Alkoxyl-containing inhibitors for lower layer film formation

Abstract

A composition for forming a resist lower layer film for EB or EUV lithography, comprising a film-forming component and a solvent, wherein the aforementioned film-forming component comprises at least 20% by mass of a component containing a specific structure, and the component containing the specific structure comprises at least one of a first structure containing an aromatic ring and a second structure containing a nitrogen atom, wherein the aforementioned first structure comprises a group directly linked to the aforementioned aromatic ring as represented by the following formula (1), and the aforementioned second structure comprises a group directly linked to the aforementioned nitrogen atom as represented by the following formula (1), (in formula (1), R1 represents an alkyl group having 1 to 6 carbon atoms, and R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 10 total carbon atoms. * represents a bond.)

Description

Technical Field

[0001] This invention relates to a composition for forming a resist underlayer film for EB or EUV lithography, a resist underlayer film for EB or EUV lithography, a substrate for semiconductor processing, a method for manufacturing a semiconductor device, a pattern forming method, and a method for improving the LWR of the resist pattern. Prior Technology

[0002] In semiconductor devices such as LSI (Low-Semiconductor Integrated Circuit), as the density of aggregation increases, the formation of fine patterns becomes more demanding, and in recent years the smallest pattern size has reached below 100 nm. The formation of such fine patterns in semiconductor devices is achieved by shortening the wavelength of the light source in the exposure apparatus and improving the resist materials. Currently, an immersion exposure method is being used, which uses ArF (argon fluoride) excimer laser light with a wavelength of 193nm in deep ultraviolet light as the light source and exposes the device in a water-isolated environment. Regarding resist materials, various ArF-compatible resist materials with acrylic resin as the matrix are also being developed.

[0003] Furthermore, as a next-generation exposure technology, the EB exposure method, which uses an electron beam (EB), or the EUV (extreme ultraviolet) exposure method, which uses soft X-rays with a wavelength of 13.5nm as a light source, is being reviewed, and the pattern size is being further miniaturized to below 30nm. However, with the miniaturization of these patterns, the voids in the resist pattern sidewalls (LER; line edge roughness) and the non-uniformity of the resist pattern width (LWR; line width roughness) increase, raising concerns about their adverse effects on apparatus performance. Although efforts are underway to suppress these issues through optimization of exposure equipment, resist materials, and process conditions, sufficient results have not yet been obtained. Furthermore, LWR and LER are related; improving LWR will also improve LER.

[0004] As a solution to the above problems, a method is disclosed in which, in the rinsing step after development, an aqueous solution containing a specific ionic surfactant is used to treat the resist pattern, so that while the defects (such as the generation of residual parts or pattern collapse) are suppressed by development, the unevenness of the resist pattern is dissolved, and the aforementioned LWR and LER are improved (see Patent Document 1). [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2007-213013 Summary of the Invention

[0006] [The problem that the invention aims to solve]

[0007] The purpose of this invention is to provide a composition for forming a resist underlayer film for EB or EUV lithography, a resist underlayer film for EB or EUV lithography, a semiconductor processing substrate, a semiconductor device manufacturing method, a pattern forming method, and a method for improving the resist pattern LWR. [Methods used to solve problems]

[0008] As a result of active review in order to solve the above-mentioned problems, the inventors discovered a way to solve the above-mentioned problems and completed the present invention having the following key points. That is, the present invention includes the following contents. [1] A composition for forming a resist lower layer film for EB or EUV lithography, comprising a film-forming component and a solvent, and The aforementioned film-forming component comprises at least 20% by mass of a component containing a specific structure, and the component containing the specific structure comprises at least one of a first structure containing an aromatic ring and a second structure containing a nitrogen atom. The aforementioned first structure comprises a base directly linked to the aforementioned aromatic ring, as represented by the following formula (1). The aforementioned second structure comprises a base directly linked to the aforementioned nitrogen atom as represented by the following formula (1). (In formula (1), R1 represents an alkyl group with 1 to 6 carbon atoms, and R2 represents an alkyl group with 1 to 6 carbon atoms, or an alkoxyalkyl group with 2 to 10 total carbon atoms. * represents a bond.) [2] As described in [1], the composition for forming the lower layer film of the resist used in EB or EUV lithography, wherein the aforementioned component containing a specific structure comprises a polymer, and The aforementioned polymer system includes at least one of the aforementioned first structure and the aforementioned second structure. [3] The composition for forming the lower layer film of the resist for EB or EUV lithography as described in [2], wherein the polymer comprises at least one of the following structures as the first structure: the structure represented by formula (11), the structure represented by formula (12), and the structure represented by formula (13). In formulas (11) to (13), R1 represents alkyl groups with 1 to 6 carbon atoms, R2 represents hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, or alkoxyalkyl groups with 2 to 10 total carbon atoms, and R3 represents alkyl groups with 1 to 6 carbon atoms. * represents bonded bonds. In equation (11), n1 represents integers from 1 to 4, n2 represents integers from 0 to 3, and n3 represents integers from 0 to 3. n1, n2, and n3 satisfy 1 ≦ (n1 + n2 + n3) ≦ 4. In equation (12), n1 represents integers from 1 to 6, n2 represents integers from 0 to 5, and n3 represents integers from 0 to 5. n1, n2, and n3 satisfy 1 ≦ (n1 + n2 + n3) ≦ 6. In equation (13), n1 represents integers from 1 to 8, n2 represents integers from 0 to 7, and n3 represents integers from 0 to 7. n1, n2, and n3 satisfy 1≦(n1+n2+n3)≦8. In equations (11) to (13), when there are two or more R1 values, the two or more R1 values ​​can be the same or different. When there are two or more R2 values, the two or more R2 values ​​can be the same or different. When there are two or more R3 values, the two or more R3 values ​​can be the same or different. [4] The composition for forming the lower layer film of the resist for EB or EUV lithography as described in [3], wherein the polymer comprises at least one of the repeating units represented by the following formula (11-1) and the repeating units represented by the following formula (11-2) as repeating units comprising the structure represented by the aforementioned formula (11). In formulas (11-1) and (11-2), R1 represents alkyl groups with 1 to 6 carbon atoms, R2 represents hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, or alkoxyalkyl groups with 2 to 10 total carbon atoms, and R3 represents alkyl groups with 1 to 6 carbon atoms. n1 represents integers from 1 to 4, n2 represents integers from 0 to 3, and n3 represents integers from 0 to 3. In formula (11-1), X1 and X2 represent single bonds, oxygen atoms, or methylene groups, respectively. In formula (11-2), X1 and X2 series independently represent single bonds, oxygen atoms, or methylene groups, respectively. X3 series represents single bonds or divalent organic groups with 1 to 15 carbon atoms. In equation (11-1), n1, n2 and n3 satisfy 1≦(n1+n2+n3)≦4. In equation (11-2), n1, n2, and n3 in the benzene ring on the left satisfy 1≦(n1+n2+n3)≦4. n1, n2, and n3 in the benzene ring on the right satisfy 1≦(n1+n2+n3)≦4. In equations (11-1) and (11-2), when there are two or more R1 values, the two or more R1 values ​​can be the same or different. Similarly, when there are two or more R2 values, the two or more R2 values ​​can be the same or different. And when there are two or more R3 values, the two or more R3 values ​​can be the same or different. [5] The composition for forming a resist underlayer film for EB or EUV lithography as described in any of [2] to [4], wherein the aforementioned polymer comprises repeating units represented by the following formula (14). (In equation (14), Q represents the basis of 2 valence.) [6] As described in [5], the composition for forming the lower layer film of the resist for EB or EUV lithography, wherein in the aforementioned formula (14), Q represents a divalent group represented by the following formula (14-1), or an aryl group with 6 to 40 carbon atoms. (In equation (14-1), X represents the basis represented by any one of the terms in equations (14-1a) to (14-1c) below.) (In formulas (14-1a) to (14-1c), R11, R12, R13, R14, and R15 each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The aforementioned benzyl and phenyl groups can also be substituted by groups selected from the group consisting of alkyl groups with 1 to 6 carbon atoms, halogen atoms, alkoxy groups with 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups with 1 to 6 carbon atoms. Furthermore, R11 and R12 can also bond to each other to form a ring with 3 to 6 carbon atoms. R13 and R14 can also bond to each other to form a ring with 3 to 6 carbon atoms. * indicates a bond. *1 indicates a bond bonded to a carbon atom. *2 indicates a bond bonded to a nitrogen atom.) [7] As described in [1], the composition for forming the lower layer film of the resist used in EB or EUV lithography, wherein the aforementioned component containing a specific structure includes a crosslinking agent, and The aforementioned crosslinking agent comprises at least one of the compounds represented by formula (21), formula (22), and formula (23). In formulas (21) to (23), R1 represents alkyl groups with 1 to 6 carbon atoms, R2 represents alkyl groups with 1 to 6 carbon atoms or alkoxyalkyl groups with 2 to 10 total carbon atoms, and R3 represents alkyl groups with 1 to 6 carbon atoms. In equation (21), m1 and m2 each independently represent integers from 1 to 2. When m1 and m2 are both 1, Q1 represents a single bond, an oxygen atom, or an organic group with a divalent carbon number from 1 to 20. When the sum of m1 and m2 is 3 or 4, Q1 represents an organic group with a (m1+m2) valence of carbon number from 1 to 20. In equation (21), n1 represents integers from 1 to 5, n2 represents integers from 0 to 4, and n3 represents integers from 0 to 4. In each benzene ring, n1, n2, and n3 satisfy 1 ≤ (n1 + n2 + n3) ≤ 5. In formula (23), Y represents an organogroup with 1 to 20 carbon atoms in a monovalent state. [8] As described in [7], the composition for forming the lower layer of the resist for EB or EUV lithography includes a polymer that does not belong to the aforementioned composition containing a specific structure. [9] The composition for forming a resist underlayer film for EB or EUV lithography as described in any of [1] to [8], wherein the aforementioned film-forming component further contains a hardening catalyst.

[10] The composition for forming an EB or EUV lithography resist underlayer film as described in any of [1] to [9] is used for forming an EB or EUV lithography resist underlayer film with a thickness of less than 10 nm.

[11] An EB or EUV lithography resist underlayer film, which is a hardened form of the composition for forming an EB or EUV lithography resist underlayer film as described in any of [1] to

[10] .

[12] A semiconductor processing substrate, comprising a semiconductor substrate, and As described in

[11] , the resist lower layer film for EB or EUV lithography.

[13] A method for manufacturing a semiconductor device, comprising: The steps of forming a resist underlayer film on a semiconductor substrate using a composition for forming an EB or EUV lithography resist underlayer film as described in any of [1] to

[10] , and The step of forming a resist film on top of the aforementioned resist lower layer film using an EB or EUV lithography resist.

[14] A method for forming a graphic, comprising: The steps of forming a resist underlayer film on a semiconductor substrate using a composition for forming an EB or EUV lithography resist underlayer film as described in any of [1] to

[10] , and The steps of forming a resist film on top of the aforementioned resist lower layer film using an EB or EUV lithography resist, and... The steps of irradiating the aforementioned resist film with EB or EUV, followed by developing the resist film to obtain a resist pattern, and... Using the aforementioned resist pattern as a mask, the aforementioned step of etching the resist underlayer film is performed.

[15] A method for improving the LWR of an inhibitor pattern, comprising: The steps of forming a resist underlayer film on a semiconductor substrate using a composition for forming an EB or EUV lithography resist underlayer film as described in any of [1] to

[10] , and The steps of forming a resist film on top of the aforementioned resist lower layer film using EB or EUV lithography resist, and... The steps involve irradiating the aforementioned resist film with EB or EUV, and then developing the aforementioned resist film to obtain a resist pattern. [Invention Effects]

[0009] According to the present invention, a method for manufacturing a resist underlayer film for EB or EUV lithography, a resist underlayer film for EB or EUV lithography, a semiconductor processing substrate, a semiconductor device, a pattern forming method, and a method for improving the resist pattern LWR can be provided. Implementation

[0010] The inventors reviewed methods to improve the low resist rinsing (LWR) using methods other than the rinsing step. They found that the composition for resist underlayer film formation proposed by the applicant in International Publication No. 2009 / 075265 is effective in improving the LWR of resist patterns in EB or EUV lithography. In International Publication No. 2009 / 075265, the composition for forming the resist underlayer film proposed by the applicant acts as an anti-reflective film to suppress the effects of reflected waves on the resist film when the resist film is exposed in ArF lithography. On the other hand, in EB or EUV lithography, since the EB or EUV light is irradiated through the substrate, an anti-reflective film is not required. Therefore, it is not easy to find advantages when using the composition for forming the resist underlayer film proposed by the applicant in International Publication No. 2009 / 075265 for resist underlayer films in EB or EUV lithography. However, after using the composition for forming the resist underlayer film proposed by the applicant in International Publication No. 2009 / 075265 for resist underlayer films in EB or EUV lithography, the inventors unexpectedly discovered that the LWR can improve the resist pattern. Furthermore, after reviewing the materials, the inventors found that the groups in the film-forming components of the composition for forming the lower layer film of the inhibitor, represented by the following formula (1) bonded to an aromatic ring or nitrogen atom, are effective in improving the LWR of the inhibitor pattern, thus completing the present invention.

[0011] (Composition for forming the lower layer film of resist for EB or EUV lithography) The composition for forming a resist underlayer film for EB or EUV lithography (hereinafter, also referred to as "resistor underlayer film formation composition") of the present invention contains a film forming component and a solvent.

[0012] <Membrane-forming components> The membrane-forming component contains at least 20% by mass of a component with a specific structure. The term "film-forming component" refers to the component remaining in the resist underlayer film during the formation of the resist underlayer film (hereinafter referred to simply as "resistor underlayer film") using the resist underlayer film-forming composition. Examples of film-forming components include components that exist in the resist underlayer film in their original state, components that exist in the resist underlayer film as reaction products with other components, and components used as auxiliaries (e.g., curing catalysts) that facilitate the reaction of other components. Film-forming components, in other words, are the total number of substances other than solvents among all the components of the composition used to form the lower layer of the barrier film. There are no particular restrictions on the content of the component containing the specific structure in the membrane-forming component if it is 20% by mass or more. The content of the component containing the specific structure in the membrane-forming component can be 20% by mass to 100% by mass, or 20% by mass to 99.5% by mass. The content of the component containing a specific structure in the composition for forming the lower layer of the resist for EB or EUV lithography is not particularly limited if the content of the component containing a specific structure in the film-forming component is 20% by mass or more. However, if the film-forming component includes polymers that do not contain a specific structure as described below, the content is preferably 10% to 90% by mass, more preferably 15% to 70% by mass, and especially preferably 20% to 50% by mass, relative to polymers that do not contain a specific structure.

[0013] <<Components containing specific structures>> As a component containing a specific structure, it is not particularly limited if it includes at least one of a first structure containing an aromatic ring and a second structure containing a nitrogen atom. The first structure comprises the base represented by the following formula (1) directly linked to the aromatic ring. The second structure contains the base represented by the following formula (1) directly linked to the nitrogen atom. Hereinafter, "at least one of the first structure containing an aromatic ring and the second structure containing a nitrogen atom" will also be referred to as "specific structure". (In formula (1), R1 represents an alkyl group with 1 to 6 carbon atoms, and R2 represents an alkyl group with 1 to 6 carbon atoms, or an alkoxyalkyl group with 2 to 10 total carbon atoms. * represents a bond.)

[0014] The alkyl group having 1 to 6 carbon atoms in this invention can be any of the following: linear, branched, or cyclic. For example, alkyl groups having 1 to 4 carbon atoms can be cited as examples of alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methylene, 1,2-electroethyl, 1,1-electroethyl, 1,2-electropropyl, 1,3-electropropyl, tetramethylene, 1-methyl-1,3-electropropyl, 2-methyl-1,3-electropropyl, 2-methyl-1,2-electropropyl, pentamethylene, hexamethylene, 1,3-electrocyclohexyl, and 1,4-electrocyclohexyl. From the viewpoint of achieving the desired effects of the present invention, alkyl groups having 1 to 4 carbon atoms are preferred, and methylene groups are even more preferred.

[0015] The alkyl group having 1 to 6 carbon atoms in this invention can be any of the following: linear, branched, or cyclic. For example, alkyl groups having 1 to 4 carbon atoms can be cited as examples of alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1- Methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3- Dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl It includes 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, etc. Of these, from the viewpoint of suitably obtaining the effects of the present invention, alkyl groups having 1 to 4 carbon atoms are preferred, and methyl groups are even more preferred.

[0016] Examples of alkoxyalkyl groups with a total carbon number of 2 to 10 in this invention include methoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-methoxypropyl, 2-methoxypropyl, 3-methoxypropyl, 1-methoxy-1-methylethyl, 2-methoxy-1-methylethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, 1-ethoxypropyl, 2-ethoxypropyl, 3-ethoxypropyl, 1-ethoxy-1-methylethyl, 2-ethoxy-1-methylethyl, propoxymethyl, 1-propoxyethyl, 2-propoxyethyl, 1-propoxy-1-methylethyl, 2-propoxy-1-methylethyl, isopropoxymethyl, 1-isopropoxyethyl, 2-isopropoxyethyl, butoxymethyl, sec-butoxymethyl, isobutoxymethyl, and tert-butoxymethyl. The number of carbon atoms in the alkoxyalkyl group is preferably 1 to 6, and more preferably 1 to 4. The number of carbon atoms in the alkyl group of the alkoxyalkyl group is preferably 1 to 4, more preferably 1 to 2. Of these, 2-methoxy-1-methylethyl is preferred from the viewpoint of achieving the desired effects of the present invention.

[0017] <<<Polymers containing components with specific structures>>> It contains components with a specific structure, for example, it contains polymers with a specific structure. The polymer containing a specific structure preferably includes at least one of the following structures as a first structure: the structure represented by formula (11), the structure represented by formula (12), and the structure represented by formula (13). In formulas (11) to (13), R1 represents alkyl groups with 1 to 6 carbon atoms, R2 represents hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, or alkoxyalkyl groups with 2 to 10 total carbon atoms, and R3 represents alkyl groups with 1 to 6 carbon atoms. * represents bonded bonds. In equation (11), n1 represents integers from 1 to 4, n2 represents integers from 0 to 3, and n3 represents integers from 0 to 3. n1, n2, and n3 satisfy 1 ≦ (n1 + n2 + n3) ≦ 4. In equation (12), n1 represents integers from 1 to 6, n2 represents integers from 0 to 5, and n3 represents integers from 0 to 5. n1, n2, and n3 satisfy 1 ≦ (n1 + n2 + n3) ≦ 6. In equation (13), n1 represents integers from 1 to 8, n2 represents integers from 0 to 7, and n3 represents integers from 0 to 7. n1, n2, and n3 satisfy 1≦(n1+n2+n3)≦8. In equations (11) to (13), when there are two or more R1 values, the two or more R1 values ​​can be the same or different. When there are two or more R2 values, the two or more R2 values ​​can be the same or different. When there are two or more R3 values, the two or more R3 values ​​can be the same or different.

[0018] In equation (11), n1 is preferably an integer between 2 and 3, and more preferably 2. In equation (12), n1 is preferably an integer from 2 to 4, and more preferably 2. In equation (13), n1 is preferably an integer from 2 to 6, and more preferably 2. In equation (11), n2 is preferably an integer between 0 and 1, and more preferably 0. In equation (12), n2 is preferably an integer from 0 to 3, and more preferably 0. In equation (13), n2 is preferably an integer from 0 to 5, and more preferably 0. In equation (11), n3 is preferably an integer from 0 to 1, and more preferably 1. In equation (12), n3 is preferably an integer from 0 to 3, and more preferably 1. In equation (13), n3 is preferably an integer from 0 to 5, and more preferably 1.

[0019] The polymer containing a specific structure preferably contains at least one of the repeating units represented by formula (11-1) and the repeating units represented by formula (11-2) as repeating units containing the structure represented by formula (11). In formulas (11-1) and (11-2), R1 represents alkyl groups with 1 to 6 carbon atoms, R2 represents hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, or alkoxyalkyl groups with 2 to 10 total carbon atoms, and R3 represents alkyl groups with 1 to 6 carbon atoms. n1 represents integers from 1 to 4, n2 represents integers from 0 to 3, and n3 represents integers from 0 to 3. In formula (11-1), X1 and X2 represent single bonds, oxygen atoms, or methylene groups, respectively. In formula (11-2), X1 and X2 series independently represent single bonds, oxygen atoms, or methylene groups, respectively. X3 series represents single bonds or divalent organic groups with 1 to 15 carbon atoms. In equation (11-1), n1, n2 and n3 satisfy 1≦(n1+n2+n3)≦4. In equation (11-2), n1, n2, and n3 in the benzene ring on the left satisfy 1≦(n1+n2+n3)≦4. n1, n2, and n3 in the benzene ring on the right satisfy 1≦(n1+n2+n3)≦4. In equations (11-1) and (11-2), when there are two or more R1 values, the two or more R1 values ​​can be the same or different. Similarly, when there are two or more R2 values, the two or more R2 values ​​can be the same or different. And when there are two or more R3 values, the two or more R3 values ​​can be the same or different.

[0020] The preferred state samples of n1, n2 and n3 in equation (11-1) are the same as the preferred state samples of n1, n2 and n3 in equation (11). The preferred states of n1, n2 and n3 in the benzene ring on the left side of formula (11-2) and the preferred states of n1, n2 and n3 in the benzene ring on the right side are the same as the preferred states of n1, n2 and n3 in formula (11).

[0021] As an organogroup with 1 to 15 carbon atoms in X3 in formula (11-2), for example, an organogroup with divalent oxidation can be represented by the following formula (11-2-1). (In formula (11-2-1), Ra and Rb series independently represent hydrogen atoms and alkyl groups with ~6 carbon atoms, or -CF3. * series represents bonded bonds.)

[0022] Polymers containing a specific structure preferably further contain repeating units represented by the following formula (14). (In equation (14), Q represents the basis of 2 valence.)

[0023] The polymer containing a specific structure is preferably a repeating unit represented by formula (14) together with a repeating unit represented by formula (11-1) containing a repeating unit represented by formula (15) below. In equation (15), R1, R2, R3, n1, n2, n3, X1, X2, and Q are the same as those in equations (11-1) and (14). The specific examples and suitable examples are also the same.

[0024] In formula (14), Q is preferably represented by a divalent group as shown in formula (14-1) below, or an aryl group with 6 to 40 carbon atoms, from the viewpoint of obtaining the effects of the present invention. (In equation (14-1), X represents the basis represented by any one of the terms in equations (14-1a) to (14-1c) below.)

[0025] (In formulas (14-1a) to (14-1c), R11, R12, R13, R14, and R15 each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The aforementioned benzyl and phenyl groups can also be substituted by groups selected from the group consisting of alkyl groups with 1 to 6 carbon atoms, halogen atoms, alkoxy groups with 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups with 1 to 6 carbon atoms. Furthermore, R11 and R12 can also bond to each other to form a ring with 3 to 6 carbon atoms. R13 and R14 can also bond to each other to form a ring with 3 to 6 carbon atoms. * indicates a bond. *1 indicates a bond bonded to a carbon atom. *2 indicates a bond bonded to a nitrogen atom.)

[0026] In this invention, examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, and 2-methyl-n-pentoxy. Oxygen compounds, 3-methyl-n-pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy, etc. In this invention, examples of alkylthio groups with 1 to 6 carbon atoms include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, and hexylthio.

[0027] Aryl groups with 6 to 40 carbon atoms, belonging to the category of Q, may also have substituents on the aromatic ring. Examples of substituents include halogen atoms, nitro groups, cyano groups, alkyl groups with 1 to 6 carbon atoms, and alkyl groups with 1 to 6 carbon atoms. The number of substituents on the aromatic ring may be one or more. Examples of aryl groups with 6 to 40 carbon atoms include divalent groups obtained by removing one hydrogen atom from the aromatic ring of any monovalent group selected from phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, and β-naphthyl; 4,4'-epienylphenyl; and divalent groups obtained by removing two hydrogen atoms from any of anthracene and phenanthrene.

[0028] The molecular weight of a polymer containing a specific structure is not particularly limited, but the weight-average molecular weight obtained by gel permeation chromatography is preferably 1,500 to 100,000, more preferably 2,000 to 50,000.

[0029] The content of polymers containing specific structures in the composition of the lower layer film forming agent for EB or EUV lithography is not particularly limited if the content of the component containing specific structures in the film forming component is 20% by mass or more. However, relative to the film forming component, it can be 20% by mass to 100% by mass or 20% by mass to 99.5% by mass.

[0030] The content of polymers containing specific structures in the composition for forming the lower layer film of resists for EB or EUV lithography is not particularly limited if the content of the component containing the specific structure in the film-forming component is 20% by mass or more. However, in the case where the film-forming component includes polymers that do not contain specific structures as described below, the content is preferably 10% to 90% by mass, more preferably 15% to 70% by mass, and especially preferably 20% to 50% by mass, relative to polymers that do not contain specific structures.

[0031] <<<As a cross-linking agent containing components with specific structures>>> It contains components with a specific structure, for example, it contains crosslinking agents with a specific structure. The crosslinking agent containing a specific structure preferably includes at least one of the compounds represented by formula (21), formula (22), and formula (23). In formulas (21) to (23), R1 represents alkyl groups with 1 to 6 carbon atoms, R2 represents alkyl groups with 1 to 6 carbon atoms or alkoxyalkyl groups with 2 to 10 total carbon atoms, and R3 represents alkyl groups with 1 to 6 carbon atoms. In equation (21), m1 and m2 each independently represent integers from 1 to 2. When m1 and m2 are both 1, Q1 represents a single bond, an oxygen atom, or an organic group with a divalent carbon number from 1 to 20. When the sum of m1 and m2 is 3 or 4, Q1 represents an organic group with a (m1+m2) valence of carbon number from 1 to 20. In equation (21), n1 represents integers from 1 to 5, n2 represents integers from 0 to 4, and n3 represents integers from 0 to 4. In each benzene ring, n1, n2, and n3 satisfy 1 ≤ (n1 + n2 + n3) ≤ 5. In formula (23), Y represents an organogroup with 1 to 20 carbon atoms in a monovalent state.

[0032] As an organic group with a carbon number of 1 to 20 and a valence of (m1+m2) in Q1, for example, the group represented by any one of the following formulas (21-1) to (21-5) can be cited.

[0033] In formula (21-1), Ra and Rb respectively represent hydrogen atoms, or alkyl groups with 1 to 4 carbon atoms, or -CF3 groups. In equation (21-3), X series represents trivalent groups with 1 to 30 carbon atoms. In formula (21-4), Ar series represents divalent aromatic hydrocarbon groups. * indicates a bond.

[0034] Ar, for example, represents a divalent residue of a compound selected from benzene, biphenyl, naphthalene, and anthracene.

[0035] The basis represented by equation (21-1) is a 2-valent basis. The basis represented by equation (21-2) is a four-valent basis. The basis represented by equation (21-3) is a trivalent basis. The basis represented by equation (21-4) is a 2-valent basis. The basis represented by equation (21-5) is a trivalent basis.

[0036] Examples of monovalent organic groups with 1 to 20 carbon atoms in Y include phenyl groups and groups represented by the following formula (23-1). (In formula (23-1), R1 series independently represents alkyl groups with 1 to 6 carbon atoms, and R2 series independently represents hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, or alkoxyalkyl groups with 2 to 10 total carbon atoms. * series indicates bonded bonds.) As specific and suitable examples of R1 and R2 in equation (23-1), for example, specific and suitable examples of R1 and R2 in equation (1) can be given.

[0037] The molecular weight of a crosslinking agent containing a specific structure is not particularly limited, but it is preferably less than 1,500, and more preferably less than 1,000.

[0038] The content of a crosslinking agent containing a specific structure in the composition for forming the lower layer of the resist used in EB or EUV lithography is not particularly limited if the content of the component containing the specific structure in the film forming component is 20% by mass or more. However, relative to the film forming component, it can be 20% by mass to 100% by mass or 20% by mass to 99.5% by mass.

[0039] The content of the crosslinking agent containing a specific structure in the composition for forming the lower layer film of the resist used in EB or EUV lithography is not particularly limited if the content of the component containing the specific structure in the film forming component is 20% by mass or more. However, if the film forming component includes polymers that do not contain a specific structure as described below, the content is preferably 10% to 90% by mass, more preferably 15% to 70% by mass, and especially preferably 20% to 50% by mass, relative to polymers that do not contain a specific structure.

[0040] <<Not belonging to polymers containing components with a specific structure>> The film-forming component may also include polymers that do not belong to the category of components containing a specific structure. Such polymers do not contain a specific structure. As such polymers are not particularly restricted, however, for example, the reaction product of epoxy resin and diamine compound represented by the following general formula (3) as described in Japanese Patent Application Publication No. 2007-262013 can be cited. (In general formula (3), R3 represents a hydrogen atom or a methyl group, Ar represents naphthyl, phenyl, or naphthyl or phenyl with 1 to 4 carbon atoms as a substituent, R2 represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, n and m are integers from 0 to 2, and either n or m is 1 or more, R1 represents a hydrogen atom or an epoxy group represented by the general formula (3-2) below containing an aromatic hydrocarbon group. However, the total number of aromatic nuclei in the formula is 2 to 8. Also, in general formula (3), the bonding position in the naphthalene skeleton can be any one of the two rings constituting the naphthalene ring.) (In the general formula (3-2), R3 series represents a hydrogen atom or a methyl group, Ar series independently represent a trivalent group formed by removing three hydrogen atoms from a naphthalene ring, a trivalent group formed by removing three hydrogen atoms from a benzene ring, or a trivalent group formed by removing three hydrogen atoms from a naphthalene ring or a benzene ring with alkyl or phenyl groups having 1 to 4 carbon atoms as substituents, and p is an integer of 1 or 2.)

[0041] Examples of diamine compounds include compounds represented by formula (4) below. (In formula (4), R1 and R2 are independently hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, alkenyl groups with 3 to 6 carbon atoms, benzyl groups or phenyl groups. The aforementioned phenyl groups can also be substituted by at least one group selected from the group consisting of alkyl groups with 1 to 6 carbon atoms, halogen atoms, alkoxy groups with 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups and alkylthio groups with 1 to 6 carbon atoms. Furthermore, R1 and R2 can also be bonded to each other and together with the carbon atoms bonded to them to form a ring with 3 to 6 carbon atoms.)

[0042] Furthermore, as a polymer that does not contain components with a specific structure, phenolic varnish resins containing halogen atoms can be cited as an example. For example, the phenolic varnish resin containing halogen atoms described in WO2010 / 122948 can be cited as an example.

[0043] Furthermore, as a polymer that does not contain components with a specific structure, for example, a polymer having a repeating unit structure represented by the following formula (1A) can be cited. For example, the polymer described in WO2011 / 074494 can be cited as such a polymer. (In formula (1A), X represents an ester bond or an ether bond, A1, A2, A3, A4, A5 and A6 represent hydrogen atoms, methyl or ethyl groups, respectively, and Q represents the radicals represented by formula (2A) or formula (3A) below.) (In formulas (2A) and (3A), Q1 represents an alkyl, phenyl, naphthyl, or anthracene group having 1 to 10 carbon atoms. Furthermore, the aforementioned phenyl, naphthyl, and anthracene groups can be substituted by groups selected from the group consisting of alkyl, halogen, alkoxy, nitro, cyano, hydroxyl, and alkylthio groups having 1 to 6 carbon atoms, respectively. n1 and n2 represent the number 0 or 1, respectively. X1 represents the group represented by formula (4A), formula (5A), or formula (6A) below.) (In formulas (4A) to (6A), R1 and R2 represent hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, benzyl groups, or phenyl groups, respectively. In addition, the aforementioned benzyl and phenyl groups can also be substituted by groups selected from the group consisting of alkyl groups with 1 to 6 carbon atoms, halogen atoms, alkoxy groups with 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups with 1 to 6 carbon atoms. Furthermore, R1 and R2 can also bond to each other to form a ring with 3 to 6 carbon atoms. R3 represents alkyl groups with 1 to 6 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, benzyl groups, or phenyl groups. In addition, the aforementioned benzyl and phenyl groups can also be substituted by groups selected from the group consisting of alkyl groups with 1 to 6 carbon atoms, halogen atoms, alkoxy groups with 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups with 1 to 6 carbon atoms.)

[0044] Furthermore, polymers that do not contain components with a specific structure can be exemplified by polymers in which diphenyl ether or its derivatives are introduced into the main chain via ether bonds. Examples of such polymers include, for instance, the polymer described in WO2012 / 067040.

[0045] Furthermore, as a polymer that does not contain components with a specific structure, examples include polymers having structural units represented by the following formulas (1B) and (2B). Examples of such polymers include, for instance, the polymer described in WO2012 / 081619. (In formulas (1B) and (2B), R1 and R2 represent hydrogen atoms or methyl groups, respectively; L1 represents a single bond or a divalent linking group of an alkyl group having 1 to 13 carbon atoms in a straight or branched chain; A represents an aromatic cyclic group containing a hydroxyl group and having at least one substituent; and D represents a hydroxyalkyl group having 1 to 13 carbon atoms in a straight or branched chain.)

[0046] Furthermore, as a polymer that does not contain components with a specific structure, for example, a polymer having a repeating unit structure represented by the following formula (1C) can be cited. For example, the polymer described in WO2013 / 018802 can be cited as such a polymer. (In formula (1C), A1, A2, A3, A4, A5 and A6 series represent hydrogen atoms, methyl or ethyl, respectively; X1 series represents formula (2C), formula (3C), formula (4C) or formula (0C) below; Q series represents formula (5C) or formula (6C) below.) In formulas (2C)~(4C) and (0C), R1 and R2 represent hydrogen atoms, halogen atoms, alkyl groups with 1 to 6 carbon atoms, alkenyl groups with 3 to 6 carbon atoms, benzyl groups, or phenyl groups, respectively. Furthermore, the aforementioned alkyl groups with 1 to 6 carbon atoms, alkenyl groups with 3 to 6 carbon atoms, benzyl groups, and phenyl groups can also be substituted by groups selected from the group consisting of alkyl groups with 1 to 6 carbon atoms, halogen atoms, alkoxy groups with 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, and alkylthio groups with 1 to 6 carbon atoms. Additionally, R1 and R2 can also bond together to form a ring with 3 to 6 carbon atoms. 3 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group. Furthermore, the aforementioned phenyl group may also be substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms. (In formulas (5C) and (6C), Q1 represents an alkyl, phenyl, naphthyl, or anthracene group having 1 to 10 carbon atoms. Furthermore, the aforementioned alkyl, phenyl, naphthyl, and anthracene groups may be substituted by an alkyl group having 1 to 6 carbon atoms, a carbonyl alkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxyl group, an alkylthio group having 1 to 6 carbon atoms, a disulfide group, a carboxyl group, or a group consisting of combinations thereof. n1 and n2 represent the number 0 or 1, respectively. X2 represents formula (2C), formula (3C), or formula (0C).)

[0047] Furthermore, polymers that do not contain components with a specific structure can be exemplified by polymers whose polymer chains have structures represented by formula (1D) or formula (2D) at their ends. Examples of such polymers include those described in WO2015 / 163195. (In formulas (1D) and (2D), R1 represents alkyl, phenyl, pyridyl, halogen or hydroxyl groups with 1 to 6 carbon atoms that may have substituents; R2 represents hydrogen, alkyl, hydroxyl, halogen or ester group represented by -C(=O)OX; X represents alkyl with 1 to 6 carbon atoms that may have substituents; R3 represents hydrogen, alkyl, hydroxyl or halogen with 1 to 6 carbon atoms; R4 represents direct bonding or divalent organic group with 1 to 8 carbon atoms; R5 represents divalent organic group with 1 to 8 carbon atoms; A represents aromatic ring or aromatic heterocycle; t represents 0 or 1; u represents 1 or 2.)

[0048] Furthermore, as polymers that do not contain components with a specific structure, examples include polymers containing aliphatic rings whose carbon-carbon bonds can be terminated by heteroatoms at the ends and can be substituted by substituents. Examples of such polymers include, for instance, the polymer described in WO2020 / 226141.

[0049] The molecular weight of a polymer that does not contain a specific structure is not particularly limited; however, the weight-average molecular weight obtained by gel permeation chromatography (hereinafter also referred to as GPC) is preferably 1,500 to 100,000, more preferably 2,000 to 50,000.

[0050] In cases where the film-forming component contains polymers that do not belong to the category of components containing a specific structure, the content of polymers that do not belong to the category of components containing a specific structure in the composition for forming the lower layer of the resist for EB or EUV lithography is not particularly limited. However, relative to the film-forming component, it is preferably 30% or more but less than 80% by mass, more preferably 50% or more but less than 80% by mass, and especially preferably 60% or more but less than 80% by mass.

[0051] Hardening Catalyst The curing catalyst included in the composition for forming the lower layer film of the inhibitor can be any component, such as a thermal acid generator or a photoacid generator, but it is preferred to use a thermal acid generator.

[0052] Examples of sulfonic acid and carboxylic acid compounds that can be cited as thermal acid generating agents include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (p-phenolsulfonic acid pyridinium salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, etc.

[0053] Examples of photoacid generators include, for example, onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0054] Examples of onium salt compounds include, for example, diphenylmenium hexafluorophosphate, diphenylmenium trifluoromethane sulfonate, diphenylmenium nonafluoron-butane sulfonate, diphenylmenium perfluoron-octane sulfonate, diphenylmenium camphor sulfonate, bis(4-tert-butylphenyl)menium camphor sulfonate, and bis(4-tert-butylphenyl)menium trifluoromethane sulfonate, as well as strontium salt compounds such as triphenylstrontium hexafluoroantimonate, triphenylstrontium nonafluoron-butane sulfonate, triphenylstrontium camphor sulfonate, and triphenylstrontium trifluoromethane sulfonate.

[0055] Examples of sulfonylimine compounds include N-(trifluoromethanesulfonyloxy)succinylimine, N-(nonafluoron-butanesulfonyloxy)succinylimine, N-(camphorsulfonyloxy)succinylimine, and N-(trifluoromethanesulfonyloxy)naphthylimine.

[0056] Examples of disulfonyldiazomethane compounds include, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0057] Hardening catalysts can be used alone or in combination of two or more.

[0058] When using a hardening catalyst, the proportion of the hardening catalyst relative to the component containing the specific structure is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass.

[0059] <<Other Ingredients>> In order to prevent pinholes or streaks and further improve the coating properties for uneven surfaces, surfactants can be added to the composition for forming the lower layer film of the inhibitor.

[0060] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers (e.g., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene acetylated ether, polyoxyethylene oleyl ether), polyoxyethylene alkyl allyl ethers (e.g., polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether), polyoxyethylene-polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc.), and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Eftop Fluorinated surfactants such as EF301, EF303, EF352 (manufactured by TOCHEM Products, trade name), Megafac F171, F173, R-30 (manufactured by DIC, trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M, trade name), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass, trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry, Ltd.), etc. The amount of these surfactants is not particularly limited; however, relative to the total solid content of the composition for forming the lower layer film of the inhibitor, it is usually 2.0% by mass or less, and preferably 1.0% by mass or less. These surfactants can be added individually or in combination of two or more.

[0061] The film-forming component included in the composition for forming the lower layer of the resistor film, that is, the component other than the aforementioned solvent, is, for example, 0.01% to 10% by mass of the composition for forming the lower layer of the resistor film.

[0062] Solvent As a solvent, organic solvents commonly used in semiconductor lithography processes are preferred. Specifically, examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl methacrylate ceroxoxene, ethyl methacrylate ceroxoxene, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, and 2-hydroxy Ethyl isobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0063] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0064] The composition for forming the resist underlayer film for EB or EUV lithography is preferably used for forming the resist underlayer film for EB or EUV lithography with a film thickness of less than 10 nm.

[0065] (Resistant lower layer film for EB or EUV lithography) The resist underlayer film for EB or EUV lithography of the present invention (hereinafter also referred to as "resist underlayer film") is a hardened form of the aforementioned composition for forming the resist underlayer film for EB or EUV lithography. The resist underlayer film, for example, can be manufactured by coating and firing the aforementioned EB or EUV lithography resist underlayer film formation composition onto a semiconductor substrate.

[0066] Semiconductor substrates coated with components used for forming resistive lower layers include, for example, silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0067] In the case of using a semiconductor substrate with an inorganic film formed on its surface, the inorganic film is formed, for example, by ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum evaporation, or spin coating (spin-coated glass: SOG). Examples of such inorganic films include polycrystalline silicon films, silicon oxide films, silicon nitride films, BPSG (Boro-Phospho Silicate Glass) films, titanium nitride films, titanium oxynitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0068] On such a semiconductor substrate, the composition for forming the resist underlayer film of the present invention is coated using a suitable coating method such as a spinner or coating machine. Then, it is baked using a heating means such as a heating plate to form the resist underlayer film. The baking conditions can be suitably selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes; more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes.

[0069] From the viewpoint of achieving the desired effects of the present invention, the thickness of the lower layer film as the resist is preferably 10 nm or less, more preferably 9 nm or less, even more preferably 8 nm or less, and particularly preferably 7 nm or less. Furthermore, the thickness of the lower layer film as the resist can be 1 nm or more, 2 nm or more, or 3 nm or more. The thickness of the lower layer film used as the inhibitor is, for example, 0.001 μm (1 nm) ~ 10 μm, 0.002 μm (2 nm) ~ 1 μm, 0.005 μm (5 nm) ~ 0.5 μm (500 nm), 0.001 μm (1 nm) ~ 0.05 μm (50 nm), 0.002 μm (2 nm) ~ 0.05 μm (50 nm), 0.003 μm (3 nm) ~ 0.05 μm (50 nm), 0.004 μm (4 nm) ~ 0.05 μm (50 nm), 0.005 μm (5 nm) ~ 0.05 μm (50 nm), 0.003 μm (3nm)~0.03μm(30nm), 0.003μm(3nm)~0.02μm(20nm), 0.005μm(5nm)~0.02μm(20nm), 0.005μm(5nm)~0.02μm(20nm), 0.003μm(3nm)~0.01μm(10nm), 0.005μm(5nm)~0.01μm(10nm), 0.003μm(3nm)~0.006μm(6nm) or 0.005μm(5nm).

[0070] The method for determining the thickness of the resist underlayer film in this specification is as follows. • Measuring device name: Elliptical film thickness measuring device RE-3100 (SCREEN) • SWE (Single Wavelength Elliptic Polarizer) Mode • Arithmetic mean of 8 points (e.g., measured at 1cm intervals along the X-axis of the wafer).

[0071] (Substrate for semiconductor processing) The semiconductor processing substrate of the present invention comprises a semiconductor substrate and the resist lower layer film for EB or EUV lithography of the present invention. As a semiconductor substrate, for example, the aforementioned semiconductor substrate can be cited. The resistive underlayer film, for example, is disposed on a semiconductor substrate.

[0072] (Semiconductor device manufacturing methods, pattern forming methods, and methods for improving resist pattern LWR) The method for manufacturing a semiconductor device according to the present invention includes at least the following steps. • The step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film formation composition for EB or EUV lithography of the present invention, and • The step of forming a resist film on top of the resist underlayer using an EB or EUV lithography resist.

[0073] The pattern forming method of the present invention includes at least the following steps. • The step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film formation composition for EB or EUV lithography of the present invention. • The step of forming a resist film on top of the resist underlayer using an EB or EUV lithography resist. • The steps of irradiating the resist film with EB or EUV, followed by developing the resist film to obtain the resist pattern, and • The step of etching the underlying resist film using the resist pattern as a mask.

[0074] The method for improving the LWR of the resist pattern of the present invention includes at least the following steps. • The step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film formation composition for EB or EUV lithography of the present invention. • The step of forming a resist film on top of the resist film using an EB or EUV lithography resist, and • The process involves irradiating the resist film with EB or EUV, followed by developing the resist film to obtain the resist pattern. In the method for improving the line width roughness (LWR) of the resist pattern, by applying the resist underlayer film obtained by the composition for forming the resist underlayer film of EB or EUV lithography of the present invention under the resist film, the line width roughness (LWR) of the resist pattern in EB or EUV lithography can be improved.

[0075] Typically, the resist film is formed on top of the resist film. The thickness of the resist film is preferably 200 nm or less, more preferably 150 nm or less, even more preferably 100 nm or less, and particularly preferably 80 nm or less. Furthermore, the thickness of the resist film is preferably 10 nm or more, more preferably 20 nm or more, and particularly preferably 30 nm or more.

[0076] As a resist formed by coating and firing on a resist underlayer film using well-known methods, it is not particularly limited if it is intended for use in EB or EUV irradiation. Both negative and positive photoresists can be used. Furthermore, in this specification, the resist that responds to EB is also referred to as photoresist. As photoresists, there are positive photoresists composed of phenolic varnish resin and 1,2-naphthoquinone diazidesulfonate; chemically amplified photoresists composed of a binder with a group that decomposes in acid and increases the rate of alkali dissolution, and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that decomposes in acid and increases the rate of alkali dissolution, an alkali-soluble binder, and a photoacid generator; and chemically amplified photoresists composed of a binder with a group that decomposes in acid and increases the rate of alkali dissolution, a low-molecular-weight compound that decomposes in acid and increases the rate of alkali dissolution, and a photoacid generator; and photoresists containing metal elements. Examples include JSR Corporation's product V146G, Shipley Corporation's product APEX-E, Sumitomo Chemical's product PAR710, and Shin-Etsu Chemical Industry's products AR2772 and SEPR430. For example, examples include fluorinated atom polymer photoresists as described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000) or Proc. SPIE, Vol. 3999, 365-374 (2000).

[0077] Also, available for use: WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, W O2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 0 58890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO2019 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Patent Publication No. 2018-180525, WO2018 / 190088, Japanese Patent Publication No. 2018-070596, Japanese Patent Publication No. 2018-028090, Japanese Patent Publication No. 2016-153409, Japanese Patent Publication No. 2016-130240, Japanese Patent Publication No. 2016-108325, Japanese Patent Publication No. 2016-047920, Japanese Patent Publication No. 2016-035570, Japanese Patent Publication No. 2016-035567, Japanese Patent Publication No. 2016-035565, Japanese Patent Publication No. 2019-101417, Japan Japanese Patent Publication No. 2019-117373, Japanese Patent Publication No. 2019-052294, Japanese Patent Publication No. 2019-008280, Japanese Patent Publication No. 2019-008279, Japanese Patent Publication No. 2019-003176, Japanese Patent Publication No. 2019-003175, Japanese Patent Publication No. 2018-197853, Japanese Patent Publication No. 2019-191298, Japanese Patent Publication No. 2019-061217, Japanese Patent Publication No. 2018-045152, Japanese Patent Publication No. 2018- 022039, Japanese Patent Publication No. 2016-090441, Japanese Patent Publication No. 2015-10878, Japanese Patent Publication No. 2012-168279, Japanese Patent Publication No. 2012-022261, Japanese Patent Publication No. 2012-022258, Japanese Patent Publication No. 2011-043749, Japanese Patent Publication No. 2010-181857, Japanese Patent Publication No. 2010-128369, WO2018 / 031896, Japanese Patent Publication No. 2019-113855, WO20 17 / 156388, WO2017 / 066319, Japanese Patent Application Publication No. 2018-41099, WO2016 / 065120, WO2015 / 026482, Japanese Patent Application Publication No. 2016-29498, Japan JP-A-2011-253185, so-called blocking compositions, such as blocking compositions, radiation-sensitive resin compositions, high-resolution patterning compositions based on organic metal solutions, blocking compositions containing metal, etc., but without limitation.

[0078] Examples of inhibitor components include the following.

[0079] A photosensitive or radiosensitive linear resin composition comprising a resin A having a repeating unit, and a compound represented by the following general formula (21), wherein the repeating unit is an acid-degradable group having a polar group that is desorbed by the action of an acid.

[0080] In the general formula (21), m represents an integer from 1 to 6. The R1 and R2 series respectively represent fluorine atoms or perfluoroalkyl groups. L1 series represents -O-, -S-, -COO-, -SO2-, or -SO3-. L2 series indicates that it may have substituents such as alkyl groups or single bonds. W1 series represents cyclic organic groups that can have substituents. M+ series represents cations.

[0081] An extreme ultraviolet or electron beam lithography film-forming composition containing metal contains a compound with metal-oxygen covalent bonds and a solvent, wherein the metal element constituting the compound belongs to the 3rd to 7th periods of Groups 3 to 15 of the periodic table.

[0082] A radiosensitive linear resin composition comprising a polymer and an acid generating agent, wherein the polymer has a second structural unit comprising a first structural unit represented by formula (31) and an acid dissociative group represented by formula (32).

[0083] (In formula (31), Ar is a group consisting of an aromatic hydrocarbon with 6 to 20 carbon atoms from which (n+1) hydrogen atoms have been removed. R1 is a hydroxyl group, a thiosulfate group, or an organogroup with 1 to 20 carbon atoms and a monovalent charge. n is an integer from 0 to 11. In the case where n is 2 or more, the multiple R1s are the same or different. R2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), R3 is a group consisting of a carbon atom from 1 to 20 carbon atoms and a monovalent charge containing the above-mentioned acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R4 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0084] An inhibitor composition comprising a resin (A1) and an acid generating agent, wherein the resin (A1) comprises: a structural unit having a cyclic carbonate structure, a structural unit represented by the following formula, and a structural unit having an acid-instantaneous group.

[0085] [In the formula, The R2 series represents alkyl groups with 1 to 6 carbon atoms, hydrogen atoms, or halogen atoms; the X1 series represents single bonds, -CO-O-*, or -CO-NR 4-*; the * series represents bonds with -Ar; the R4 series represents hydrogen atoms or alkyl groups with 1 to 4 carbon atoms; and the Ar series represents aromatic hydrocarbon groups with 6 to 20 carbon atoms, having 1 or more groups selected from the group consisting of hydroxyl and carboxyl groups.

[0086] Examples of barrier films include the following.

[0087] An inhibitor film comprising a matrix resin, wherein the matrix resin comprises repeating units represented by formula (a1) and / or repeating units represented by formula (a2) below, and repeating units that generate acid bonded to the polymer backbone by exposure.

[0088] (In formulas (a1) and (a2), RA is independently a hydrogen atom or a methyl group. R1 and R2 are independently ternary alkyl groups with 4 to 6 carbon atoms. R3 is independently a fluorine atom or a methyl group. m is an integer from 0 to 4. X1 is a single bond, an phenyl group, or a naphthyl group, or a linking group with 1 to 12 carbon atoms selected from ester bonds, lactone rings, phenyl groups, and naphthyl groups. X2 is a single bond, an ester bond, or an amide bond.)

[0089] Examples of materials that can be used as inhibitors include the following.

[0090] An inhibitor material comprising a polymer having repeating units represented by formula (b1) or formula (b2) below.

[0091] In formulas (b1) and (b2), RA is a hydrogen atom or a methyl group. X1 is a single bond or an ester group. X2 is a linear, branched, or cyclic alkyl group with 1 to 12 carbon atoms or an aryl group with 6 to 10 carbon atoms. A portion of the methylene group constituting the alkyl group may be substituted with an ether group, an ester group, or a group containing an lactone ring. Furthermore, at least one hydrogen atom in X2 is substituted with a bromine atom. X3 is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkyl group with 1 to 12 carbon atoms. A portion of the methylene group constituting the alkyl group may be substituted with an ether group or an ester group. Rf1 to Rf4 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Furthermore, Rf1 and Rf2 may also combine to form a carbonyl group. R1 to R The 5-group can be independently composed of linear, branched, or cyclic alkyl groups with 1 to 12 carbon atoms, linear, branched, or cyclic alkenyl groups with 2 to 12 carbon atoms, alkynyl groups with 2 to 12 carbon atoms, aryl groups with 6 to 20 carbon atoms, aralkyl groups with 7 to 12 carbon atoms, or aryloxyalkyl groups with 7 to 12 carbon atoms. Some or all of the hydrogen atoms in these groups can be substituted with hydroxyl, carboxyl, halogen, oxy, cyano, amide, nitro, sulopentalide, sulfonic acid, or groups containing strontium salts. A portion of the methylene group constituting these groups can also be substituted with ether, ester, carbonyl, carbonate, or sulfonate groups. Furthermore, R1 and R2 can be bonded together and form a ring with the sulfur atoms to which they are bonded.

[0092] An inhibitor material comprising a matrix resin comprising a polymer containing repeating units represented by formula (a) below.

[0093] (In formula (a), RA is a hydrogen atom or a methyl group. R1 is a hydrogen atom or an acid-unstable group. R2 is a straight-chain, branched, or cyclic alkyl group with 1 to 6 carbon atoms, or a halogen atom other than bromine. X1 is a single bond or an extended phenyl group, or a straight-chain, branched, or cyclic alkyl group with 1 to 12 carbon atoms that may contain an ester group or an lactone ring. X2 is -O-, -O-CH2-, or -NH-. m is an integer from 1 to 4. u is an integer from 0 to 3. However, m+u is an integer from 1 to 4.)

[0094] An inhibitor composition that generates acid upon exposure and alters its solubility in a developer through the action of the acid, wherein the inhibitor composition contains... Regarding the substrate component (A) whose solubility in developer changes due to acid action and the fluorine additive component (F) which exhibits decomposability in alkaline developer, and The aforementioned fluorine additive component (F) contains a fluororesin component (F1), and the fluororesin component (F1) has a structural unit (f1) containing an alkali dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).

[0095] [In formula (f2-r-1), Rf 21 is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group or a cyano group. n” is an integer from 0 to 2. * is a bonding bond.]

[0096] The aforementioned structural unit (f1) contains a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0097] [In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group not having an acid dissociable site. A aryl is a divalent aromatic cyclic group which may have a substituent. X 01 is a single bond or a divalent linking group. R 2 is independently an organic group having a fluorine atom.]

[0098] Examples of the coating, coating solution and coating composition include the following.

[0099] A coating layer containing a metal-oxygen / hydroxy network having an organic ligand through a metal-carbon bond and / or a metal carboxylate bond.

[0100] A composition of an inorganic oxygen / hydroxyl matrix.

[0101] A coating solution containing: an organic solvent; a first organometallic composition represented by the formula R zSnO (2-(z / 2)-(x / 2))(OH) x (where 0 < z ≦ 2 and 0 < (z + x) ≦ 4), the formula R’ nSnX 4-n (where n = 1 or 2), or a mixture thereof, where R and R’ are independently hydrocarbon groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof; and a hydrolyzable metal compound represented by the formula MX’ v (where M is a metal selected from Groups 2 to 16 of the Periodic Table of the Elements, v is a number from 2 to 6, and X’ is a ligand having a hydrolyzable M-X bond or a combination thereof).

[0102] A coating solution comprising an organic solvent and a first organometallic compound represented by the formula RSnO(3 / 2 - x / 2)(OH)x (where 0 < x < 3), wherein the solution contains from about 0.0025 M to about 1.5 M of tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, and the alkyl or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom.

[0103] An aqueous solution of an inorganic pattern-forming precursor, which comprises a mixture containing water, metal suboxide cations, polyatomic inorganic anions, and a radiation-sensitive ligand containing a peroxide group.

[0104] Irradiation with EB or EUV, for example, is carried out through a mask (reticle) for forming a specific pattern. The composition for forming a resist underlayer film of the present invention is suitable for irradiation with EB (electron beam) or EUV (extreme ultraviolet ray: 13.5 nm), and is preferably suitable for EUV (extreme ultraviolet ray) exposure. The irradiation energy of EB and the exposure dose of EUV are not particularly limited.

[0105] Baking (PEB: Post Exposure Bake) may also be carried out before development after irradiation with EB or EUV. The baking temperature is not particularly limited, but is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C. The baking time is not particularly limited, but is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0106] During development, for example, an alkaline developer can be used. As the development temperature, for example, 5°C to 50°C can be cited. As the development time, for example, 10 seconds to 300 seconds can be cited. As an alkaline developer, for example, aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alkanolamines such as dimethylethanolamine and triethanolamine; fourth-order ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and cyclic amines such as pyrrole and piperidine can be used. Furthermore, an appropriate amount of alcohols such as isopropanol and nonionic surfactants can be added to the above-mentioned alkaline aqueous solutions. Among these, aqueous solutions of fourth-order ammonium salts are preferred, and aqueous solutions of tetramethylammonium hydroxide and choline are more preferred. In addition, surfactants can also be added to these developers. Alternatively, an organic solvent such as butyl acetate can be used to replace the alkaline developer for development, and the portion of the photoresist whose alkaline dissolution rate has not been improved can be developed.

[0107] Next, the formed resist pattern is used as a mask to etch the underlying resist film. Etching can be dry etching or wet etching, but dry etching is preferred. In the case where the aforementioned inorganic film is formed on the surface of the semiconductor substrate to be used, the surface of the inorganic film is exposed. In the case where the aforementioned inorganic film is not formed on the surface of the semiconductor substrate to be used, the surface of the semiconductor substrate is exposed. Subsequently, by processing the semiconductor substrate using well-known methods (such as dry etching), a semiconductor device can be manufactured. [Example]

[0108] The present invention will then be illustrated by examples, but the invention is not limited thereto.

[0109] The weight-average molecular weights of the polymers shown in the following synthetic examples and comparative synthetic examples in this specification are determined by gel permeation chromatography (hereinafter referred to as GPC). The determination was performed using a GPC apparatus manufactured by Tosoh Corporation, and the determination conditions were as described below. GPC tubing: TSKgel Super-MultiporeHZ-N (2 tubes) Column temperature: 40℃ Solvent: Tetrahydrofuran (THF) Flow rate: 0.35 ml / min Standard sample: Polystyrene (Tosoh Corporation)

[0110] <Synthesis example 1> 7.00 g of allyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 11.79 g of 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol (manufactured by Honshu Chemical Industry Co., Ltd., trade name TMOM-BP), and 0.64 g of tetrabutylphosphine bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 29.14 g of propylene glycol monomethyl ether in a reaction vessel. After nitrogen substitution of the reaction vessel, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 1. After GPC analysis, the obtained polymer 1 had a weight average molecular weight of 8,500 and a dispersion of 3.5, converted from standard polystyrene. The structure present in polymer 1 is represented by the following formula.

[0111]

[0112] <Synthesis example 2> 4.49 g of monomethyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 9.06 g of 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol (manufactured by Honshu Chemical Industry Co., Ltd., trade name TMOM-BP), and 0.46 g of tetrabutylphosphine bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 21.01 g of propylene glycol monomethyl ether in a reaction vessel. After nitrogen substitution of the reaction vessel, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 2. After GPC analysis, the obtained polymer 2 had a weight average molecular weight of 4,800 and a dispersion of 3.1, converted from standard polystyrene. The structure present in polymer 2 is represented by the following formula.

[0113]

[0114] <Synthesis example 3> 15.00 g of EPICLON WR-400 (manufactured by DIC Corporation, propylene glycol monomethyl ether solution), 2.77 g of 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol (manufactured by Honshu Chemical Industry Co., Ltd., trade name TMOM-BP), and 0.14 g of tetrabutylphosphine bromide (manufactured by Hokkien Chemical Industry Co., Ltd.) were dissolved in 4.27 g of propylene glycol monomethyl ether in a reaction vessel. After nitrogen substitution of the reaction vessel, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 3. GPC analysis showed that polymer 3, converted to standard polystyrene, had a weight average molecular weight of 5,300 and a dispersion of 3.2. The structure present in polymer 3 is represented by the following formula.

[0115]

[0116] <Synthesis example 4> 15.00 g of EPICLON WR-600 (manufactured by DIC Corporation, propylene glycol monomethyl ether solution), 4.78 g of 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol (manufactured by Honshu Chemical Industry Co., Ltd., trade name TMOM-BP), and 0.24 g of tetrabutylphosphine bromide (manufactured by Hokkien Chemical Industry Co., Ltd.) were dissolved in 27.80 g of propylene glycol monomethyl ether in a reaction vessel. After nitrogen substitution of the reaction vessel, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 4. GPC analysis showed that polymer 4, converted to standard polystyrene, had a weight average molecular weight of 8,000 and a dispersion of 4.7.

[0117] <Synthesis example 5> 4.00 g of EPICLON HP-4770 (manufactured by DIC Corporation), 5.69 g of 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol (manufactured by Honshu Chemical Industry Co., Ltd., trade name TMOM-BP), and 0.25 g of tetrabutylphosphine bromide (manufactured by Hokkien Chemical Industry Co., Ltd.) were dissolved in 39.74 g of propylene glycol monomethyl ether in a reaction vessel. After nitrogen substitution of the reaction vessel, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 5. GPC analysis showed that polymer 5, converted to standard polystyrene, had a weight average molecular weight of 13,200 and a dispersity of 9.6.

[0118] <Synthesis example 6> 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 6.48 g of 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol (manufactured by Honshu Chemical Industry Co., Ltd., trade name TMOM-BP), 1.77 g of 4-iodobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.46 g of tetrabutylphosphine bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) were dissolved in 20.56 g of propylene glycol monomethyl ether in a reaction vessel. After nitrogen substitution of the reaction vessel, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 6. After GPC analysis, the obtained polymer 6 had a weight average molecular weight of 4,000 and a dispersion of 3.9, converted from standard polystyrene. The structure present in polymer 6 is represented by the following formula.

[0119]

[0120] <Synthesis Example 7> 7.00 g of EPICLON HP-4770 (manufactured by DIC Corporation), 1.92 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemical Co., Ltd.), 1.43 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.31 g of tetrabutylphosphine bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) were dissolved in 49.10 g of propylene glycol monomethyl ether in a reaction vessel. After nitrogen substitution of the reaction vessel, the reaction was carried out at 140 °C for 24 hours to obtain a solution containing polymer 7. GPC analysis showed that polymer 7, converted to standard polystyrene, had a weight average molecular weight of 3,200 and a dispersity of 3.7.

[0121] <Synthesis example 8> 260.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.) and 1,430 g of PGME (propylene glycol monomethyl ether acetate) were placed in a reaction vessel. The mixture was then heated to approximately 90°C under nitrogen atmosphere, and 17.26 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 130.00 g of PGME was added dropwise. After approximately 45 hours, the mixture was precipitated with methanol and water and dried to obtain polymer 8. Furthermore, the actual structural unit is any ROCH 2- group containing a methoxymethyl group and a hydroxyl group, or cross-linked ROCH 2- groups; however, this state would become extremely complex if represented by a chemical formula, so only the structural unit is shown. After GPC analysis, the weight average molecular weight of polymer 8, converted to standard polystyrene, was 4,500. The structure present in polymer 8 is represented by the following formula.

[0122]

[0123] <Comparative Synthesis Example 1> 100.00 g of allyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 66.4 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemical Co., Ltd.), and 4.1 g of benzyltriethylammonium chloride were dissolved in 682.00 g of propylene glycol monomethyl ether in a reaction vessel. After nitrogen substitution of the reaction vessel, the reaction was carried out at 130°C for 24 hours to obtain a solution containing comparative polymer 1. GPC analysis showed that comparative polymer 1, converted to standard polystyrene, had a weight-average molecular weight of 6,800 and a dispersity of 4.8. The structure present in comparative polymer 1 is represented by the following formula.

[0124]

[0125] (Modulation of the lower layer film of the resistor) (Example, Comparative Example) By mixing the components in the proportions shown in Table 1 and filtering them through a fluoropolymer filter with a pore size of 0.1 μm, the compositions for forming the resist underlayer film for EB or EUV lithography in Examples 1 to 24 and the composition for forming the resist underlayer film in Comparative Example 1 were prepared respectively.

[0126] The abbreviations in Table 1 are as follows. PL-LI: Tetramethoxymethylglycourea PyPSA: Pyridinium-p-hydroxybenzenesulfonic acid R-30N: Surfactant (trade name: R-40, manufactured by DIC Company) PGMEA: Propylene Glycol Monomethyl Ether Acetate PGME: Propylene Glycol Monomethyl Ether

[0127] GPCL-11: A polymer having the following repeating units (trade name: GPCL-11, manufactured by Chung Yung Chemical Industry Co., Ltd.)

[0128] GPCL-20: A polymer having the following repeating units (trade name: GPCL-20, manufactured by Chung Yung Chemical Industry Co., Ltd.)

[0129] Nikalac Mw-390: 2,4,6-Tris[bis(methoxymethyl)amino]-1,3,5-triazine (trade name: Nikalac Mw-390, manufactured by Sanwa Chemical Co., Ltd., structural formula below)

[0130] TMOM-BP: 3,3',5,5'-Tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol (Trade name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd., lower structural formula)

[0131] PGME-BIP-A: Phenol,4,4'-(1-methylethylidene)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-(hypo-structure)

[0132] TM-BIP-ANT:1,3-Benzenedimethanol,2-hydroxy-5-[[10-[4-hydroxy-3,5-bis(hydroxymethyl)phenol]-9-anthracenyl]methyl]-(lower structural formula)

[0133] BIP-PHBZ-6MX: 1,1,1-Tris(3,5-dimethoxymethyl-4-hydroxyphenyl)methane (lower structural formula)

[0134] HMOM-TPPA:Phenol,4,4'-[1-[4-[1-[4-hydroxy-3,5-bis(methoxymethyl)phenyl]-1-methylethyl] phenyl]ethylidene]bis[2,6-bis(methoxymethyl)-(lower structural formula)

[0135] TPA-8MX:α,α,α',α'-Tetrakis(3,5-dimethoxymethyl-4-hydroxyphenyl)-p-xylene (lower structural formula)

[0136] GPCL-05: A polymer having the following repeating units (trade name: GPCL-05, manufactured by Chung Jung Chemical Industry Co., Ltd.)

[0137] GPCL-25: A compound having the following repeating unit (trade name: GPCL-25, manufactured by Chung Jung Chemical Industry Co., Ltd.)

[0138]

[0139] (Dissolution test of photoresist solvent) The resist underlayer film formation compositions of Examples 1-24 for EB or EUV lithography and the resist underlayer film formation composition of Comparative Example 1 were each coated onto a silicon wafer using a spin coater. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a film with a thickness of 5 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 70 / 30 (volume ratio) used as a solvent for photoresist. Cases with a film thickness change of less than 5 Å were defined as good, and cases with a thickness change of more than 5 Å were defined as poor. The results are shown in Table 2.

[0140]

[0141] (Inhibitor Pattern Evaluation) [Experimental study on resist pattern formation using electron beam lithography] The resist underlayer film formation compositions of Examples 1-5, 8-17, and 19-24, as well as Comparative Example 1, were each spin-coated onto a silicon wafer. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer film with a thickness of 5 nm. An EUV positive resist solution was spin-coated onto this resist underlayer film and heated at 130°C for 60 seconds to form an EUV resist film. This resist film was then irradiated with electron beam lithography (EB) under specific conditions using an electron beam lithography apparatus (ELS-G130). After irradiation, it was baked at 90°C for 60 seconds (PEB) and cooled to room temperature on a cooling plate. Puddle development was performed for 30 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) as the photoresist developer. Resist patterns with line dimensions of 16 nm to 28 nm were formed. The length of the resist pattern was measured using a scanning electron microscope (manufactured by Hitachi Advanced Technology Co., Ltd., CG4100).

[0142] The feasibility of forming a 22nm line-to-spacing (L / S) pattern was evaluated for the photoresist pattern obtained. The formation of the 22nm L / S pattern was confirmed in Examples 1-5, 8-17, and 19-24. Furthermore, the charge amount required to form a 22nm line / 44nm spacing (line-to-spacing (L / S=1 / 1)) was taken as the optimal irradiation energy, and the irradiation energy (μC / cm²) and LWR at that time are shown in Table 3. In Examples 1-5, 8-17, and 19-24, compared to Comparative Example 1, an improvement in LWR and an improvement in the minimum CD size were confirmed. In addition, the minimum CD size represents the limit of CD size that will not produce pattern collapse, and LWR is the value displayed for a pattern of 22 nml / s.

[0143]

[0144] Examples 1 to 24, in which the content of the component containing the specific structure in the film-forming component is 20% by mass or more, can reduce the LWR of the inhibitor pattern compared to Comparative Example 1, in which the content of the component containing the specific structure in the film-forming component is less than 20% by mass.

Claims

1. A composition for forming a resist lower layer film for EB or EUV lithography, comprising a film-forming component and a solvent, wherein the film-forming component comprises at least 20% by mass of a polymer, and the polymer comprises at least one of a first structure containing an aromatic ring and a second structure containing a nitrogen atom, wherein the polymer comprises at least one of the structure represented by formula (11), the structure represented by formula (12), and the structure represented by formula (13) as the first structure, wherein the polymer comprises at least one of the repeating unit represented by formula (11-1) and the repeating unit represented by formula (11-2) as the repeating unit comprising the structure represented by formula (11), and wherein the second structure comprises a base represented by formula (1) directly linked to the nitrogen atom. (In formula (1), R1 represents an alkyl group with 1 to 6 carbon atoms, R2 represents an alkyl group with 1 to 6 carbon atoms, or an alkoxyalkyl group with 2 to 10 total carbon atoms; * represents a bond) (In formulas (11) to (13), R1 represents an alkyl group with 1 to 6 carbon atoms, R2 represents an alkyl group with 1 to 6 carbon atoms, or an alkoxyalkyl group with 2 to 10 total carbon atoms, R3 represents an alkyl group with 1 to 6 carbon atoms; * represents a bond; In formula (11), n1 represents an integer from 1 to 4, n2 represents an integer from 0 to 3, n3 represents an integer from 0 to 3, and n1, n2 and n3 satisfy 1≦(n1+n2+n3)≦4; In equation (12), n1 represents an integer from 1 to 6, n2 represents an integer from 0 to 5, and n3 represents an integer from 0 to 5. n1, n2, and n3 satisfy 1 ≦ (n1 + n2 + n3) ≦ 6. In equation (13), n1 represents an integer from 1 to 8, n2 represents an integer from 0 to 7, and n3 represents an integer from 0 to 7. n1, n2, and n3 satisfy 1 ≦ (n1 + n2 + n3) ≦ 8. In equations (11) to (13), when there are two or more R1s, the two or more R1s can be the same or different. When there are two or more R2s, the two or more R2s can be the same or different. When there are two or more R3s, the two or more R3s can be the same or different. In formulas (11-1) and (11-2), R1 represents alkyl groups with 1 to 6 carbon atoms, R2 represents hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, or alkoxyalkyl groups with 2 to 10 total carbon atoms, and R3 represents alkyl groups with 1 to 6 carbon atoms; n1 represents integers 1 to 4, n2 represents integers 0 to 3, and n3 represents integers 0 to 3; in formula (11-1), X1 and X2 represent single bonds, oxygen atoms, or methylene groups; in formula (11-2), X1 and X2 represent single bonds, oxygen atoms, or methylene groups.X3 represents a single bond, or a divalent organic group with 1 to 15 carbon atoms; In formula (11-1), n1, n2, and n3 satisfy 1 ≦ (n1 + n2 + n3) ≦ 4; In formula (11-2), n1, n2, and n3 in the benzene ring on the left satisfy 1 ≦ (n1 + n2 + n3) ≦ 4; n1, n2, and n3 in the benzene ring on the right satisfy 1 ≦ (n1 + n2 + n3) ≦ 4; In formulas (11-1) and (11-2), if there are two or more R1s, the two or more R1s can be the same or different; if there are two or more R2s, the two or more R2s can be the same or different; if there are two or more R3s, the two or more R3s can be the same or different.

2. The composition for forming the resist underlayer film for EB or EUV lithography as described in claim 1, wherein, The aforementioned polymer system comprises repeating units represented by the following formula (14), (in formula (14), Q represents a divalent group).

3. The composition for forming the resist underlayer film for EB or EUV lithography as described in claim 2, wherein, In the aforementioned formula (14), Q represents a divalent group as represented by formula (14-1) below, or an aryl group with 6 to 40 carbon atoms. (In formula (14-1), X represents a group represented by any one of formulas (14-1a) to (14-1c) below.) (In formulas (14-1a) to (14-1c), R11, R12, R13, R14, and R15 each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The aforementioned benzyl and phenyl groups can also be substituted by groups selected from the group consisting of alkyl groups with 1 to 6 carbon atoms, halogen atoms, alkoxy groups with 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups with 1 to 6 carbon atoms. Furthermore, R11 and R12 can also bond to each other to form a ring with 3 to 6 carbon atoms; R13 and R14 can also bond to each other to form a ring with 3 to 6 carbon atoms; * indicates a bond; *1 indicates a bond bonded to a carbon atom; *2 indicates a bond bonded to a nitrogen atom).

4. The composition for forming the resist underlayer film for EB or EUV lithography as described in claim 1, wherein, The aforementioned component containing a specific structure includes a crosslinking agent, and the aforementioned crosslinking agent includes at least one of the following compounds represented by formula (21), formula (22), and formula (23): (In formulas (21) to (23), R1 represents an alkyl group with 1 to 6 carbon atoms, R2 represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, or an alkoxyalkyl group with 2 to 10 carbon atoms, and R3 represents an alkyl group with 1 to 6 carbon atoms; In formula (21), m1 and m2 represent integers 1 to 2; when m1 and m2 are 1, Q1 represents a single bond, an oxygen atom, or a divalent organic group with 1 to 20 carbon atoms; when the sum of m1 and m2 is 3 or 4, Q1 represents an organic group with (m1+m2) valence with 1 to 20 carbon atoms. In equation (21), n1 represents integers from 1 to 5, n2 represents integers from 0 to 4, and n3 represents integers from 0 to 4. In each benzene ring, n1, n2, and n3 satisfy 1 ≤ (n1 + n2 + n3) ≤ 5. In equation (23), Y represents an organogroup with 1 to 20 carbon atoms in a monovalent state.

5. The composition for forming the resist underlayer film for EB or EUV lithography as described in claim 4, wherein, The aforementioned film-forming components include polymers that are not among the aforementioned components containing a specific structure.

6. The composition for forming the resist underlayer film for EB or EUV lithography as described in claim 1, wherein, The aforementioned film-forming components further contain a hardening catalyst.

7. The composition for forming a resist underlayer film for EB or EUV lithography as described in claim 1 is used for forming a resist underlayer film for EB or EUV lithography with a film thickness of 10 nm or less.

8. A resist underlayer film for EB or EUV lithography, which is a cured form of the composition for forming a resist underlayer film for EB or EUV lithography as described in any one of claims 1 to 7.

9. A semiconductor processing substrate comprising a semiconductor substrate and an EB or EUV lithography resist underlayer as described in claim 8.

10. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using a composition for forming an EB or EUV lithography resist underlayer film as described in any one of claims 1 to 7; and forming a resist film on the aforementioned resist underlayer film using an EB or EUV lithography resist.

11. A pattern forming method comprising: forming a resist underlayer film on a semiconductor substrate using an EB or EUV lithography resist underlayer film forming composition as described in any one of claims 1 to 7; forming a resist film on the resist underlayer film using an EB or EUV lithography resist; irradiating the resist film with EB or EUV light, and then developing the resist film to obtain a resist pattern; and using the resist pattern as a mask to etch the resist underlayer film.

12. A method for improving the LWR of a resist pattern, comprising: forming a resist underlayer film on a semiconductor substrate using an EB or EUV lithography resist underlayer film forming composition as described in any one of claims 1 to 7; forming a resist film on the aforementioned resist underlayer film using an EB or EUV lithography resist; irradiating the aforementioned resist film with EB or EUV; and then developing the aforementioned resist film to obtain a resist pattern.