusted, for example, by treating the solution of the materials used or the composition solution with an ion exchange resin, or by washing the solution of the materials used with pure water. The acid component content can be determined by non-aqueous potential difference measurement. The non-chemically amplified negative resist composition according to the present disclosure is preferably filtered and then used after being prepared.

[0104] Since the non-chemically amplified negative resist composition of the present disclosure enables alkali development and can form a pattern with high sensitivity and excellent resolution in pattern formation by irradiation with an electron beam, an ion beam, or EUV, it can be suitably used in micro-lithography processes such as semiconductor integrated circuits, recording media, MEMS, optical devices, and the manufacture of imprint molds used therefor. Further, the non-chemically amplified negative resist composition of the present disclosure can achieve a slope γ of 2.0 or less at the rising edge of the resist film thickness in the sensitivity curve (contrast curve) of the exposure dose and the resist film thickness after development, and has high sensitivity, so it is suitable for a negative resist composition for tone exposure. Note that the slope γ is a value calculated as the slope of an approximate straight line in the range of the resist film thickness (Normalized thickness) of 0.0 - 0.5 after development, and the exposure dose (Dose) at that time is calculated in mC / cm 2 at that time.

[0105] II. Method for manufacturing a resist pattern Other embodiments of the present disclosure are After applying the non-chemically amplified negative resist composition of the present disclosure onto a substrate, performing a heat treatment to form a resist film, and providing a method for manufacturing a resist pattern including the step of exposing and developing the resist film with an electron beam, an ion beam, EUV, or X-ray.

[0106] According to the method for manufacturing a resist pattern according to the present disclosure, since the non-chemically amplified negative resist composition according to the present disclosure is used, alkali development is possible, and a pattern with high sensitivity, high resolution, and good shape can be formed.

[0107] Hereinafter, each step will be described respectively. (i) The step of applying the non-chemically amplified negative resist composition according to the present disclosure onto a substrate, performing a heat treatment to form a resist film In this step, first, the above non-chemically amplified negative resist composition is applied onto a substrate. The coating method is not particularly limited as long as it can uniformly coat the non-chemically amplified negative 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 can be used.

[0108] Next, pre-baking (PAB) is performed on the non-chemically amplified negative resist composition applied onto the substrate to remove the organic solvent and form a resist film. The temperature of the pre-baking may be appropriately determined according to the components of the composition, the usage ratio, the type of the organic solvent, etc., and is usually 80 to 160 °C, preferably 90 to 150 °C. Also, the pre-baking time is usually about 30 seconds to 15 minutes.

[0109] (ii) The step of exposing and developing the resist film with an electron beam, an ion beam, EUV, or X-ray In this process, first, the resist film is selectively exposed by, for example, exposure through a mask having a predetermined pattern shape using an exposure apparatus such as an electron beam lithography apparatus or an EUV exposure apparatus, or by direct irradiation of an electron beam without using the mask, such as by drawing. As the exposure, tone exposure in which gray-scale exposure is performed may be carried out. As the method of tone exposure, a known method can be appropriately selected and used. For example, tone exposure can be carried out by using, for example, focus adjustment of exposure, the tone exposure function of a drawing exposure machine, a tone exposure mask, and the like. By performing tone exposure on the resist film, an uneven pattern including convex portions having different heights and / or convex portions having inclined surfaces can be formed. The exposure light source is not particularly limited, and can be performed using an ArF excimer laser, a KrF excimer laser, an F2 excimer laser, EUV (Extreme Ultraviolet), an electron beam, an X-ray, an ion beam such as helium or hydrogen, and the like.

[0110] Next, post-exposure bake (PEB) may be performed after the exposure. Since the non-chemically amplified resist composition does not substantially contain a photoacid generator, there is no need to perform post-exposure heating for diffusing acid. However, for the non-chemically amplified negative resist composition of the present disclosure, since the sensitivity is improved by performing post-exposure heating, it is preferably performed as appropriate. The conditions for the PEB treatment are usually a temperature of 50 to 160 °C and a time of about 0.1 to 15 minutes.

[0111] Next, the substrate that has been PEB-treated above is developed using an alkaline developer to remove the unexposed portion of the exposure light. Examples of the development method include a spray method, a slit method, a liquid puddle method, a dipping method, a rocking immersion method, and the like. In addition, as the alkaline developer for the non-chemically amplified negative resist composition of the present disclosure, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldimethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and choline, and aqueous solutions of alkalis such as cyclic amines such as pyrrole and piperidine can be used. Furthermore, an appropriate amount of alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants can be added to the aqueous solutions of the above alkalis and used. Among these alkaline developers, quaternary ammonium salts are preferred, and more preferably, aqueous solutions of tetramethylammonium hydroxide and choline.

[0112] When an aqueous solution of tetramethylammonium hydroxide (TMAH) is used as the alkaline developer, the concentration of the aqueous solution of tetramethylammonium hydroxide is preferably 0.1% to 25%, more preferably 0.2% to 5%, and particularly preferably 0.2% to 2.38%. An aqueous solution of tetramethylammonium hydroxide with a concentration of 2.38% is generally the most readily available in the semiconductor industry. Also, when the concentration of the aqueous solution of tetramethylammonium hydroxide is less than 0.1%, the developer is neutralized by carbon dioxide in the air, and it becomes difficult to obtain products stably due to fluctuations in sensitivity.

[0113] After the development process, a rinsing process is performed to wash away the alkaline developer on the substrate and the resist composition dissolved by the alkaline developer, and then dried to obtain a resist pattern.

[0114] III. Mold Other embodiments of the present disclosure provide a mold having an uneven pattern, wherein at least the convex portions contain a cured product of the non-chemically amplified negative resist composition of the present disclosure. Regarding the mold according to the present disclosure, other configurations can be the same as those conventionally known as long as they include the cured product of the non-chemically amplified negative resist composition of the present disclosure. The mold according to the present disclosure can be produced by the method for producing a resist pattern of the present disclosure. The mold according to the present disclosure may be a three-dimensional mold having an uneven pattern including at least one of convex portions with different heights and convex portions having inclined surfaces. The mold according to the present disclosure can be suitably used, for example, as a mold for imprinting (molding), a stamper for a recording medium, an injection mold, and a mold for manufacturing these.

[0115] Note that the present disclosure is not limited to the above embodiments. The above embodiments are examples, and any configuration that has a configuration substantially the same as the technical idea described in the claims of the present disclosure and exhibits the same operational effects is included in the technical scope of the present disclosure.

Examples

[0116] Hereinafter, the present disclosure will be specifically described with reference to examples. These descriptions do not limit the present disclosure. In the production examples, the confirmation of the structure and physical properties was performed using the following apparatuses. MALDI-TOF MS: REFLEX II manufactured by BRUKER 1 H-NMR: JEOL JNM-LA400WB manufactured by JEOL Ltd. Purity: Measured by high performance liquid chromatography (HPLC) (LC-10ADvp manufactured by Shimadzu Corporation) under the following conditions (temperature: 40 ° C, flow rate: 1.0 mL / min, column: VP-ODS (4.7 mm × 150 mm), detector SPD-M10Avp, mobile phase: acetonitrile / water). Glass transition temperature (Tg): Using a differential thermal analyzer ("DSC-60" manufactured by Shimadzu Corporation), after heating approximately 4 mg of the pattern-forming material to 200°C at a rate of 10°C / min, cooling it to room temperature, and then heating it to 200°C again at a rate of 10°C / min, the glass transition temperature was determined as the intersection of the two smooth tangents before and after the inflection temperature part of the DTA curve. When no inflection point of the DTA curve corresponding to the glass transition temperature was observed up to 200°C, Tg was judged to be 200°C or higher.

[0117] <Synthesis Example 1: Synthesis of phenolic compound A> To a solution consisting of 20 mL of a 10% by mass potassium hydroxide aqueous solution and 20 mL of ethanol, 6.3 g (10 mmol) of a phenolic compound (TekOC-4HBPA: Honshu Chemical Industry Co., Ltd.) represented by the following chemical formula (10) was added, and the mixture was stirred and dissolved at room temperature. To this solution, 7.0 mL (80 mmol) of a 37% formalin aqueous solution was slowly added at room temperature. Further, after stirring at 40°C for 24 hours under a nitrogen atmosphere, it was poured into 200 mL of water in a beaker. While cooling this in an ice bath, a 2.0 wt% acetic acid aqueous solution was slowly added until the pH reached 5.0. The precipitate was filtered off, washed thoroughly with water, dried, and purified by high-performance liquid chromatography to obtain 4.8 g of a phenolic compound A represented by the following chemical formula (11). The structural confirmation of the obtained phenolic compound A was 1 performed by 1H-NMR spectrum and MALDI-TOF MS. The glass transition temperature (Tg) was determined by differential scanning calorimetry. The analysis results are shown below.

[0118]

Chemical formula

[0119]

Chemical formula

[0120] (Analysis results) 1 1H-NMR: 0.44 (6H, -CH3), 1.09 - 1.67 (14H, cHex), 2.03 (12H, Ph-CH3), 2.64 - 2.67 (4H, cHex), 4.44 - 4.51 (8H, Ph-CH2-OH), 5.19 - 5.25 (4H, Ph-CH2-OH), 6.74 - 7.02 (8H, Aromatic H), 8.10 - 8.13 (4H, Ph-OH) Purity: 92% MALDI-TOF MS: 752.97 Glass transition temperature (Tg): 200 °C or higher

[0121] <Synthesis Example 2: Synthesis of nitrogenous basic compound (B-01)>[[]] Under a nitrogen atmosphere, in a 100 mL three-necked flask, 0.25 g (1.69 mmol) of N-(2-chloroethyl)dibenzylamine hydrochloride and 0.54 g (1.69 mmol) of (TekOC-4HBPA: manufactured by Honshu Chemical Industry Co., Ltd.) were dissolved in 30 mL of acetone. Then, 1.17 g (8.5 mmol) of potassium carbonate was added and the mixture was reacted at 60 °C for 48 hours. After the reaction, the residual potassium carbonate was removed. Once the solvent was distilled off and the reaction product was dried to a solid, it was dissolved in water. Then, ethyl acetate was added to extract the target product from the aqueous phase. After further distilling off the ethyl acetate, it was separated by high performance liquid chromatography and purified to obtain a waxy solid nitrogenous basic compound (B-01') (molecular weight: 856.2) and (B-01") (molecular weight 856.2). The structure was confirmed by MALDI-TOF MS, high performance liquid chromatography, and 1 1H-NMR spectrum. Note that 1 Since the 1H-NMR spectrum and the retention time of HPLC are different, it can be seen that the basic compounds (B-01') and (B-01") are in an isomeric relationship.

[0122]

Chemical Structure

[0123] (B-01') Confirmed by MALDI-TOF MS: [M+H] 856.8 ​HPLC (acetonitrile / water = 8 / 2) retention time: 73.5 minutes 1 H-NMR (400 MHz, DMSO-d6, TMS): 9.00 & 8.98 (d) δ (ppm) (aromatic-OH), 8.90 (aromatic-OH), 6.54 - 7.37 (aromatic-H), 3.98 (aromatic-O-CH2-), 3.65 (aromatic-CH2-N), 2.75 (N-CH2-CH2-), 2.63 (Cyclohexane―H2) 2.01 - 2.05 (aromatic-CH3), 1.65 (Cyclohexane―H2), 1.50 (Cyclohexane―H2), 1.32 (Cyclohexane―H), 1.08 (Cyclohexane―H2), 0.44 (-C(-CH3)2―)

[0124] (B-01”) Confirmed by MALDI-TOF MS: [M+H] 856.8 HPLC (acetonitrile / water = 8 / 2) retention time: 89.0 minutes 1 H-NMR (400 MHz, DMSO-d6, TMS): 8.98 δ (ppm) (aromatic-OH), 8.92 & 8.90 (d) (aromatic-OH), 6.54 - 7.40 (aromatic-H), 4.04 (aromatic-O-CH2-), 3.68 (aromatic-CH2-N), 2.79 (N-CH2-CH2-), 2.65 (Cyclohexane―H2) 2.01 - 2.10 (aromatic-CH3), 1.65 (Cyclohexane―H2), 1.51 (Cyclohexane―H2), 1.32 (Cyclohexane―H), 1.07 (Cyclohexane―H2), 0.43 (-C(-CH3)2―)

[0125] [Examples 1 - 3, Comparative Example 1: Non-chemically amplified negative resist composition] The phenolic compound (A) obtained in Synthesis Example 1, the nitrogen-containing basic compound (B) obtained in Synthesis Example 2, and an organic solvent (propylene glycol monomethyl ether) were made into a uniform solution in the blending amounts shown in Table 1, and each sample solution was filtered through a 0.1-μm Teflon (registered trademark) filter to prepare the non-chemically amplified negative resist compositions of Examples 1 to 3. Also, without using the nitrogen-containing basic compound (B), the phenolic compound (A) and the organic solvent were made into a uniform solution in the blending amounts shown in Table 1, and filtered through a 0.1-μm Teflon (registered trademark) filter to prepare the non-chemically amplified negative resist composition of Comparative Example 1.

[0126]

Table 1

[0127] [Manufacture of Resist Pattern] Using the non-chemically amplified negative resist compositions obtained in Examples 1 to 3 and Comparative Example 1, a resist pattern was formed and evaluated by the method shown below. (1) Acquisition of Sensitivity Curve Each non-chemically amplified negative resist composition was uniformly applied onto a 6-inch silicon substrate using a spinner, and prebaked (PAB) at 110°C for 60 seconds to form a resist film with a thickness of 2 μm. With respect to the above resist film, using an electron beam lithography apparatus (acceleration voltage: 100 keV), exposure was performed while changing the exposure dose by 50 μC / cm for each 1-mm square region. 2 After the completion of the exposure, development treatment was performed with a 2.38% TMAH aqueous solution (23°C) for 60 seconds, and rinsing treatment was performed with pure water for 60 seconds to obtain a resist cured pattern according to the exposure dose.

[0128] [Evaluation (Sensitivity Curve)] The sensitivity was measured by a fine shape measuring instrument (ET4000 manufactured by Kosaka Laboratory Ltd.) for the height of the resist cured product with respect to the exposure dose, and a sensitivity curve (contrast curve) of the exposure dose and the resist film thickness after development shown in FIG. 1 was obtained.

[0129] (2) Formation of Resist Uneven Pattern Each non-chemically amplified negative resist composition was uniformly coated on a 6-inch silicon substrate using a spinner, and pre-baked (PAB) at 110 °C for 60 seconds to form a resist film having the same film thickness as when the sensitivity curve was obtained. Drawing was performed on the above resist film using an electron beam lithography apparatus (acceleration voltage 100 keV). Specifically, from the sensitivity curve acquired in advance, it was allocated as a layer for each resist height finally to be formed, and drawing was performed by setting an appropriate exposure amount for the layer. After completion of the drawing, development treatment was performed for 60 seconds with a 2.38% TMAH aqueous solution (23 degrees), and rinsing treatment was performed for 60 seconds with pure water to form a concavo-convex pattern.

[0130] [Evaluation (Cross-sectional shape of concavo-convex pattern)] The cross-sectional shape of the concavo-convex pattern was observed with a scanning electron microscope (SEM) (manufactured by ZEISS). Fig. 2 shows the scanning electron micrograph of Example 1 and the scanning electron micrograph of Comparative Example 1.

[0131] [Summary of results] From the comparison between Comparative Example 1 and Examples 1 to 3 in the sensitivity curve of Fig. 1, in the non-chemically amplified negative resist composition of the present disclosure in which the specific phenolic compound (A) functioning as a resist substrate and a crosslinking agent is combined with a specific nitrogen-containing basic compound (B), it was clarified that alkali development is possible, and a pattern with higher sensitivity and excellent resolution can be formed. Further, from the comparison of Examples 1 to 3, it was shown that the higher the addition amount of the specific nitrogen-containing basic compound (B), the higher the sensitivity. Referring to Fig. 2, in the non-chemically amplified negative resist composition of the present disclosure, since the sensitivity is high, it was clarified that the height of the concavo-convex pattern can be increased as compared with the comparative example. < / mw> < / mw>

Claims

1. a phenolic compound (A) having two or more phenolic hydroxyl groups in one molecule and two or more substituents in one molecule selected from the group consisting of hydroxymethyl groups and alkoxymethyl groups at the ortho-positions of the phenolic hydroxyl groups, the compound having a molecular weight of 400 to 2500; a nitrogen-containing basic compound (B) having one or more aromatic rings in one molecule, and one or more phenolic hydroxyl groups and / or phenoxy groups in one molecule, and having a molecular weight of 400 or more and 3000 or less, the phenolic compound (A) has a glass transition temperature (Tg) of 60°C or higher; The nitrogen-containing basic compound (B) is represented by the following formula (I): a non-chemically amplified negative resist composition, wherein the content of the phenolic compound (A) is 70 mass% or more of the total solid content of the negative resist composition, and the content of the acid generator is less than 1 part by mass per 100 parts by mass of the phenolic compound (A). 【Chemical 1】 (In formula (I), R a represents a direct bond or an alkylene group which may have an oxy group (—O—), R b and R c each independently represent a monovalent organic group which may have an oxy group (—O—), and Ar represents a monovalent organic group having an aromatic ring, provided that each molecule contains one or more phenolic hydroxyl groups and / or phenoxy groups.)

2. A non-chemically amplified negative resist composition as described in claim 1, wherein the content of the nitrogen-containing basic compound (B) is 0.1 to 5 parts by mass per 100 parts by mass of the phenolic compound (A).

3. A non-chemically amplified negative resist composition according to claim 1 or 2, wherein the nitrogen-containing basic compound (B) has the same carbon skeleton as the phenolic compound (A).

4. A non-chemically amplified negative resist composition described in any one of claims 1 to 3, wherein the nitrogen-containing basic compound (B) does not have one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group.

5. A process of applying the non-chemically amplified negative resist composition according to any one of claims 1 to 4 onto a substrate, followed by a heat treatment to form a resist film; and exposing the resist film to electron beams, ion beams, EUV, or X-rays, and developing the resist film; A method for producing a resist pattern comprising the steps of:

6. A mold having a concave-convex pattern, wherein at least the convex portions contain a cured product of the non-chemically amplified negative resist composition described in any one of claims 1 to 4.

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