Method for manufacturing semiconductor substrate, method for manufacturing composition and method for manufacturing compound

Abstract

Provided is a method for producing a semiconductor substrate capable of forming a film excellent in embeddability, heat resistance, etching resistance, and bending resistance, a composition, and a method for producing a compound. A method for producing a semiconductor substrate includes: a step of directly or indirectly applying a composition for resist underlayer film formation on a substrate; a step of directly or indirectly forming a resist pattern on a resist underlayer film formed by the application step; and a step of performing etching with the resist pattern as a mask, and the composition for resist underlayer film formation contains a compound represented by Formula (1A) or Formula (1B) below and a solvent. (In Formula (1A), Ar 1A and Ar 2A are each independently a substituted or unsubstituted aromatic ring having 3 to 20 carbon atoms; Y is a single bond, an oxygen atom, a sulfur atom, or a methylene group; X is an n-valent organic group having an aromatic ring; the bonding bond extending from X is from the aromatic ring in X; n is an integer of 1 to 10; and in Formula (1B), Ar 1B and Ar 2B are each independently an unsubstituted monovalent aromatic ring group having 3 to 20 carbon atoms or a monovalent aromatic ring group having 3 to 20 carbon atoms substituted with a group selected from the group consisting of a hydroxyl group and a halogen atom; and X and n have the same meanings as in Formula (1A).

Description

Technical Field

[0001] This invention relates to a method for manufacturing a semiconductor substrate, a composition, and a method for manufacturing a compound. Background Technology

[0002] In the manufacture of semiconductor devices, for example, a multilayer resist process is used. This process involves exposing and developing a resist film, which is a resist film layered on a substrate and containing an organic substrate or a silicon-containing film, to form a resist pattern. In this process, the resist substrate is etched using the resist pattern as a mask, and the substrate is then etched using the obtained resist substrate pattern as a mask, thereby forming a desired pattern on the semiconductor substrate (see Japanese Patent Application Publication No. 2004-177668).

[0003] Various studies have been conducted on the materials used in this composition for forming the resist underlayer (refer to International Publication No. 2011 / 108365).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2011 / 108365 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] In multilayer resist processes, the organic substrate film, which serves as the resist base film, is required to have good embeddability, heat resistance, etching resistance, and flexural strength.

[0009] The present invention is based on the facts described above, and its purpose is to provide a method for manufacturing a semiconductor substrate, a composition, and a compound capable of forming a film with excellent embedding properties, heat resistance, etch resistance, and bending resistance.

[0010] Technical means to solve the problem

[0011] In one embodiment, the present invention relates to a method for manufacturing a semiconductor substrate, comprising:

[0012] The process of directly or indirectly coating a composition for forming a resist underlayer film on a substrate;

[0013] The process of directly or indirectly forming a resist pattern on the resist underlayer film formed by the coating process; and

[0014] An etching process is performed using the resist pattern as a mask, and

[0015] The composition for forming the resist underlayer film contains:

[0016] The compounds represented by formula (1A) or formula (1B) below (hereinafter also referred to as "[A] compounds"), and

[0017] Solvent (hereinafter also referred to as "[B] solvent").

[0018] [Chemistry 1]

[0019]

[0020] (In formula (1A), Ar) 1A and Ar 2A Each is an aromatic ring with 3 to 20 carbon atoms, either substituted or unsubstituted; Y is a single bond, an oxygen atom, a sulfur atom, or a methylene group; X is an n-valent organogroup having an aromatic ring; the bond extending from X is an extension of the aromatic ring in X; n is an integer from 1 to 10;

[0021] In equation (1B), Ar 1B and Ar 2B Each is independently an unsubstituted monovalent aromatic cyclic group having 3 to 20 carbon atoms or a monovalent aromatic cyclic group having 3 to 20 carbon atoms substituted by a group selected from the group consisting of hydroxyl and halogen atoms; X and n have the same meaning as in the above formula (1A).

[0022] Furthermore, the hydrogen atoms bonded to the carbon atoms bonded to X in formulas (1A) and (1B) are sometimes omitted in the structural formulas (including formulas (1A) and (1B) and other general formulas) in this specification.

[0023] In one embodiment, the present invention relates to a composition comprising:

[0024] The compounds represented by formula (1A) or formula (1B) below, and

[0025] solvent.

[0026] [Chemistry 2]

[0027]

[0028] (In formula (1A), Ar) 1A and Ar 2A Each is an aromatic ring with 3 to 20 carbon atoms, either substituted or unsubstituted; Y is a single bond, an oxygen atom, a sulfur atom, or a methylene group; X is an n-valent organogroup having an aromatic ring; the bond extending from X is an extension of the aromatic ring in X; n is an integer from 1 to 10;

[0029] In equation (1B), Ar 1B and Ar 2BEach is independently an unsubstituted monovalent aromatic cyclic group having 3 to 20 carbon atoms or a monovalent aromatic cyclic group having 3 to 20 carbon atoms substituted by a group selected from the group consisting of hydroxyl and halogen atoms; X and n have the same meaning as in the above formula (1A).

[0030] In one embodiment, the present invention relates to a method for manufacturing a compound, comprising:

[0031] A process for reacting an aromatic ring-containing compound (hereinafter also referred to as "[a] aromatic ring-containing compound") with a compound represented by formula (1a) or formula (1b) below (hereinafter also referred to as "[b] compound").

[0032] [Chemistry 3]

[0033]

[0034] (In formula (1a), Ar) 1A and Ar 2A Each is an aromatic ring with 3 to 20 carbon atoms, either substituted or unsubstituted; Y is a single bond, an oxygen atom, a sulfur atom, or a methylene group;

[0035] In equation (1b), Ar 1B and Ar 2B (Each is independently an unsubstituted monovalent aromatic cycloalloy with 3 to 20 carbon atoms or a monovalent aromatic cycloalloy with 3 to 20 carbon atoms substituted by a group selected from the group consisting of hydroxyl and halogen atoms)

[0036] In this specification, the term "organic group" refers to a group containing at least one carbon atom. "Hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "hydrocarbon group" includes saturated hydrocarbon groups and unsaturated hydrocarbon groups. The term "chain hydrocarbon group" refers to a hydrocarbon group that contains only a chain structure without a ring structure, including both straight-chain hydrocarbon groups and branched-chain hydrocarbon groups. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic structure as its ring structure and does not contain an aromatic ring structure, including both monocyclic and polycyclic alicyclic hydrocarbon groups (wherein, it is not necessary to contain only an alicyclic structure; a chain structure may also be included in a portion thereof). The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as its ring structure (wherein, it is not necessary to contain only an aromatic ring structure; an alicyclic structure or a chain structure may also be included in a portion thereof).

[0037] The effects of the invention

[0038] By means of the semiconductor substrate manufacturing method described above, a good semiconductor substrate can be obtained because a resist underlayer film with excellent embeddability, heat resistance, etch resistance, and bending resistance can be formed. By means of the composition described above, a film with excellent embeddability, heat resistance, etch resistance, and bending resistance can be formed. By means of the compound manufacturing method described above, compounds suitable for the composition can be manufactured efficiently. Therefore, these are suitable for use in the manufacture of semiconductor devices that are expected to be further miniaturized in the future. Attached Figure Description

[0039] [ Figure 1 [Illustrated diagram] is a schematic plan view used to illustrate the evaluation method of bending resistance. Detailed Implementation

[0040] Hereinafter, methods for manufacturing semiconductor substrates, compositions, and compounds according to various embodiments of the present invention will be described in detail. Furthermore, suitable combinations of forms are preferred in the embodiments.

[0041] Manufacturing Methods of Semiconductor Substrates

[0042] The method for manufacturing the semiconductor substrate includes: a step of directly or indirectly coating a composition for forming a resist underlayer film onto a substrate (hereinafter also referred to as the "coating step"); a step of directly or indirectly forming a resist pattern on the resist underlayer film formed by the coating step (hereinafter also referred to as the "resist pattern forming step"); and a step of etching using the resist pattern as a mask (hereinafter also referred to as the "etching step").

[0043] According to the semiconductor substrate manufacturing method, in the coating process, the composition described later is used as a composition for forming a resist underlayer film, thereby forming a resist underlayer film with excellent embedding properties, heat resistance, etch resistance and bending resistance, and thus a semiconductor substrate with good pattern shape can be manufactured.

[0044] The method for manufacturing the semiconductor substrate may also include, as needed, a step of directly or indirectly forming a silicon-containing film on the resist underlayer film before the formation of the resist pattern (hereinafter also referred to as the "silicon-containing film formation step").

[0045] The composition and each step used in the manufacturing method of the semiconductor substrate are described below.

[0046] <Composition>

[0047] The composition used as a resist underlayer film formation comprises compound [A] and solvent [B]. The composition may also contain any components without impairing the effects of the present invention.

[0048] The composition, containing compound [A] and solvent [B], can form a film with excellent embeddability, heat resistance, etching resistance, and flexural strength. Therefore, the composition can be used as a composition for forming films. More specifically, the composition is suitably used as a composition for forming a resist underlayer film in a multilayer resist process.

[0049] The components contained in the composition are described below.

[0050] <[A]compound>

[0051] [A] The compound is a compound represented by formula (1A) or formula (1B) (hereinafter, the compound represented by formula (1A) is also referred to as "[A1] compound", and the compound represented by formula (1B) is also referred to as "[A2] compound"). The composition may contain one or more [A] compounds.

[0052] In the aforementioned formula (1A), Ar is used as... 1A and Ar 2A Aromatic rings with 3 to 20 carbon atoms include, for example, aromatic hydrocarbon rings with 6 to 20 carbon atoms such as benzene rings, naphthalene rings, anthracene rings, ferroene rings, phenanthrene rings, pyrene rings, fluorene rings, and perylene rings; aromatic heterocycles with 3 to 20 carbon atoms such as triazole rings, imidazole rings, furan rings, pyrrole rings, thiophene rings, phosphole rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, triazine rings, and carbazole rings, or combinations thereof. These ring combinations can be condensed rings, aggregate rings (structures where two rings are bonded by a single bond), or spirocyclic structures.

[0053] Ar 1A and Ar 2A It may have substituents. Examples of substituents include: monovalent chain hydrocarbons with 1 to 10 carbon atoms; hydroxyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkoxy groups such as methoxy, ethoxy, and propoxy; alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl; alkoxycarbonyl groups such as methoxycarbonyloxy and ethoxycarbonyloxy; acyl groups such as formyl, acetyl, propionyl, and butyryl; carboxyl groups; cyano groups; nitro groups; and amino groups.

[0054] In the aforementioned formula (1A), Ar 1A and Ar 2APreferably, each of the aromatic hydrocarbon rings is independently an aromatic hydrocarbon ring having 6 to 20 carbon atoms, or is a ring structure formed by substituting part or all of the hydrogen atoms of the aromatic hydrocarbon ring with a hydrocarbon group, hydroxyl group, cyano group, nitro group, carboxyl group, or amino group having 1 to 6 carbon atoms. The aromatic hydrocarbon ring having 6 to 20 carbon atoms is preferably at least one aromatic hydrocarbon ring selected from the group consisting of benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and pyrene ring, more preferably a benzene ring, naphthalene ring, or pyrene ring, and even more preferably a benzene ring.

[0055] Y is preferably a single bond.

[0056] The n-valent organic group represented by X, which has an aromatic ring, is a group formed by removing (n-1) hydrogen atoms from a monovalent organic group having an aromatic ring. Examples of monovalent organic groups having an aromatic ring include groups formed by incorporating an aromatic ring into a monovalent organic group having 1 to 40 carbon atoms.

[0057] Examples of monovalent organic groups having 1 to 40 carbon atoms include: monovalent hydrocarbon groups having 1 to 40 carbon atoms; groups having divalent heteroatoms between carbon atoms or at the end of the hydrocarbon group; groups formed by replacing some or all of the hydrogen atoms in the hydrocarbon group with a monovalent heteroatom group; or combinations thereof.

[0058] Examples of monovalent hydrocarbon groups with 1 to 20 carbon atoms include: monovalent chain hydrocarbon groups with 1 to 40 carbon atoms, monovalent alicyclic hydrocarbon groups with 3 to 40 carbon atoms, monovalent aromatic hydrocarbon groups with 6 to 40 carbon atoms as aromatic rings, or combinations thereof.

[0059] Examples of monovalent chain hydrocarbon groups having 1 to 40 carbon atoms (hereinafter also referred to as "chain hydrocarbon groups (1x)") include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc.; alkenyl groups such as vinyl, propenyl, butenyl, etc.; alkynyl groups such as ethynyl, propynyl, butynyl, etc.

[0060] Examples of monovalent alicyclic hydrocarbon groups with 3 to 40 carbon atoms (hereinafter also referred to as "alicyclic hydrocarbon groups (2x)") include: cyclopentyl, cyclohexyl and other cycloalkyl groups; cyclopropenyl, cyclopentenyl, cyclohexenyl and other cycloalkenyl groups; bridged cyclic saturated hydrocarbon groups such as norbornyl, adamantyl, tricyclodecyl and other bridged cyclic unsaturated hydrocarbon groups such as norbornyl, tricyclodecenyl and other other bridged cyclic unsaturated hydrocarbon groups.

[0061] Regarding the monovalent aromatic hydrocarbon group with 6 to 40 carbon atoms as the aromatic ring (hereinafter also referred to as "aromatic hydrocarbon group (3x)"), it is suitable to use Ar 1A and Ar 2A The radical shown is formed by removing one hydrogen atom from an aromatic hydrocarbon ring with 3 to 20 carbon atoms, which is then expanded to 40 carbon atoms. Examples of aromatic hydrocarbon rings with more than 20 carbon atoms include: benzo[a]perylene ring, indene[a]pyrene ring, cardinium ring, and ovobenzene ring.

[0062] Examples of heteroatoms that form divalent or monovalent groups containing heteroatoms include: oxygen, nitrogen, sulfur, phosphorus, silicon, and halogen atoms. Examples of halogen atoms include: fluorine, chlorine, bromine, and iodine atoms.

[0063] Examples of divalent heteroatom-containing groups include: -CO-, -CS-, -NR'-, -O-, -S-, and groups formed by combining these. R' is a monovalent hydrocarbon group with 1 to 10 carbon atoms.

[0064] Examples of monovalent groups containing heteroatoms include: hydroxyl, hydrogen sulfide, cyano, nitro, halogen atom, carboxyl, etc.

[0065] As the aromatic ring in X, in addition to the monovalent aromatic hydrocarbon group having 6 to 40 carbon atoms, the Ar group can be suitably used. 1A and Ar 2A The rings shown are obtained by expanding aromatic heterocycles with 3 to 20 carbon atoms to 40 carbon atoms.

[0066] The number of carbons in X is preferably 6 or more and 70 or less. The lower limit of the number of carbons in X is preferably 8, more preferably 10, and even more preferably 12. The upper limit of the number of carbons in X is preferably 60, more preferably 55, and even more preferably 50.

[0067] As the monovalent organic group having an aromatic ring shown in X, preferably:

[0068] Monovalent aromatic hydrocarbon groups with 6 to 40 carbon atoms; and

[0069] A monovalent base is formed by combining at least one of the groups consisting of aromatic hydrocarbons with 6 to 40 carbon atoms and chain hydrocarbons selected from those with 1 to 5 carbon atoms and alicyclic hydrocarbons with 3 to 10 carbon atoms.

[0070] Examples of aromatic hydrocarbons with 6 to 40 carbon atoms include structures corresponding to the aromatic hydrocarbon group (3x). Preferred examples include benzene, naphthalene, biphenyl, fluorene, anthracene, phenanthrene, pyrene, and cardamom. In X, these aromatic hydrocarbons are preferably monovalent to trivalent.

[0071] Examples of chain hydrocarbons having 1 to 5 carbon atoms include structures corresponding to 1 to 5 carbon atoms in the chain hydrocarbon group (1x). Methane, ethane, propane, butane, and isobutane are preferred. In X, these chain hydrocarbons are preferably monovalent to tetravalent.

[0072] Examples of alicyclic hydrocarbons with 3 to 10 carbon atoms include structures corresponding to 3 to 10 carbon atoms in the alicyclic hydrocarbon group (2x). Cyclopentane and cyclohexane are preferred. In X, these alicyclic hydrocarbons are preferably divalent to trivalent.

[0073] The aromatic hydrocarbon group or the aromatic hydrocarbon preferably has a hydroxyl group as a substituent.

[0074] n is preferably 2 or more. More preferably, n is an integer from 2 to 8, and even more preferably, an integer from 2 to 6.

[0075] Examples of compounds represented by formula (1A) ([A1]) include compounds represented by formulas (1A-1) to (1A-26). In the following formulas, the R in the aromatic ring-containing structure on the left corresponds to the structure shown as R on the right side of the formula. In the following formulas, The bond is the aromatic ring bonded to R. It is not necessary that all R in the aromatic ring-containing structures on the left side of the following formula corresponds to the aromatic ring-containing structures on the right side; a portion of R may also be a hydrogen atom. If the right side of the following formula describes two or more aromatic ring-containing structures as R, at least the aromatic ring-containing structure on the left end ( The extended carbon atom has a tertiary structure (a structure with hydrogen atoms) and can be used as R. Y is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms. As a monovalent organic group with 1 to 10 carbon atoms represented by Y, the groups corresponding to 1 to 10 carbon atoms among the monovalent organic groups with 1 to 40 carbon atoms shown in X can be listed.

[0076] [Chemistry 4]

[0077]

[0078] [Chemistry 5]

[0079]

[0080] [Chemistry 6]

[0081]

[0082] [Chemistry 7]

[0083]

[0084] [Chemistry 8]

[0085]

[0086] [Chemistry 9]

[0087]

[0088] In the formula, in each [A1] compound The proportion of the extended carbon atoms in R that form tertiary aromatic rings is not particularly limited. When the total molar ratio of R is set to 1, the lower limit of this proportion can be 0.30, 0.40, 0.50, or 0.60. The upper limit of this proportion can be 0.99, 0.95, 0.92, or 0.90.

[0089] In the aforementioned formula (1B), Ar is used as 1B and Ar 2B The unsubstituted monovalent aromatic ring group with 3 to 20 carbon atoms represented may suitably be derived from Ar of formula (1A), except for the aspect of not having substituents. 1A and Ar 2A A radical is formed by removing one hydrogen atom from an aromatic ring with 3 to 20 carbon atoms.

[0090] In the aforementioned formula (1B), Ar is used as 1B and Ar 2B The monovalent aromatic ring group with 3 to 20 carbon atoms represented by the group selected from the group consisting of hydroxyl and halogen atoms, except that it only has groups selected from the group consisting of hydroxyl and halogen atoms as substituents, can suitably be Ar from the group described in formula (1A). 1A and Ar 2A A radical is formed by removing one hydrogen atom from an aromatic ring with 3 to 20 carbon atoms.

[0091] Examples of compounds represented by formula (1B) for [A2] include those represented by formulas (1B-1) to (1B-4). In the following formulas, the R in the aromatic ring-containing structure on the left corresponds to the structure shown as R on the right side of the formula. In the following formulas, The bond is the aromatic ring bonded to R. It is not necessary that all R in the aromatic ring structure on the left side of the following formula corresponds to the aromatic ring structure on the right side; a portion of R may also be a hydrogen atom.

[0092] [Chemistry 10]

[0093]

[0094] As a compound [A2] The proportion of the extended carbon atoms in R that form a tertiary aromatic ring structure can be appropriately adopted from the proportion in the [A1] compound.

[0095] The lower limit for the weight-average molecular weight of compound [A] is preferably 500, more preferably 600, further preferably 700, and particularly preferably 800. The upper limit for the molecular weight is preferably 3000, more preferably 2500, further preferably 2000, and particularly preferably 1800. Furthermore, the method for determining the weight-average molecular weight is based on the description in the examples.

[0096] The composition for forming the resist underlayer film preferably contains [A] compound at a content of 1% by mass or more in the components other than the solvent. The content of [A] compound can be 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 100% by mass.

[0097] As a lower limit for the content of compound [A] in the composition, it is preferably 0.01% by mass, more preferably 0.1% by mass, and even more preferably 0.2% by mass, in the total mass of compound [A] and solvent [B]. As an upper limit for the content, it is preferably 20% by mass, more preferably 15% by mass, and even more preferably 12% by mass, in the total mass of compound [A] and solvent [B].

[0098] <[A] Method for manufacturing compound>

[0099] The method for producing compound [A] includes the step of reacting compound [a], which contains an aromatic ring, with compound [b]. The target compound [A] can be efficiently produced through an electrophilic substitution reaction based on the reaction between compound [a], which contains an aromatic ring, and compound [b]. For example, the reaction proceeds under an acid catalyst by attacking and dehydrating the carbon atom bonded to the OH group in compound [b] by compound [a] containing an aromatic ring (further proton removal if necessary). However, the reaction mechanism is not limited to this; other mechanisms can also be used to produce compound [A].

[0100] ([a] Compounds containing aromatic rings)

[0101] As a compound containing an aromatic ring, in order to provide X in the formulas (1A) and (1B), a compound containing a structure corresponding to the n-valent organic group having an aromatic ring represented by X may be suitably used.

[0102] [a] Compounds containing an aromatic ring are preferably those with phenolic hydroxyl groups. This can stabilize the reaction conditions or improve the reaction efficiency.

[0103] While there is no limitation on specific examples of compounds containing aromatic rings, examples such as formulas (2-1) to (2-20) can be listed below.

[0104] [Chemistry 11]

[0105]

[0106] [Chemistry 12]

[0107]

[0108] ([b]compound)

[0109] [b] The compound is a compound represented by formula (1a) or formula (1b) below (the compound represented by formula (1a) below is also called [b1] compound, and the compound represented by formula (1b) below is also called [b2] compound).

[0110] [Chemistry 13]

[0111]

[0112] (In formula (1a), Ar) 1A and Ar 2A Each is an aromatic ring with 3 to 20 carbon atoms, either substituted or unsubstituted; Y is a single bond, an oxygen atom, a sulfur atom, or a methylene group;

[0113] In equation (1b), Ar 1B and Ar 2B (Each is independently an unsubstituted monovalent aromatic cycloalloy with 3 to 20 carbon atoms or a monovalent aromatic cycloalloy with 3 to 20 carbon atoms substituted by a group selected from the group consisting of hydroxyl and halogen atoms)

[0114] In the aforementioned formula (1a), Ar is used as 1A and Ar 2A The aromatic rings with 3 to 20 carbon atoms in the formula (1A) can be suitably represented by Ar. 1A and Ar 2A The aromatic ring containing 3 to 20 carbon atoms. As described in (1a), Ar... 1A and Ar 2A When substituents are present, Ar of formula (1A) may be suitable. 1A and Ar 2A Possible substituents.

[0115] In the formula (1a), Y is preferably a single bond.

[0116] While there are no specific examples of [b1] compounds, examples such as formulas (1a-1) to (1a-6) can be listed.

[0117] [Chemistry 14]

[0118]

[0119] In equation (1b), Ar is used as 1B and Ar 2B The monovalent aromatic ring group with 3 to 20 carbon atoms in it can be suitably represented by Ar of formula (1B). 1B and Ar 2B The monovalent aromatic cyclic group with 3 to 20 carbon atoms. In formula (1b), Ar 1B and Ar 2B In a monovalent aromatic ring group with 3 to 20 carbon atoms, some or all of the hydrogen atoms may be substituted by groups selected from the group consisting of hydroxyl and halogen atoms.

[0120] While there are no specific examples of [b2] compounds, examples such as formulas (1b-1) to (1b-4) can be listed.

[0121] [Chemistry 15]

[0122]

[0123] In addition, compounds can also be formed together with [b] compounds and with the hydrogen atoms (H) in formulas (1a) and (1b) substituted by other substituents. Examples of substituents include alkyl, alkenyl, alkynyl, etc.

[0124] The reaction of compound [a] containing an aromatic ring with compound [b] can be carried out according to known methods, preferably in an inert gas environment such as nitrogen, in a reaction solvent. For example, mixing compound [a] containing an aromatic ring with compound [b] and heating the mixture allows for a batch reaction.

[0125] Regarding the reaction, if it is considered as a reaction in which the aromatic ring-containing compound [a] is regarded as the parent skeleton structure and a structure derived from compound [b] is introduced therein, the molar amount of compound [b] relative to the aromatic ring-containing compound [a] can be appropriately set considering the introduction rate of the structure derived from compound [b] into the aromatic ring-containing compound [a]. The molar amount of compound [b] relative to 1 mole of the aromatic ring-containing compound [a] can be appropriately selected in the range of more than 1 mole and less than 10 moles. The lower limit of the molar amount of compound [b] relative to 1 mole of the aromatic ring-containing compound [a] can be 2 moles, 3 moles, or 4 moles. The upper limit of the molar amount can be 9 moles, 8 moles, 7 moles, or 6 moles.

[0126] The lower limit of the reaction temperature is preferably 40°C, more preferably 50°C, and even more preferably 60°C. The upper limit of the reaction temperature is preferably 200°C, more preferably 160°C, and even more preferably 140°C. The lower limit of the reaction time is preferably 1 hour, more preferably 2 hours, and more preferably 5 hours. It can also be set to the temperature at which the solvent generates reflux. The upper limit of the reaction time is preferably 36 hours, more preferably 24 hours, and even more preferably 18 hours. An acid catalyst can also be added during the reaction. There are no particular limitations on the acid catalyst, and known inorganic acids and organic acids can be used. After the reaction, compound [A] can be obtained by separation, purification, drying, etc. As the reaction solvent, solvent [B] described later can be used appropriately.

[0127] <[B] Solvent>

[0128] [B] There are no particular limitations on the solvent if it can dissolve or disperse the [A] compound and any other components that may be present as needed.

[0129] Examples of solvents that can be classified as [B] include: hydrocarbon solvents, ester solvents, alcohol solvents, ketone solvents, ether solvents, nitrogen-containing solvents, etc. A single [B] solvent can be used alone or in combination of two or more.

[0130] Examples of hydrocarbon solvents include: aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and cyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

[0131] Examples of ester-based solvents include: carbonate solvents such as diethyl carbonate; monoacetic acid ester solvents such as methyl acetate and ethyl acetate; lactone solvents such as γ-butyrolactone; polyol partial ether carboxylic acid ester solvents such as diethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; and lactate solvents such as methyl lactate and ethyl lactate.

[0132] Examples of alcohol-based solvents include: mono-alcohol solvents such as methanol, ethanol, and n-propanol; and poly-alcohol solvents such as ethylene glycol and 1,2-propanediol.

[0133] Examples of ketone solvents include: chain ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; cyclic ketone solvents such as cyclohexanone.

[0134] Examples of ether-based solvents include: chain ether solvents such as n-butyl ether; cyclic ether solvents such as tetrahydrofuran and dioxane; polyol ether solvents such as propylene glycol dimethyl ether; and polyol partial ether solvents such as diethylene glycol monomethyl ether.

[0135] Examples of nitrogen-containing solvents include chain-like nitrogen-containing solvents such as N,N-dimethylacetamide and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.

[0136] As the solvent for [B], ester-based solvents or ketone-based solvents are preferred, more preferably polyol partial ether carboxylic acid ester-based solvents or cyclic ketone-based solvents, and even more preferably propylene glycol monomethyl ether acetate or cyclohexanone.

[0137] The lower limit of the content of [B] solvent in the composition is preferably 50% by mass, more preferably 60% by mass, and even more preferably 70% by mass. The upper limit of the content is preferably 99.9% by mass, more preferably 99% by mass, and even more preferably 95% by mass.

[0138] [Any ingredients]

[0139] The composition may contain any component without impairing the effects of the invention. Examples of such components include: acid generating agents, crosslinking agents, hot alkali generating agents, surfactants, polymers, defoamers, etc. As defoamers, known defoamers can be used, such as: alcohol defoamers, phosphate ester defoamers, fatty acid ester defoamers, polyether defoamers, silicone defoamers, etc. Examples of fatty acid ester defoamers include methyl laurate, methyl palmitate, methyl stearate, propyl butyrate, butyl butyrate, ethyl isovalerate, isobutyl propionate, etc., preferably propyl butyrate and butyl butyrate. Ketone solvents such as 2-heptanone can be used as defoamers. Any component may be used alone or in combination of two or more. The proportion of any component in the composition may be appropriately determined according to the type of any component, etc.

[0140] [Preparation method of the composition]

[0141] The composition can be prepared by mixing compound [A], solvent [B] and any other desired components in a specified ratio, preferably by filtering the obtained mixture using a membrane filter with a pore size of 0.5 μm or less.

[0142] [Coating Process]

[0143] In this process, a resist underlayer film forming composition is applied directly or indirectly onto a substrate. In this process, the composition described above is used as the resist underlayer film forming composition.

[0144] The coating method for the composition used to form the resist underlayer film is not particularly limited, and can be carried out by suitable methods such as spin coating, cast coating, or roller coating. A coating film is thus formed, and the resist underlayer film is formed by the evaporation of the [B] solvent.

[0145] Examples of substrates include silicon substrates, aluminum substrates, nickel substrates, chromium substrates, molybdenum substrates, tungsten substrates, copper substrates, tantalum substrates, titanium substrates, and other metal or semi-metal substrates, among which silicon substrates are preferred. The substrate may also be a substrate on which a silicon nitride film, an aluminum oxide film, a silicon dioxide film, a tantalum nitride film, a titanium nitride film, etc., are formed.

[0146] As an example of indirectly applying a resist underlayer film composition to a substrate, the case of applying a resist underlayer film composition to a silicon-containing film formed on the substrate (described later) can be cited.

[0147] [Heating Process]

[0148] The method for manufacturing the semiconductor substrate may also include a step of heating the coating film formed by the coating process. Heating the coating film can promote the formation of the resist underlayer film. More specifically, heating the coating film can promote the evaporation of solvent [B], etc.

[0149] The heating of the coating film can be performed in an atmospheric environment or in a nitrogen environment. The lower limit of the heating temperature is preferably 150°C, more preferably 200°C, and even more preferably 250°C. The upper limit of the heating temperature is preferably 600°C, more preferably 500°C. The lower limit of the heating time is preferably 15 seconds, more preferably 30 seconds. The upper limit of the heating time is preferably 1,200 seconds, more preferably 600 seconds.

[0150] Furthermore, the resist underlayer can be exposed after the coating process. Plasma can also be exposed to the resist underlayer after the coating process. Ion implantation can also be performed on the resist underlayer after the coating process. Exposure of the resist underlayer improves its etch resistance. Exposure of the resist underlayer to plasma improves its etch resistance. Ion implantation of the resist underlayer improves its etch resistance.

[0151] The radiation used in the exposure of the resist underlayer film can be appropriately selected from electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, X-rays, and gamma rays; and particle beams such as electron beams, molecular beams, and ion beams.

[0152] Methods for exposing the resist underlayer to plasma include, for example, the direct method based on placing the substrate in various gas environments and performing plasma discharge. The conditions for plasma exposure typically include a gas flow rate of 50 cc / min or more and 100 cc / min or less, and a power supply of 100 W or more and 1,500 W or less.

[0153] The lower limit for plasma exposure time is preferably 10 seconds, more preferably 30 seconds, and even more preferably 1 minute. The upper limit for said time is preferably 10 minutes, more preferably 5 minutes, and even more preferably 2 minutes.

[0154] Regarding plasma, plasma can be generated, for example, in an environment containing a mixture of H2 and Ar gases. In addition to H2 and Ar gases, carbon-containing gases such as CF4 or CH4 can also be introduced. Furthermore, at least one of CF4, NF3, CHF3, CO2, CH2F2, CH4, and C4F8 gases can be introduced to replace either or both of H2 and Ar gases.

[0155] Ion implantation into the resist underlayer involves implanting a dopant into the resist underlayer. Dopant can be selected from the group consisting of boron, carbon, nitrogen, phosphorus, arsenic, aluminum, and tungsten. Regarding the implantation energy used to apply a voltage to the dopant, it ranges from approximately 0.5 keV to 60 keV, depending on the type of dopant used and the desired implantation depth.

[0156] The lower limit for the average thickness of the formed resist underlayer film is preferably 30 nm, more preferably 50 nm, and even more preferably 100 nm. The upper limit for the average thickness is preferably 3,000 nm, more preferably 2,000 nm, and even more preferably 500 nm. Furthermore, the method for measuring the average thickness is based on the description in the examples.

[0157] [Silicone film formation process]

[0158] In this process, a silicon-containing film is formed directly or indirectly on the resist underlayer film formed by the coating process or the heating process. For example, a surface-modified resist film can be formed on the resist underlayer film indirectly. This surface-modified resist film is, for example, a film with a different contact angle with water than the resist underlayer film.

[0159] Silicon-containing films can be formed by coating with a silicon-containing film forming composition, chemical vapor deposition (CVD), atomic layer deposition (ALD), etc. Examples of methods for forming silicon-containing films by coating with a silicon-containing film forming composition include directly or indirectly coating the silicon-containing film forming composition onto a resist underlayer, and then exposing and / or heating the formed coating film to harden it. Commercially available silicon-containing film forming compositions include, for example, "NFC SOG01," "NFC SOG04," and "NFC SOG080" (all from JSR Corporation). Silicon oxide films, silicon nitride films, silicon oxynitride films, and amorphous silicon films can be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0160] Examples of radiation used in the exposure include: visible light, ultraviolet light, far ultraviolet light, X-rays, gamma rays, and other electromagnetic waves; and particle beams such as electron beams, molecular beams, and ion beams.

[0161] The lower limit of the temperature for heating the coating film is preferably 90°C, more preferably 150°C, and even more preferably 200°C. The upper limit of the temperature is preferably 550°C, more preferably 450°C, and even more preferably 300°C. Heating can also be performed in stages.

[0162] The lower limit for the average thickness of the silicon-containing film is preferably 1 nm, more preferably 10 nm, and even more preferably 20 nm. The upper limit is preferably 20,000 nm, more preferably 1,000 nm, and even more preferably 100 nm. The average thickness of the silicon-containing film is a value obtained by measuring it using the same spectroscopic ellipsometer as the average thickness of the resist underlayer film.

[0163] [Resist Pattern Forming Process]

[0164] In this process, a resist pattern is formed directly or indirectly on the resist underlayer film. Examples of methods for performing this process include: using a resist composition, using nanoimprint lithography, and using a self-organizing composition. Examples of indirectly forming a resist pattern on the resist underlayer film include forming a resist pattern on a silicon-containing film.

[0165] Examples of such resist compositions include: positive or negative chemically amplified resist compositions containing a radiosensitive linear acid generator; positive resist compositions containing an alkali-soluble resin and a quinone diazide-based photosensitive agent; negative resist compositions containing an alkali-soluble resin and a crosslinking agent; and metal-containing resist compositions containing metals such as tin, zirconium, and hafnium.

[0166] Methods for applying the resist composition include, for example, spin coating. The pre-baking temperature and time can be adjusted appropriately depending on the type of resist composition used.

[0167] Next, the formed resist film is exposed to selective radiation. The radiation used in the exposure can be appropriately selected depending on the type of radioactive linear acid generator used in the resist composition, such as: visible light, ultraviolet light, far ultraviolet light, X-rays, gamma rays, and other electromagnetic waves; electron beams, molecular beams, ion beams, and other particle beams. Among these, far ultraviolet light is preferred, more preferably KrF excimer laser light (wavelength 248 nm), ArF excimer laser light (wavelength 193 nm), F2 excimer laser light (wavelength 157 nm), Kr2 excimer laser light (wavelength 147 nm), ArKr excimer laser light (wavelength 134 nm), or extreme ultraviolet light (wavelength 13.5 nm, etc., hereinafter also referred to as "EUV (Extreme Ultraviolet)"), and even more preferably KrF excimer laser light, ArF excimer laser light, or EUV.

[0168] After exposure, post-baking can be performed to improve resolution, pattern outline, and developability. The temperature and time of post-baking can be appropriately determined depending on the type of resist composition used.

[0169] Next, the exposed resist film is developed using a developing solution to form a resist pattern. The development can be alkaline or organic solvent development. Examples of alkaline developing solutions include: ammonia, triethanolamine, tetramethylammonium hydroxide (TMAH), and tetraethylammonium hydroxide, etc. Appropriate amounts of water-soluble organic solvents such as methanol and ethanol, and surfactants, can also be added to these alkaline aqueous solutions. In the case of organic solvent development, examples of organic solvents used as the developing solution include various organic solvents exemplified as the solvent [B] in the composition described above.

[0170] After development using the developer, a specified resist pattern can be formed by cleaning and drying.

[0171] [Etching Process]

[0172] In this process, etching is performed using the resist pattern as a mask. The number of etching operations can be single or multiple; that is, etching can be performed sequentially using the pattern obtained through etching as a mask. From the viewpoint of obtaining a better pattern shape, multiple etching operations are preferred. In the case of multiple etching operations, for example, etching is performed sequentially in the order of the silicon film, the resist underlayer, and the substrate. Examples of etching methods include dry etching and wet etching. From the viewpoint of obtaining a better shape for the substrate pattern, dry etching is preferred. In dry etching, gas plasmas such as oxygen plasma can be used. Through this etching, a semiconductor substrate with a predetermined pattern can be obtained.

[0173] Dry etching can be performed using, for example, a known dry etching apparatus. The etching gas used in dry etching can be appropriately selected based on the mask pattern and the elemental composition of the film being etched. Examples include: fluorine-based gases such as CHF3, CF4, C2F6, C3F8, and SF6; chlorine-based gases such as Cl2 and BCl3; oxygen-based gases such as O2, O3, and H2O; reducing gases such as H2, NH3, CO, CO2, CH4, C2H2, C2H4, C2H6, C3H4, C3H6, C3H8, HF, HI, HBr, HCl, NO, and BCl3; and inert gases such as He, N2, and Ar. These gases can also be mixed. When etching the substrate using the pattern of the resist underlayer as a mask, fluorine-based gases are typically used.

[0174] Composition

[0175] The composition contains compound [A] and solvent [B]. This composition is suitable for use in the method for manufacturing the semiconductor substrate.

[0176] Methods for Manufacturing Compounds

[0177] The method for manufacturing the compound includes a step of reacting compound [a] with a compound containing an aromatic ring. The method for manufacturing compound [A] in the semiconductor substrate manufacturing method may be suitably employed as the manufacturing method.

[0178] Example

[0179] The present invention will now be described in detail based on embodiments, but the present invention is not limited to these embodiments.

[0180] [Weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (polymer dispersity index, PDI: Mw / Mn)]

[0181] The Mw and Mn of the polymer were determined using Tosoh (stock) gel permeation chromatography (GPC) columns (two "G2000HXL", one "G3000HXL", and one "G4000HXL") under analytical conditions of 1.0 mL / min flow rate, tetrahydrofuran dissolution solvent, and 40°C column temperature, by gel permeation chromatography using monodisperse polystyrene as a standard (detector: differential refractometer). The polydispersity (PDI) was calculated based on the determined Mw and Mn.

[0182] Average thickness of the resist underlayer film

[0183] The average thickness of the resist underlayer film was determined by measuring the film thickness at any 9 points, including the center, of the resist underlayer film formed on the silicon wafer (substrate) using a spectroellipsomerometer (JA WOOLLAM's "M2000D"). The average thickness of these film thicknesses was then calculated.

[0184] <[A] Synthesis of Compound>

[0185] In the synthesis of compound [A], the starting material compounds are compounds (a-1) to (a-18) represented by formulas (a-1) to (a-18) as compounds containing an aromatic ring, compounds (b-1) to (b-6) represented by formulas (b-1) to (b-6) as compounds [b], and compounds (c-1) to (c-2) represented by formulas (c-1) to (c-2) as compounds [c]. Compound [d], used as a modifying compound, is compounds (d-1) to (d-4) represented by formulas (d-1) to (d-4).

[0186] [Chemistry 16]

[0187]

[0188] [Chemistry 17]

[0189]

[0190] [Chemistry 18]

[0191]

[0192] [Chemistry 19]

[0193]

[0194] [Chemistry 20]

[0195]

[0196] <[A] Synthesis of Compound>

[0197] Compounds (A-1) to (A-37), represented by the following formulas, are synthesized as compounds [A] using the procedure shown below. In the following formulas, The number represents the bond of the aromatic ring to which R is bonded. The numbers added to the structures of R and Y represent the molar ratio of each compound in the total R and Y (totaling 1).

[0198] [Chemistry 21]

[0199]

[0200] [Chemistry 22]

[0201]

[0202] [Chemistry 23]

[0203]

[0204] [Chemistry 24]

[0205]

[0206] [Chemistry 25]

[0207]

[0208] [Chemistry 26]

[0209]

[0210] [Chemistry 27]

[0211]

[0212] [Chemistry 28]

[0213]

[0214] [Chemistry 29]

[0215]

[0216] [Example 1-1] (Synthesis of compound (A-1))

[0217] Under nitrogen atmosphere, 20.0 g of compound (a-1), 50.2 g of compound (b-1), 40.0 g of p-toluenesulfonic acid monohydrate, and 200 g of dioxane (molar ratio of compound (a-1) to compound (b-1) 1.0:4.0) were added to a reaction vessel, and the reaction was carried out under reflux for 8 hours. After the reaction was completed, the reaction solution was transferred to a separatory funnel, and 400 g of methyl isobutyl ketone and 400 g of water were added to wash the organic phase. After separating the aqueous phase, the obtained organic phase was washed several times with water. Then, the solution was concentrated using an evaporator, and the residue was added dropwise to 100 g of a methanol / water = 7 / 3 (v / v) solution to obtain a precipitate. The precipitate was recovered by suction filtration and washed several times with 100 g of methanol. Then, the solution was dried in a vacuum dryer at 60 °C for 12 hours to obtain compound (A-1). The Mw of compound (A-1) is 850 and the PDI is 1.02.

[0218] [Examples 1-2 to Example 1-21, Example 1-30 to Example 1-31, Example 1-33 to Example 1-37] (Synthesis of compounds (A-2) to (A-21), (A-30) to (A-31), (A-33) to (A-37))

[0219] Except for the types and amounts of starting compounds shown in Table 1 below, compounds (A-2) to (A-21), (A-30) to (A-31), and (A-33) to (A-37) were obtained as products under the same reaction conditions as in Examples 1-1. Mw and PDI are shown in Table 1.

[0220] [Examples 1-22] (Synthesis of compound (A-22))

[0221] Under nitrogen atmosphere, 20.0 g of compound (a-16), 40.4 g of compound (b-1), 2.0 g of trifluoromethanesulfonic acid, and 200 g of dioxane (molar ratio of compound (a-16) to compound (b-1) 1.0:3.0) were added to a reaction vessel, and the reaction was carried out at 80°C for 8 hours. After the reaction was completed, the reaction solution was transferred to a separatory funnel, and 400 g of methyl isobutyl ketone and 400 g of water were added to wash the organic phase. After separating the aqueous phase, the obtained organic phase was washed several times with water. Then, the solution was concentrated using an evaporator, and the residue was added dropwise to 100 g of a methanol / water = 7 / 3 (v / v) solution to obtain a precipitate. The precipitate was recovered by suction filtration and washed several times with 100 g of methanol. Then, the solution was dried in a vacuum dryer at 60°C for 12 hours to obtain compound (A-22). The Mw of compound (A-22) is 620, and the PDI is 1.06.

[0222] [Examples 1-23 to Examples 1-25, Examples 1-32] (Synthesis of compounds (A-23) to (A-25), and (A-32))

[0223] Except for the types and amounts of starting compounds shown in Table 1 below, compounds (A-23) to (A-25) and (A-32) were obtained as products under the same reaction conditions as in Examples 1-22. Mw and PDI are shown in Table 1.

[0224] [Examples 1-26] (Synthesis of compound (A-26))

[0225] In a reaction vessel under nitrogen atmosphere, 10.0 g of compound (A-13) was dissolved in 50.0 g of tetrahydrofuran, 4.52 g of potassium carbonate was added, and 3.89 g of compound (d-1) was added dropwise. The reaction was carried out at 50 °C for 3 hours. After the reaction was completed, an aqueous solution of oxalic acid was added to make the reaction system acidic. The reaction solution was then transferred to a separatory funnel, and 200 g of methyl isobutyl ketone and 200 g of water were added to wash the organic phase. After separating the aqueous phase, the obtained organic phase was washed several times with water. Then, the solution was concentrated using an evaporator, and the residue was added dropwise to 200 g of a methanol / water = 7 / 3 (v / v) solution to obtain a precipitate. The precipitate was recovered by suction filtration and washed several times with 50 g of methanol. The solution was dried in a vacuum dryer at 60 °C for 12 hours to obtain compound (A-26). The Mw of compound (A-26) was 990, and the PDI was 1.05.

[0226] [Examples 1-27] (Synthesis of compound (A-27))

[0227] In a reaction vessel under nitrogen atmosphere, 10.0 g of compound (A-13) was dissolved in 50.0 g of tetrahydrofuran, 4.52 g of potassium carbonate was added, and 5.40 g of compound (d-2) was added dropwise. The reaction was carried out at 50°C for 3 hours. After the reaction was completed, compound (A-27) was obtained by the same procedure as in Examples 1-26. The Mw of compound (A-27) was 1080, and the PDI was 1.08.

[0228] [Examples 1-28] (Synthesis of compound (A-28))

[0229] In a reaction vessel under nitrogen atmosphere, 10.0 g of compound (A-13) was dissolved in 50.0 g of tetrahydrofuran. The mixture was cooled to below 10°C, and 4.23 g of N,N-diisopropylethylamine was added, followed by dropwise addition of 1.32 g of compound (d-3). The mixture was then allowed to return to room temperature and reacted for 1 hour. After the reaction was complete, compound (A-28) was obtained by the same procedure as in Examples 1-26. Compound (A-28) has a Mw of 960 and a PDI of 1.06.

[0230] [Examples 1-29] (Synthesis of compound (A-29))

[0231] In a reaction vessel under nitrogen atmosphere, 10.0 g of compound (A-13) was dissolved in 50.0 g of tetrahydrofuran. The mixture was cooled to below 10°C, and 1.33 g of N,N-dimethylaminopyridine was added, followed by dropwise addition of 1.18 g of compound (d-4). The reaction was carried out at 50°C for 1 hour. After the reaction was complete, compound (A-29) was obtained by the same procedure as in Examples 1-26. Compound (A-29) has a Mw of 970 and a PDI of 1.06.

[0232] [Comparative Synthesis Example 1-1] (Synthesis of polymer (x-1))

[0233] Under nitrogen atmosphere, 250.0 g of m-cresol, 125.0 g of 37% formalin, and 2 g of oxalic anhydride were added to a reaction vessel. The reaction was carried out at 100°C for 3 hours and at 180°C for 1 hour. Unreacted monomers were then removed under reduced pressure to obtain polymer (x-1) represented by the following formula (x-1). The Mw of the obtained polymer (x-1) is 11,000.

[0234] [Chemistry 30]

[0235]

[0236] [Table 1]

[0237]

[0238] <Preparation of Compositions for Forming Resist Underlayer Film>

[0239] The following shows the [A] compound, [B] solvent, [C] acid generator, [D] crosslinking agent and other components used in the preparation of the composition for forming the resist underlayer film (hereinafter also referred to as the "composition").

[0240] [[A]compound]

[0241] A-1 to A-37: The synthesized compounds (A-1) to (A-37).

[0242] [[B]solvent]

[0243] B-1: Propylene glycol monomethyl ether acetate

[0244] B-2: Cyclohexanone

[0245] [[C] Acid generating agent]

[0246] C-1: The compound represented by the following formula (C-1)

[0247] [Chemistry 31]

[0248]

[0249] [[D] Crosslinking agent]

[0250] D-1: The compound represented by the following formula (D-1)

[0251] [Chemistry 32]

[0252]

[0253] D-2: The compound represented by the following formula (D-2)

[0254] [Chemistry 33]

[0255]

[0256] [Other ingredients]

[0257] E-1: The compound represented by the following formula (E-1) as a hot alkali generating agent.

[0258] [Chemistry 34]

[0259]

[0260] E-2: The compound represented by the following formula (E-2) as a hot alkali generating agent.

[0261] [Chemistry 35]

[0262]

[0263] x-1: The synthesized polymer (x-1)

[0264] [Example 2-1]

[0265] Three parts by mass of compound (A-1) as [A] were dissolved in 97 parts by mass of solvent (B-1) as [B]. The resulting solution was filtered using a polytetrafluoroethylene (PTFE) membrane filter with a pore size of 0.45 μm to prepare composition (J-1).

[0266] [Examples 2-2 to 2-48 and Comparative Example 2-1]

[0267] Compositions (J-2) to (J-48) and composition (CJ-1) were prepared in the same manner as in Examples 2-1, except that the types and amounts of each component shown in Table 2 below were used. “-” in Table 2 indicates that a matching component was not used.

[0268] [Table 2]

[0269]

[0270] <Evaluation>

[0271] [Examples 3-1 to 3-48 and Comparative Example 3-1]

[0272] The obtained composition was used, and its embeddability, heat resistance, etch resistance, and flexural strength were evaluated using the methods described below. The evaluation results are shown in Table 3 below.

[0273] [Embedded]

[0274] The prepared composition was applied to a substrate with a trench pattern having a depth of 65 nm and a width of 20 nm and 25 nm using a spin coater (Tokyo Electron, Ltd.'s "LITHIUS Pro Z") by spin coating. The spin coater was operated under conditions similar to those required to obtain a substrate with a film having an average thickness of 100 nm. Next, the substrate was heated at 400°C for 90 seconds under atmospheric conditions and then cooled at 23°C for 60 seconds. The cross-sectional shape of the substrate was observed (200,000x magnification) using a scanning electron microscope (Hitachi High-technologies, Ltd.'s "S-4800"), and the embedding properties were evaluated. Regarding embedding performance, the case where the resist underlayer film is embedded at the bottom of the 20 nm wide spatial pattern of the substrate is rated as "A" (good), the case where it is embedded at the bottom of the 25 nm wide spatial pattern but not at the bottom of the 20 nm wide spatial pattern is rated as "B" (slightly good), and the case where it is not embedded at the bottom of the 25 nm wide spatial pattern is rated as "C" (poor).

[0275] [Heat resistance]

[0276] The prepared composition was coated onto a silicon wafer (substrate) using a spin coater (Tokyo Electron, Inc.'s "CLEAN TRACK ACT12") via spin coating. Next, the mixture was heated at 200°C for 60 seconds under atmospheric conditions and then cooled at 23°C for 60 seconds to form a film with an average thickness of 200 nm, thus obtaining a substrate with a resist underlayer. The obtained substrate with the film was peeled off, and the powder was recovered. The recovered powder was placed in a container used for measurement using a Thermogravimetry-Differential Thermal Analysis (TG-DTA) apparatus (NETZSCH's "TG-DTA2000SR") to determine its mass before heating. Next, the powder was heated to 400°C under nitrogen atmosphere at a heating rate of 10°C / min using the TG-DTA apparatus, and the mass of the powder at 400°C was determined. Then, the mass reduction rate (%) is determined by the following formula, and the mass reduction rate is set as the standard for heat resistance.

[0277] M L ={(m1-m2) / m1}×100

[0278] Here, in the formula, M L The mass reduction rate is % (m1), where m1 is the mass before heating (mg) and m2 is the mass at 400℃ (mg).

[0279] The smaller the mass reduction rate of the powder used as the sample, the less sublimation or decomposition products are generated when the film is heated, and the better the heat resistance. That is, the smaller the mass reduction rate, the higher the heat resistance. Regarding heat resistance, a mass reduction rate of less than 5% is rated as "A" (extremely good), a mass reduction rate of 5% or more but less than 10% is rated as "B" (good), and a mass reduction rate of more than 10% is rated as "C" (poor).

[0280] [Etching Resistance]

[0281] Using a spin coater (Tokyo Electron Inc.'s "CLEAN TRACK ACT12"), the prepared composition was coated onto a silicon wafer (substrate) by spin coating. Next, the mixture was heated at 350°C for 60 seconds under atmospheric conditions and then cooled at 23°C for 60 seconds, thereby forming a film with an average thickness of 200 nm, thus obtaining a substrate with a resist underlayer formed on the substrate. The film in the obtained substrate with the film was processed using an etching apparatus (TACTRAS of Tokyo Electron Co., Ltd.) under the following conditions: CF4 / Ar = 110 / 440 sccm, PRESS. = 30 MT, HF RF (high-frequency power for plasma generation) = 500 W, LF RF (high-frequency power for bias) = ​​3000 W, DCS = -150 V, RDC (gas sensor flow ratio) = 50%, and 30 seconds. The etching rate (nm / min) was calculated based on the average thickness of the film before and after processing. Then, the ratio relative to Comparative Example 1 was calculated using the etching rate of Comparative Example 1 as a benchmark, and this ratio was set as the standard for etch resistance. Regarding etch resistance, a ratio of 0.90 or less was rated as "A" (extremely good), a ratio exceeding 0.90 but less than 0.92 was rated as "B" (good), and a ratio of 0.92 or more was rated as "C" (poor). In addition, “-” in Table 3 indicates the evaluation criteria for etch resistance.

[0282] [Bending resistance]

[0283] Using a spin coater (Tokyo Electron, Inc.'s "CLEAN TRACK ACT12"), the prepared composition was applied to a silicon substrate having a silicon dioxide film with an average thickness of 500 nm formed by spin coating. Next, the substrate was heated at 400°C for 60 seconds under atmospheric conditions and then cooled at 23°C for 60 seconds, thereby obtaining a substrate with a resist underlayer film having an average thickness of 200 nm. After applying a silicon-containing film forming composition (JSR, Inc.'s "NFC SOG080") to the obtained substrate with the film by spin coating, the substrate was heated at 200°C for 60 seconds under atmospheric conditions and then at 300°C for 60 seconds, forming a silicon-containing film with an average thickness of 50 nm. ArF resist composition (JSR Corporation's "AR1682J") was applied to the silicon-containing film using spin coating. The film was then heated (calcined) at 130°C for 60 seconds under atmospheric conditions to form a resist film with an average thickness of 200 nm. For the resist film, an ArF excimer laser exposure apparatus (lens numerical aperture 0.78, exposure wavelength 193 nm) was used to expose a 1:1 line-and-space mask pattern with a target size of 100 nm by varying the exposure amount. The film was then heated (calcined) at 130°C for 60 seconds under atmospheric conditions, developed at 25°C for 1 minute using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution, and washed and dried to obtain a substrate with a line-and-space resist pattern having a linewidth of 30 nm to 100 nm and a spacing of 200 nm.

[0284] Using the resist pattern as a mask, the etching apparatus is used to etch the silicon-containing film under the following conditions: CF4 = 200 sccm, PRESS. = 85 mT, HF RF (high-frequency power for plasma generation) = 500 W, LF RF (high-frequency power for bias voltage) = 0 W, DCS = -150 V, and RDC (gas sensor flow ratio) = 50%, to obtain a substrate with a pattern formed on the silicon-containing film. Next, using the silicon-containing film pattern as a mask, the etching apparatus is used to etch the resist underlayer film under the following conditions: O2 = 400 sccm, PRESS. = 25 mT, HFRF (high-frequency power for plasma generation) = 400 W, LF RF (high-frequency power for bias voltage) = 0 W, DCS = 0 V, and RDC (gas sensor flow ratio) = 50%, to obtain a substrate with a pattern formed on the resist underlayer film. Using the resist underlayer pattern as a mask, the etching apparatus is used to etch the silicon dioxide film under the following conditions: CF4 = 180 sccm, Ar = 360 sccm, PRESS. = 150 mT, HF RF (high-frequency power for plasma generation) = 1,000 W, LF RF (high-frequency power for bias) = ​​1,000 W, DCS = -150 V, RDC (gas sensor flow ratio) = 50%, and 60 seconds, to obtain a substrate with a pattern formed on the silicon dioxide film.

[0285] Subsequently, for the substrate with the pattern formed on the silicon dioxide film, an image was obtained by magnifying the shape of the resist underlayer film pattern of each linewidth by 250,000 times using a scanning electron microscope (Hitachi High-technologies, Inc.'s "CG-4000"), and image processing was performed on it, thereby... Figure 1 As shown, for the transverse side 3a of the resist underlayer film pattern 3 (line pattern) with a length of 1,000 nm, a 3-sigma value is obtained by multiplying the standard deviation calculated by the position Xn (n=1 to 10) in the linewidth direction obtained by measuring 10 locations at 100 nm intervals and the position Xa of the average position in these linewidth directions. This value is set as the line edge roughness (LER). The LER, which represents the degree of bending of the resist underlayer film pattern, increases as the linewidth of the resist underlayer film pattern becomes thinner. Regarding bending resistance, a film pattern with an LER of 5.5 nm and a linewidth of less than 35.0 nm is evaluated as "A" (good), a linewidth of 35.0 nm or more but less than 40.0 nm is evaluated as "B" (slightly good), and a linewidth of 40.0 nm or more is evaluated as "C" (poor). Furthermore, Figure 1 The curvature of the membrane pattern shown is exaggerated compared to reality.

[0286] [Table 3]

[0287]

[0288] As can be seen from the results in Table 3, compared with the resist underlayer film formed by the composition of the comparative example, the resist underlayer film formed by the composition of the example has excellent embeddability, heat resistance, etching resistance and bending resistance.

[0289] Industrial availability

[0290] The semiconductor substrate manufacturing method of the present invention provides a well-patterned substrate. The compositions of the present invention can form a resist underlayer film with excellent embeddability, heat resistance, etch resistance, and flexural strength. The method for manufacturing the compounds of the present invention can efficiently produce compounds suitable for said compositions. Therefore, these are suitable for use in the manufacture of semiconductor devices that are expected to be further miniaturized in the future.

[0291] Explanation of icon numbers

[0292] 3: Pattern of the resist underlayer film

[0293] 3a: Lateral side view of the resist underlayer pattern

Claims

1. A method for manufacturing a semiconductor substrate, comprising: The process of directly or indirectly coating a composition for forming a resist underlayer film on a substrate; The process of directly or indirectly forming a resist pattern on the resist underlayer film formed by the coating process; and An etching process is performed using the resist pattern as a mask, and The composition for forming the resist underlayer film contains: The compounds represented by formula (1A) or formula (1B) below, and solvent; [Chemistry 1] (In formula (1A), Ar) 1A and Ar 2A Each is an aromatic ring with 3 to 20 carbon atoms, either substituted or unsubstituted; Y is a single bond, an oxygen atom, a sulfur atom, or a methylene group; X is an n-valent organogroup having an aromatic ring; the bond extending from X is an extension of the aromatic ring in X; n is an integer from 1 to 10; In equation (1B), Ar 1B and Ar 2B Each is independently an unsubstituted monovalent aromatic cyclic group having 3 to 20 carbon atoms or a monovalent aromatic cyclic group having 3 to 20 carbon atoms substituted by a group selected from the group consisting of hydroxyl and halogen atoms; X and n have the same meaning as in the above formula (1A).

2. The method for manufacturing a semiconductor substrate according to claim 1, further comprising, before the resist pattern is formed, The process of forming a silicon-containing film directly or indirectly on the resist underlayer film.

3. A composition comprising: The compounds represented by formula (1A) or formula (1B) below, and solvent; [Chemistry 2] (In formula (1A), Ar) 1A and Ar 2A Each is an aromatic ring with 3 to 20 carbon atoms, either substituted or unsubstituted; Y is a single bond, an oxygen atom, a sulfur atom, or a methylene group; X is an n-valent organogroup having an aromatic ring; the bond extending from X is an extension of the aromatic ring in X; n is an integer from 1 to 10; In equation (1B), Ar 1B and Ar 2B Each is independently an unsubstituted monovalent aromatic cyclic group having 3 to 20 carbon atoms or a monovalent aromatic cyclic group having 3 to 20 carbon atoms substituted by a group selected from the group consisting of hydroxyl and halogen atoms; X and n have the same meaning as in the above formula (1A).

4. The composition according to claim 3, wherein in formulas (1A) and (1B), X has 6 or more and 70 or fewer carbon atoms.

5. The composition according to claim 3 or 4, wherein in formula (1A) and formula (1B), n is 2 or more.

6. The composition according to claim 3 or 4, wherein in formula (1A), Ar 1A and Ar 2A Each is an aromatic hydrocarbon ring having 6 to 20 carbon atoms, or a ring structure formed by substituting part or all of the hydrogen atoms of the aromatic hydrocarbon ring with a hydrocarbon group, hydroxyl group, cyano group, nitro group, carboxyl group or amino group having 1 to 6 carbon atoms.

7. The composition according to claim 3 or 4, wherein in formula (1B), Ar 1B and Ar 2B Each is independently a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monovalent group formed by substituting part or all of the hydrogen atoms of the aromatic hydrocarbon group with a group selected from the group consisting of hydroxyl and halogen atoms.

8. The composition according to claim 3 or 4, wherein the compound in the composition comprises 1% by mass or more of the components other than the solvent.

9. The composition according to claim 3 or 4, used to form a resist underlayer film.

10. A method for manufacturing a compound, comprising: A process for reacting an aromatic ring-containing compound with a compound represented by formula (1a) or formula (1b) below; [Chemistry 3] (In formula (1a), Ar) 1A and Ar 2A Each is an aromatic ring with 3 to 20 carbon atoms, either substituted or unsubstituted; Y is a single bond, an oxygen atom, a sulfur atom, or a methylene group; In equation (1b), Ar 1B and Ar 2B Each is independently an unsubstituted monovalent aromatic cycloalloy with 3 to 20 carbon atoms or a monovalent aromatic cycloalloy with 3 to 20 carbon atoms substituted by a group selected from the group consisting of hydroxyl and halogen atoms.

11. The method for manufacturing the compound according to claim 10, wherein the aromatic ring-containing compound has a phenolic hydroxyl group.

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