Lower membrane formation components

Abstract

Provided is an underlayer film-forming composition used when an underlayer film material is applied over a film to be processed of a substrate having the film to be processed, an organic film is formed using a pattern-forming material, and after patterning, the underlayer film and the film to be processed are processed using a composite film obtained by impregnating the organic film with a metal compound as a mask pattern, wherein impregnation of the metal compound is minimized when the organic film is impregnated with the metal compound. The underlayer film-forming composition is used to form a composite film mask pattern obtained by impregnating a patterned organic film with a metal compound on a semiconductor substrate, and the composition includes a polymer containing a hydroxy group, and imparts an underlayer film containing 22 mass% or less of a carbonyl group.

Description

[Technical Field]

[0001] Embodiments of the present invention relate to a resist underlayer film forming material, a resist underlayer film forming composition, a pattern forming method, and a method for manufacturing a semiconductor device. [Background technology]

[0002] Conventionally, microfabrication using lithography with photoresist compositions has been performed in the manufacturing of semiconductor devices. This microfabrication method involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with an active light such as ultraviolet light through a mask pattern on which the device pattern is drawn, developing the film, and then etching the substrate using the resulting photoresist pattern as a protective film to form fine irregularities on the substrate surface corresponding to the pattern. In recent years, as semiconductor devices have become more highly integrated, the active light used has also been shortened to shorter wavelengths, such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and extreme ultraviolet (EUV) (13.5 nm). With miniaturization, there are concerns that the contact area between the resist pattern and the underlying substrate will decrease, leading to a larger aspect ratio of the resist pattern (height of the resist pattern / line width of the resist pattern) and making the resist pattern more prone to collapse. Therefore, the thickness of the resist film tends to decrease. Therefore, in the resist underlayer film or anti-reflective film that comes into contact with the resist pattern, high adhesion to the resist pattern is required to prevent the aforementioned collapse from occurring.

[0003] On the one hand, in the manufacturing process of semiconductor devices, the demand for technologies to form patterns with a high aspect ratio is increasing. Since the mask patterns used in such processes are exposed to etching gases for a long time, high etching resistance is required. Therefore, after forming and patterning an organic film using a pattern-forming material containing a specific polymer, a composite film obtained by impregnating the organic film with a metal compound is used as a mask pattern, and it is known that a mask pattern with high etching resistance can be obtained. Impregnating the organic film with a metal compound is called "metalize". Specifically, metalize can be performed by bonding a metal compound to a site of an organic film having a site to which the metal compound can bind.

[0004] Patent Document 1 discloses a pattern-forming method including a film-forming step of forming a pattern-forming material film containing a pattern-forming material containing a specific polymer on a substrate, and a contacting step of contacting the pattern-forming material film with a metal compound containing a metal element.

[0005] The above mask pattern is created using the pattern-forming material (resist) described in Patent Document 1. Under the resist, a resist underlayer film for forming a good resist pattern is used. In a specific process, in the above metalize process, a resist underlayer film material that is not metalized as much as possible may be required.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] The problem to be solved by the present invention is to provide a lower layer film material used when processing a lower layer film and a processed film, which comprises applying a lower layer film material onto the processed film of a substrate having a processed film, forming an organic film using a pattern forming material, patterning, and then impregnating the organic film with a metal compound to form a composite film as a mask pattern, and suppressing the impregnation of the metal compound when the organic film is impregnated with the metal compound.

Means for Solving the Problem

[0008] The present invention includes the following. [1] A lower layer film forming composition used for forming a composite film mask pattern impregnated with a metal compound on a semiconductor substrate, comprising a polymer containing a hydroxy group and providing a lower layer film containing 22% by mass or less of a carbonyl group. [2] The polymer is represented by the following formula (I):

Chemical formula

[10] An underlayer film used to form a composite film mask pattern on a semiconductor substrate, wherein the patterned organic film is impregnated with a metal compound, and the underlayer film contains 22% by mass or less of carbonyl groups.

[11] The lower layer film according to

[10] , comprising the metal compound aluminum.

[12] A step of forming a base film by applying a base film forming composition according to any one of items [1] to [8] onto a semiconductor substrate and firing it, A process of forming a patterned organic film on the aforementioned lower layer film, and then exposing and developing it to form an organic film pattern, Next, the process of impregnating the organic film pattern with a metal compound. A method for manufacturing substrates with organic film patterns used in semiconductor manufacturing.

[13] A method for manufacturing a substrate according to

[12] , wherein the step of impregnating the organic film pattern with a metal compound is performed such that the amount of metal diffusion at a depth of 30 nm from the surface of the lower film is 10 atm% or less.

[14] A method for manufacturing a substrate according to

[12] or

[13] , wherein the metal compound comprises aluminum.

[15] A step of forming a base layer on a semiconductor substrate which may have an inorganic film formed on its surface, using a base layer forming composition according to any one of [1] to [8], A step of forming an organic film pattern on the aforementioned lower layer film, A step of impregnating the organic film pattern with a metal compound, A step of etching the inorganic film or the semiconductor substrate using the organic film pattern impregnated with the aforementioned metal as a mask. A method for manufacturing a semiconductor device, including the method described above.

[16] A method for manufacturing a semiconductor device according to

[15] , wherein the step of impregnating the organic film pattern with a metal compound is performed such that the amount of metal diffusion at a depth of 30 nm from the surface of the lower film is 10 atm% or less.

[17] A method for manufacturing a semiconductor device according to

[15] or

[16] , wherein the metal compound comprises aluminum.

[18] Use of a base film forming composition containing a polymer containing hydroxyl groups and providing a base film containing 22% by mass or less of carbonyl groups, for impregnating an organic film with a metal compound and forming a patterned composite film mask pattern on a semiconductor substrate.

[19] The aforementioned polymer is given by the following formula (I): [ka] [In formula (I), R1 represents a hydrogen atom or a methyl group. L1 represents a single bond, a -COO- group, a -CONH- group, or a linear or branched alkylene group having 1 to 5 carbon atoms. A represents a linear or branched hydroxyalkyl group having 1 to 20 carbon atoms. Use as described in

[18] , including a repeating unit structure represented by .

[20] The aforementioned polymer is given by the following formula (II): [ka] [In formula (II), T 1 represents an alkyl group having 1 to 10 carbon atoms, which may be substituted with a hydrogen atom or a halogen group. L 2 represents a single bond, a -COO- group, a -CONH- group, or a linear or branched alkylene group having 1 to 5 carbon atoms. R 1 This represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halogen group. r1 represents an integer between 0 and 3. n1 represents an integer between 0 and 2. 'a' represents an integer between 0 and 6. Use as described in

[18] , including a repeating unit structure represented by . [twenty one] The use according to any one of

[18] to

[20] , wherein the organic film impregnated with the metal compound has a metal diffusion amount of 10 atm% or less at a depth of 30 nm from the surface of the lower layer film. [twenty two] The use according to any one of

[18] to

[21] , wherein the metal compound comprises aluminum. [Effects of the Invention]

[0009] By applying the resist underlayer film forming composition according to the present invention to a lithography process, when forming an organic film using a pattern-forming material, patterning it, and then impregnating the organic film with a metal compound to produce a composite film, the impregnation of the resist underlayer film with the metal compound can be suppressed. Therefore, the composite film can be used as a mask pattern to process the underlayer film and the film to be processed. [Modes for carrying out the invention]

[0010] (Lower film forming composition) The underlying film-forming composition according to the present invention is an underlying film-forming composition used to form a composite film mask pattern on a semiconductor substrate in which a metal compound is impregnated into a patterned organic film, and comprises a polymer containing a hydroxyl group, and provides an underlying film containing 22% by mass or less of carbonyl groups.

[0011] There are no particular limitations on the polymer containing hydroxyl groups. The hydroxyl groups may be located at the polymer ends, but are preferably located in the main chain or side chains. The hydroxyl groups are preferably nonphenolic. In the case of a polymer composed of one type of unit structure (homopolymer), it is sufficient that the unit structure contains a hydroxyl group. In the case of a polymer composed of two or more types of unit structures (copolymer), it is sufficient that at least one of the unit structures contains a hydroxyl group. The number of hydroxyl groups per unit structure is not particularly limited as long as there is one or more, but is preferably five or less, four or less, three or less, or two or less.

[0012] The polymer preferably comprises a repeating unit structure represented by the following formula (I).

[0013] [Chemical formula] [In formula (I), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond, a -COO- group, a -CONH- group, or a linear or branched alkylene group having 1 to 5 carbon atoms, A represents a linear or branched hydroxyalkyl group having 1 to 20 carbon atoms.]

[0014] The polymer preferably contains a repeating unit structure represented by the following formula (II).

[0015] [Chemical formula] [In formula (II), T 1 represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom or a halogeno group, L 2 represents a single bond, a -COO- group, a -CONH- group, or a linear or branched alkylene group having 1 to 5 carbon atoms, R 1 represents a halogeno group, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or a hydroxy group or a halogeno group substituted alkyl group having 1 to 10 carbon atoms, r1 represents an integer from 0 to 3, n1 represents an integer from to 2, a represents an integer from 0 to 6.]

[0016] Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, and 3-methyl Examples include -n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group.

[0017] Furthermore, cyclic alkyl groups may also be used, for example, cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group Examples include ethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group.

[0018] The linear or branched alkylene groups having 1 to 5 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, cyclopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, cyclobutylene group, 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1 Examples include 1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene group, cyclopentylene group, 1-methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, and 2-ethyl-cyclopropylene group.

[0019] Examples of halogen groups include fluorine, chlorine, bromine, and iodine.

[0020] Examples of alkyl groups having 1 to 10 carbon atoms substituted with a halogen group include alkyl groups having 1 to 10 carbon atoms substituted with at least one of the halogen groups exemplified above.

[0021] Examples of alkyl groups having 1 to 10 carbon atoms substituted with a hydroxyl group include the alkyl groups having 1 to 10 carbon atoms substituted with at least one hydroxyl group as exemplified above.

[0022] Examples of linear or branched hydroxyalkyl groups having 1 to 20 carbon atoms include the 1 to 10 carbon atom alkyl groups exemplified above that are substituted with at least one hydroxyl group, as well as undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups substituted with at least one hydroxyl group.

[0023] Examples of alkoxy groups having 1 to 9 carbon atoms include groups in which an etheric oxygen atom (-O-) is bonded to the terminal carbon atom of an alkyl group having 1 to 9 carbon atoms, as exemplified above. Examples of such alkoxy groups include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, cyclopropoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxy group, n-pentoxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, Examples include 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, 1,1-diethyl-n-propoxy group, cyclopentoxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group, and 2-ethyl-cyclopropoxy group.

[0024] Examples of amino groups that may be substituted with alkyl groups having 1 to 3 carbon atoms include methylamino group, dimethylamino group, ethylamino group, methylethylamino group, and propylamino group.

[0025] If the polymer contains a repeating unit structure represented by formula (I), its content is preferably 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more, and 60 mol% or less, 70 mol% or less, 80 mol% or less, or 90 mol% or less, relative to the total polymer. If the polymer contains a repeating unit structure represented by formula (II), its content is preferably 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more relative to the total polymer, and 60 mol% or less, 70 mol% or less, 80 mol% or less, 90 mol% or less, or 100 mol% or less.

[0026] Some examples of the repeating unit structure described above are as follows, but the work is not limited to these.

[0027] [ka]

[0028] [ka]

[0029] The underlying film-forming composition according to the present invention may contain repeating unit structures other than the repeating unit structure described above. Examples of such repeating unit structures include unit structures derived from styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 9-vinylanthracene, vinylbenzophenone, hydroxystyrene, (meth)acrylic acid, methyl (meth)acrylate, benzyl (meth)acrylate, methyl 4-vinylbenzoate, 4-vinylbenzoic acid, and the like. The content of these components is preferably 50 mol% or less, 25 mol% or less, 10 mol% or less, 5 mol% or less, or 1 mol% or less relative to the total polymer.

[0030] The following are some examples of unit structures that can copolymerize with the repeating unit structure described above, but the invention is not limited to these.

[0031] [ka]

[0032] [ka]

[0033] The weight-average molecular weight (Mw) of the hydroxyl group-containing polymer contained in the underlying film-forming composition according to the present invention can be measured by gel permeability chromatography (GPC), and is preferably 1,000 or more, or 5,000 or more, and preferably 1,000,000 or less, or 20,000 or less.

[0034] The underlying film-forming composition according to the present invention may contain solvents, crosslinking agents, acid catalysts, and other components, to the extent that they do not impair the effects of the present invention.

[0035] (solvent) The solvent used in the underlayer film-forming composition according to the present invention is not particularly limited as long as it is a solvent that can uniformly dissolve solid components such as the polymer at room temperature, but organic solvents commonly used in semiconductor lithography process chemicals are preferred. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, 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, cyclo Examples include heptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 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 individually or in combination of two or more.

[0036] 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.

[0037] (Crosslinking agent) The crosslinking agent included as an optional component in the underlying film-forming composition according to the present invention is not particularly limited, but examples include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluryl (tetramethoxymethylglycoluryl) (POWDERLINK® 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluryl, 1,3,4,6-tetrakis(hydroxymethyl)glycoluryl, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0038] Furthermore, the crosslinking agent of this application may be a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (1d) that bond to a nitrogen atom in one molecule, as described in International Publication No. 2017 / 187969.

[0039] [ka] (In formula (1d), R1 represents a methyl group or an ethyl group.) A nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) in one molecule may be a glycoluryl derivative represented by the following formula (1E).

[0040] [ka] (In formula (1E), each of the four R1s independently represents a methyl group or an ethyl group, and R2 and R3 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.) Examples of glycoluryl derivatives represented by formula (1E) include the compounds represented by the following formulas (1E-1) to (1E-6).

[0041] [ka]

[0042] A nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) in one molecule can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2d) that bond to a nitrogen atom in one molecule with at least one compound represented by the following formula (3d).

[0043] [ka] (In formulas (2d) and (3d), R1 represents a methyl group or an ethyl group, and R4 represents an alkyl group having 1 to 4 carbon atoms.) The glycoluryl derivative represented by formula (1E) is obtained by reacting a glycoluryl derivative represented by the following formula (2E) with at least one compound represented by formula (3d).

[0044] A nitrogen-containing compound having 2 to 6 substituents represented by formula (2d) in one molecule is, for example, a glycoluryl derivative represented by the following formula (2E).

[0045] [ka] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.) Examples of glycoluryl derivatives represented by formula (2E) include the compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include the compounds represented by formulas (3d-1) and (3d-2) below.

[0046] [ka] [ka]

[0047] With regard to nitrogen-containing compounds having 2 to 6 substituents represented by the following formula (1d) bonded to the aforementioned nitrogen atom in one molecule, the full disclosure in WO2017 / 187969 is incorporated herein by reference.

[0048] Furthermore, a highly heat-resistant crosslinking agent can be used as the crosslinking agent. As a highly heat-resistant crosslinking agent, a compound containing a crosslinking substituent having an aromatic ring (e.g., a benzene ring, a naphthalene ring) in its molecule can be used. Examples of such compounds include compounds having the substructure of formula (5-1) below, and polymers or oligomers having the repeating unit of formula (5-2) below.

[0049] [ka]

[0050] The above R 11 , R 12 , R 13 , and R 14 These are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and specific examples of these alkyl groups are as described above. For m1, 1 ≤ m1 ≤ 6 - m2; for m2, 1 ≤ m2 ≤ 5; for m3, 1 ≤ m3 ≤ 4 - m2; and for m4, 1 ≤ m4 ≤ 3. Examples of compounds, polymers, and oligomers of formulas (5-1) and (5-2) are given below.

[0051] [ka]

[0052] [ka]

[0053] The above compounds can be obtained as products of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above crosslinking agents, the compound of formula (6-22) can be obtained from Asahi Organic Chemicals Co., Ltd. under the trade name TMOM-BP.

[0054] When the crosslinking agent is used, the content of the crosslinking agent is, for example, 1% to 50% by mass, preferably 5% to 30% by mass, relative to the polymer.

[0055] The acid catalyst included as an optional component in the underlying film-forming composition according to the present invention is not particularly limited, but examples include pyridinium p-toluenesulfonate, pyridinium p-hydroxybenzenesulfonate (pyridinium paraphenolsulfonic acid), pyridinium trifluoromethanesulfonate, p-toluenesulfonic acid, p-hydroxybenzenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, chlorobenzenesulfonic acid, methyl 4-phenolsulfonate, Examples of acid catalysts include sulfonic acid compounds and carboxylic acid compounds such as benzenesulfonic acid, naphthalenesulfonic acid, citric acid, and benzoic acid, as well as quaternary ammonium salts of trifluoromethanesulfonic acid, such as K-PURE® TAG2689, TAG2690, TAG2678, and CXC-1614 (all manufactured by King Industries), 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other alkyl organic sulfonates. These acid catalysts may be included individually or in combination of two or more. Among the acid catalysts, pyridinium p-hydroxybenzenesulfonate is preferred.

[0056] To prevent unreacted acids, catalysts, or inactivated catalysts from remaining in the reaction system, a catalyst ion exchange resin can be used. For example, a sulfonic acid type strong acid ion exchange resin can be used as the catalyst ion exchange resin.

[0057] The underlying film-forming composition according to the present invention may contain the acid catalyst in an amount of, for example, 1% to 30% by mass, preferably 5% to 15% by mass, relative to the content of the crosslinking agent.

[0058] (Other ingredients) The underlying film-forming composition according to the present invention does not produce pinholes or striations, and a surfactant can be added to further improve the coatability against surface unevenness. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monopalmitate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product name), Megafac F171, F173, R-30 (manufactured by Dainippon Ink, Inc., product name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., product name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added is usually 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solid content of the underlying film-forming composition according to the present invention. These surfactants may be added individually or in combination of two or more types.

[0059] The solid content of the underlying film-forming composition according to the present invention, i.e., the components excluding the solvent, is, for example, 0.01% to 10% by mass.

[0060] The underlayer film-forming composition according to the present invention is characterized by providing an underlayer film containing 22% by mass or less of carbonyl groups. For example, the underlayer film-forming composition according to the present invention is applied to a substrate used in the manufacture of semiconductor devices by an appropriate coating method, and then the underlayer film is formed by firing. At this time, the firing conditions are appropriately selected from a firing temperature of 80°C to 250°C and a firing time of 0.3 to 60 minutes. The firing temperature is preferably 150°C to 250°C, 180°C to 220°C, or 200°C to 210°C, and the firing time is preferably 0.5 to 20 minutes, 1 to 10 minutes, or 2 to 8 minutes. Here, the thickness of the underlayer film formed is, for example, 10 to 1,000 nm.

[0061] The underlying film-forming composition according to the present invention is characterized by its use in forming a composite film mask pattern on a semiconductor substrate, in which a metal compound is impregnated into a patterned organic film. The patterned organic film is not particularly limited, but in microfabrication by lithography using photoresist compositions performed in the manufacture of semiconductor devices, it is typically a photoresist layer.

[0062] As for the metal compound, there are no particular restrictions on the use of metal compounds used in CVD (Chemical Vapor Deposition) or Atomic Layer Deposition (ALD) methods.

[0063] Examples of metals included in the metal compound include aluminum, titanium, tungsten, vanadium, hafnium, zirconium, tantalum, and molybdenum. It is preferable that the metal compound contains aluminum.

[0064] The metal compound impregnated into the organic film may then be treated as appropriate and used as a mask pattern. For example, in the case of TMA, after bonding to the organic film, it may be oxidized to aluminum hydroxide or aluminum oxide, etc. Oxidation is usually carried out using an oxidizing agent such as water, ozone, or oxygen plasma, but it can also be carried out by moisture in the atmosphere without any intentional manipulation.

[0065] (Manufacturing method for substrates with organic film patterns, manufacturing method for semiconductor devices) The method for manufacturing an organic film patterned substrate used in semiconductor manufacturing according to the present invention is: The above-mentioned lower film forming composition is applied to a semiconductor substrate and fired to form a lower film. A process of forming a patterned organic film on the aforementioned lower layer film, and then exposing and developing it to form an organic film pattern, Next, the process of impregnating the organic film pattern with a metal compound. Includes.

[0066] Semiconductor substrates include semiconductor substrates on which an inorganic film is formed on the surface, such as silicon wafer substrates, silicon / silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low-dielectric material (low-k material) coated substrates. The underlying film according to the present invention is formed by applying the underlying film-forming composition according to the present invention onto such substrates used in the manufacture of semiconductor devices using an appropriate coating method such as a spinner or coater, and then firing. The firing conditions are appropriately selected from a firing temperature of 80°C to 250°C and a firing time of 0.3 to 60 minutes. The thickness of the formed underlying film is, for example, 10 to 1,000 nm, or 20 to 500 nm, or 30 to 300 nm, or 50 to 200 nm. The underlying film according to the present invention is characterized by containing 22% by mass or less of carbonyl groups.

[0067] Next, a photoresist layer is formed on the underlying film according to the present invention. The photoresist formed by coating and firing on the underlying film according to the present invention by a method known to the present invention is not particularly limited as long as it is sensitive to the light used for exposure. Both negative-type and positive-type photoresists can be used. Examples include a positive-type photoresist consisting of a novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, a chemically amplified photoresist consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, a chemically amplified photoresist consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder and a photoacid generator, a chemically amplified photoresist consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist and a photoacid generator, and a resist containing a metal element. Examples include JSR Corporation's product names V146G and AR2772, Cypree Corporation's product name APEX-E, Sumitomo Chemical Co., Ltd.'s product name PAR710, and Shin-Etsu Chemical Co., Ltd.'s product name SEPR430. In addition, examples include fluorine-containing atom polymer-based photoresists, such as those described in Proc.SPIE, Vol.3999, 330-334 (2000), Proc.SPIE, Vol.3999, 357-364 (2000), and Proc.SPIE, Vol.3999, 365-374 (2000).

[0068] Also, WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO201 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 While so-called resist compositions and metal-containing resist compositions such as those described in JP 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., can be used, they are not limited to these.

[0069] Examples of resist compositions include the following compositions.

[0070] A photosensitive or radiation-sensitive resin composition comprising resin A having repeating units with acid-degradable groups whose polar groups are protected by protecting groups that are removed by the action of an acid, and a compound represented by general formula (21).

[0071] [ka] In general formula (21), m represents an integer from 1 to 6.

[0072] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0073] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0074] L2 represents an alkylene group or single bond which may have substituents.

[0075] W1 represents a cyclic organic group which may have substituents.

[0076] M + This represents a cation.

[0077] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond 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.

[0078] A radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) that includes an acid-dissociable group, and an acid generator.

[0079] [ka] (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene with 6 to 20 carbon atoms. 1 R is a hydroxyl group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer from 0 to 11. If n is 2 or greater, multiple R groups are used. 1 They are the same or different. 2 R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), R 3 This is a monovalent group having 1 to 20 carbon atoms that contains the above-mentioned acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R 4 (This is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0080] A resist composition containing a resin (A1) comprising structural units having a cyclic carbonate ester structure, structural units represented by the following formula, and structural units having an acid-unstable group, and an acid generator.

[0081] [ka] [In the formula, R 2 X represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom, which may have a halogen atom. 1 These are single bonds, -CO-O-*, or -CO-NR 4 -* represents a bond with -Ar, and R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have one or more groups selected from the group consisting of hydroxyl groups and carboxyl groups.

[0082] Examples of resist films include the following:

[0083] A resist film comprising a base resin containing repeating units represented by the following formula (a1) and / or repeating units represented by the following formula (a2), and repeating units that generate acid bonded to the polymer main chain upon exposure.

[0084] [ka] (In equations (a1) and (a2), R A Each of these is independently either a hydrogen atom or a methyl group. 1 and R 2 Each of these is independently a tertiary alkyl group having 4 to 6 carbon atoms. 3 Each of these is independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. 1 This is a linking group having 1 to 12 carbon atoms, containing a single bond, a phenylene group or a naphthylene group, or at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. 2 (These are single bonds, ester bonds, or amide bonds.)

[0085] Examples of resist materials include the following:

[0086] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0087] [ka] (In equations (b1) and (b2), R A X is a hydrogen atom or a methyl group. 1 X is a single bond or an ester group. 2 X is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and a portion of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group, or a lactone ring-containing group, and X 2 At least one hydrogen atom in X is replaced by a bromine atom. 3 Rf is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. 1 ~Rf4 Each of these is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Also, Rf 1 and Rf 2 They may combine to form a carbonyl group. 1 ~R 5 Each of these is independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonic acid ester group. 1 and R 2 These may combine to form a ring with the sulfur atom to which they are bonded.

[0088] A resist material comprising a base resin containing a polymer containing repeating units represented by the following formula (a).

[0089] [ka] (In formula (a), R A R is a hydrogen atom or a methyl group. 1 R is a hydrogen atom or an acid-unstable group. 2 This is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. 1 This is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, which may contain a single bond or a phenylene group, or an ester group or a lactone ring. 2 (where m is -O-, -O-CH2-, or -NH-; where m is an integer from 1 to 4, and n is an integer from 0 to 3.) A resist composition that generates acid upon exposure, and whose solubility in a developer changes due to the action of the acid, It contains a base component (A) whose solubility in the developer changes due to the action of acid, and a fluorine additive component (F) that is degradable in alkaline developer. The resist composition is characterized in that the fluorine additive component (F) contains a fluororesin component (F1) having a constituent unit (f1) containing a base-dissociable group and a constituent unit (f2) containing a group represented by the following general formula (f2-r-1).

[0090] [ka] [In formula (f2-r-1), Rf 21 Each of these 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. * represents a bond.

[0091] The aforementioned constituent unit (f1) includes a constituent unit represented by the following general formula (f1-1) or a constituent unit represented by the following general formula (f1-2).

[0092] [ka] [In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. X is a divalent linking group that does not have an acid-dissociable site. A aryl X is a divalent aromatic cyclic group which may have substituents. 01 R is a single bond or a divalent linking group. 2 These are, independently, organic groups that contain a fluorine atom.

[0093] Examples of coatings, coating solutions, and coating compositions include the following:

[0094] A coating comprising a metal oxo-hydroxone network having an organic ligand by a metal-carbon bond and / or a metal carboxylate bond.

[0095] An inorganic oxo / hydroxo-based composition.

[0096] A coating solution comprising an organic solvent; a first organometallic composition represented by the formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (where 0 < z ≦ 2 and 0 < (z + x) ≦ 4), the formula R’ n SnX 4-n (where n = 1 or 2), or a mixture thereof, where R and R’ are, independently, hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof, the first organometallic composition; 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), the coating solution comprising the hydrolyzable metal compound.

[0097] 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 about 0.0025 M to about 1.5 M of tin, R is an alkyl group or a cycloalkyl group having 3 to 31 carbon atoms, and the alkyl group or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom.

[0098] An inorganic pattern-forming precursor aqueous solution comprising water, a metal oxide cation, a polyatomic inorganic anion, and a mixture with a radiation-sensitive ligand containing a peroxide group.

[0099] Exposure is performed through a mask (reticle) to form a predetermined pattern, and for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used, but the underlayer film-forming composition according to the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet) exposure, and more preferably for EUV (extreme ultraviolet) exposure. An alkaline developer is used for development, and the development temperature is appropriately selected from 5°C to 50°C and the development time from 10 seconds to 300 seconds. As the alkaline developer, aqueous solutions of alkalis such as inorganic alkalis like sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia can be used; primary amines like ethylamine and n-propylamine; secondary amines like diethylamine and di-n-butylamine; tertiary amines like triethylamine and methyldiethylamine; alcohol amines like dimethylethanolamine and triethanolamine; quaternary ammonium salts like tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines like pyrrole and piperidine can be used. Furthermore, appropriate amounts of alcohols such as isopropyl alcohol and nonionic surfactants can be added to the aqueous solutions of the above alkalis. Among these, preferred developers are quaternary ammonium salts, and more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers. Instead of an alkaline developer, a method can be used in which development is performed with an organic solvent such as butyl acetate, and the parts of the photoresist where the alkali dissolution rate has not improved are developed. After the above steps, an organic film pattern is formed.

[0100] Next, the organic film pattern is impregnated with a metal compound. The metal compound is, for example, a liquid or a gas. The metal compound to be impregnated can be an organometallic compound. Trimethylaluminum (TMA) is preferred. The metal compound can also be a chloride.

[0101] The process of impregnating the organic film pattern with a metal compound is not particularly limited and can be carried out by known methods. The organic film pattern impregnated with the metal compound may be treated in an atmosphere containing at least one selected from the group consisting of water, oxygen, and ozone. This treatment may be accompanied by heating. The heating temperature is, for example, 50°C or higher and 180°C or lower. Preferably, the treatment is carried out so that the amount of metal diffusion at a depth of 30 nm from the surface of the lower film is 10 atm% or less.

[0102] Next, the underlying film is dry-etched using the formed organic film pattern as a mask. At this time, if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed; if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed.

[0103] Subsequently, the substrate can be processed using a known method (such as dry etching) to manufacture a semiconductor device. [Examples]

[0104] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by the following examples.

[0105] The equipment used to measure the weight-average molecular weight of the polymers obtained in the synthesis examples below is shown. Equipment: HLC-8320GPC manufactured by Tosoh Corporation GPC columns: Shodex® and Asahipak® (Showa Denko K.K.) GPC measurement conditions 1 Column temperature: 40℃ Flow rate: 0.35mL / min Eluent: Tetrahydrofuran (THF) Standard sample: Polystyrene (Tosoh Corporation) GPC measurement conditions 2 Column temperature: 40℃ Flow rate: 0.6mL / min Eluent: N,N-dimethylformamide (DMF) Standard sample: Polystyrene (Tosoh Corporation)

[0106] <Synthesis Example 1> A solution of 15.0 g of styrene (manufactured by Tokyo Chemical Industry Co., Ltd.), 29.6 g of vinylnaphthalene (manufactured by Maruzen Petrochemical Co., Ltd.), 18.7 g of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.0 g of azobisisobutyronitrile (AIBN) (manufactured by Tokyo Chemical Industry Co., Ltd.), and 209.0 g of propylene glycol monomethyl ether was added to a dropping funnel. The solution was then added dropwise to a reaction flask containing 52.3 g of propylene glycol monomethyl ether under a nitrogen atmosphere at 80°C and heated and stirred for 24 hours. A resin solution corresponding to the following was obtained, and the weight-average molecular weight (Mw) measured in polystyrene equivalent by GPC (GPC measurement condition 1) was 9,313.

[0107] [ka] <Synthesis Example 2> A solution of 5.0 g of benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 14.8 g of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.2 g of azobisisobutyronitrile (AIBN) (manufactured by Tokyo Chemical Industry Co., Ltd.), and 67.0 g of propylene glycol monomethyl ether was added to a dropping funnel. This solution was then added dropwise to a reaction flask containing 16.7 g of propylene glycol monomethyl ether under a nitrogen atmosphere at 100°C and heated and stirred for 24 hours. A resin solution corresponding to the following was obtained, and the weight-average molecular weight (Mw) measured in polystyrene equivalent by GPC (GPC measurement conditions 2) was 8,824 (DMF).

[0108] [ka]

[0109] <Synthesis Example 3> A solution of 5.0 g of benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 18.2 g of glycerin monomethacrylate (product name: Bremmer GLM, manufactured by NOF Corporation), 1.2 g of azobisisobutyronitrile (AIBN) (manufactured by Tokyo Chemical Industry Co., Ltd.), and 121.7 g of propylene glycol monomethyl ether was added to a dropping funnel. This solution was then added dropwise to a reaction flask containing 19.5 g of propylene glycol monomethyl ether under a nitrogen atmosphere at 100°C and heated and stirred for 24 hours. A resin solution corresponding to the following was obtained, and the weight-average molecular weight (Mw) measured in polystyrene equivalent by GPC (GPC measurement conditions 2) was 15,480.

[0110] [ka]

[0111] <Synthesis Example 4> 25.0 g of diglycidyl terephthalate (manufactured by Nagase ChemteX Corporation, trade name: Denacol® EX711), 13.2 g of 2,2-dimethyl succinic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.46 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 59.5 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 4 hours to obtain a polymer solution. The polymer solution did not become cloudy or otherwise discolored even when cooled to room temperature, and its solubility in propylene glycol monomethyl ether was good. A resin solution corresponding to the following was obtained, and the weight-average molecular weight (Mw) measured in polystyrene equivalent by GPC (GPC measurement condition 1) was 4,267.

[0112] [ka]

[0113] <Example 1> To 2.4 g of the polymer solution containing 0.75 g of the polymer obtained in Synthesis Example 1 above, 0.23 g of tetramethoxymethyl glycoluryl (manufactured by Nippon Scitec Industries Co., Ltd., trade name: POWDERLINK® 1174) and 0.019 g of pyridinium paraphenolsulfonic acid (Patent No. 6256719, Synthesis Example 1) were mixed, and 15.1 g of propylene glycol monomethyl ether and 7.2 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a lithography resist underlayer film forming composition.

[0114] <Example 2> To 4.9 g of the polymer solution containing 0.85 g of the polymer obtained in Synthesis Example 2 above, 0.12 g of tetramethoxymethyl glycoluryl (manufactured by Nippon Scitec Industries Co., Ltd., trade name: POWDERLINK® 1174) and 0.017 g of pyridinium paraphenolsulfonic acid (Patent No. 6256719, Synthesis Example 1) were mixed, and 12.7 g of propylene glycol monomethyl ether and 7.2 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a lithography resist underlayer film forming composition.

[0115] <Example 3> To 3.9 g of the polymer solution containing 0.68 g of the polymer obtained in Synthesis Example 3 above, 0.10 g of tetramethoxymethyl glycoluryl (manufactured by Nippon Scitec Industries Co., Ltd., trade name: POWDERLINK® 1174) and 0.014 g of pyridinium paraphenolsulfonic acid (Patent No. 6256719, Synthesis Example 1) were mixed, and 14.1 g of propylene glycol monomethyl ether and 1.9 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a lithography resist underlayer forming composition.

[0116] <Example 4> 0.69 g of VP-8000 (manufactured by Nippon Soda Co., Ltd.) was mixed with 0.10 g of tetramethoxymethyl glycoluryl (manufactured by Nippon Scitec Industries Co., Ltd., trade name: POWDERLINK® 1174) and 0.021 g of pyridinium paraphenolsulfonic acid (Patent No. 6256719, Synthesis Example 1). 5.8 g of propylene glycol monomethyl ether and 13.4 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a lithography resist underlayer film forming composition.

[0117] <Comparative Example 1> To 2.4 g of the polymer solution containing 0.75 g of the polymer obtained in Synthesis Example 4 above, 0.22 g of tetramethoxymethyl glycoluryl (manufactured by Nippon Scitec Industries Co., Ltd., trade name: POWDERLINK® 1174) and 0.019 g of pyridinium paraphenolsulfonic acid (Patent No. 6256719, Synthesis Example 1) were mixed, and 15.1 g of propylene glycol monomethyl ether and 7.2 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a lithography resist underlayer film forming composition.

[0118] (Metalization properties) Organic films were formed on Si substrates using the resist underlayer compositions of Examples 1-4 and Comparative Example 1, and the metallization properties of the organic films were evaluated by metallizing them with trimethylaluminum (TMA).

[0119] Each of the above resist underlayer compositions was coated onto a 4-inch Si substrate by spin coating. The spin speed was adjusted to 1,000 to 3,500 rpm. After coating, the solvent was removed by drying, and then the substrate was fired at 205°C for 5 minutes to allow the crosslinking reaction to proceed. The film thickness after firing was adjusted to 100 nm. The resulting organic film was used as a sample for metallization treatment.

[0120] Metallization was performed using an atomic layer deposition (ALD) system (AT-400, Anric Technology). Specifically, the sample for metallization was placed inside the ALD system, and gaseous TMA was introduced into the system until it reached a predetermined pressure. After exposure to TMA, the gas phase inside the system was replaced with water vapor (H2O) and raised to a predetermined pressure. The valve was then closed, and this pressure was maintained for a predetermined time. The temperature was set to 150°C, and the process was performed for 91 cycles. Through this operation, the TMA was oxidized to aluminum hydroxide.

[0121] Here, although an ALD apparatus is used for the metallization process described above, the purpose of this operation is to impregnate the resist underlayer with TMA, and it is not so-called atomic layer deposition (ALD) which deposits atomic layers onto the substrate.

[0122] The degree of metallization is indicated by the amount of Al [atom%] per unit volume of the metallized organic film, measured using XPS;PHI 5000 VersaProbe II (ULVAC-PHI). The results are shown in the table. The calculated carbonyl group content (mass%) in the film after deposition is also shown in the table.

[0123] [Table 1]

[0124] From the above results, it can be seen that in Examples 1 to 4, the penetration rate of Al atom% at a depth of 30 nm from the film surface is approximately half that of Comparative Example 1. Furthermore, it was confirmed that the higher the carbonyl group content in the film, the higher the Al atom% in the film tends to be.

[0125] (Testing of optical parameters) The lithography resist underlayer compositions prepared in Examples 1-4 and Comparative Example 1 were each applied to silicon wafers by spin coating. The silicon wafers were then placed on a hot plate and baked at 205°C for 1 minute to form a resist underlayer (thickness 0.50 μm). The refractive index (n-value) and attenuation coefficient (k-value) of these resist underlayers were measured at wavelengths of 193 nm and 248 nm using a spectroscopic ellipsometer (JAWoollam, VUV-VASE VU-302). The results are shown in the table.

[0126] [Table 2] [Industrial applicability]

[0127] According to the present invention, a base layer material can be provided for use when processing the base layer and the workpiece, in which a base layer material is applied to the workpiece of a substrate having a workpiece, an organic film is formed using a pattern-forming material, and after patterning, a composite film is obtained by impregnating the organic film with a metal compound, and the composite film is used as a mask pattern, wherein the impregnation of the metal compound is suppressed when the metal compound is impregnated into the organic film.

Claims

1. A base layer forming composition used to form a composite film mask pattern on a semiconductor substrate in which a metal compound is impregnated into a patterned organic film, comprising a polymer containing a hydroxyl group and a base layer forming composition that gives a base layer containing 22% by mass or less of carbonyl groups, applied to a semiconductor substrate and fired to form a base layer, A process of forming a patterned organic film on the aforementioned lower layer film, and then exposing and developing it to form an organic film pattern, Next, the process of impregnating the organic film pattern with a metal compound. A method for manufacturing a substrate with an organic film pattern used in semiconductor manufacturing, wherein the metal compound contains aluminum.

2. The method for manufacturing a substrate according to claim 1, wherein the step of impregnating the organic film pattern with a metal compound is performed such that the amount of metal diffusion at a depth of 30 nm from the surface of the lower film is 10 atm% or less.

3. A base layer forming composition used to form a composite film mask pattern on a semiconductor substrate, which may have an inorganic film formed on its surface, wherein the composite film mask pattern is formed by impregnating a patterned organic film with a metal compound, and the composition comprises a polymer containing a hydroxyl group and provides a base layer containing 22% by mass or less of carbonyl groups, wherein the base layer is formed using the base layer forming composition. A step of forming an organic film pattern on the aforementioned lower layer film, A step of impregnating the organic film pattern with a metal compound, A step of etching the inorganic film or the semiconductor substrate using the organic film pattern impregnated with the aforementioned metal as a mask. A method for manufacturing a semiconductor device, wherein the metal compound comprises aluminum.

4. The method for manufacturing a semiconductor device according to claim 3, wherein the step of impregnating the organic film pattern with a metal compound is performed such that the amount of metal diffusion at a depth of 30 nm from the surface of the lower film is 10 atm% or less.

5. A use of a base film forming composition comprising a polymer containing hydroxyl groups and providing a base film containing 22% by mass or less of carbonyl groups, for impregnating an organic film with a metal compound and forming a patterned composite film mask pattern on a semiconductor substrate, wherein the metal compound comprises aluminum.

6. The polymer is of the following formula (I): 【Chemistry 1】 [In formula (I), R １ represents a hydrogen atom or a methyl group. L １ represents a single bond, a -COO- group, a -CONH- group, or a linear or branched alkylene group having 1 to 5 carbon atoms. A represents a linear or branched hydroxyalkyl group having 1 to 20 carbon atoms. The use according to claim 5, comprising a repeating unit structure represented by

7. The polymer is of the following formula (II): 【Chemistry 2】 [In formula (II), T １ This represents an alkyl group having 1 to 10 carbon atoms, which may be substituted with a hydrogen atom or a halogen group. L ２ represents a single bond, a -COO- group, a -CONH- group, or a linear or branched alkylene group having 1 to 5 carbon atoms. R １ This represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halogen group. r1 represents an integer between 0 and 3. n1 represents an integer between 0 and 2. 'a' represents an integer between 0 and 6. The use according to claim 5, comprising a repeating unit structure represented by

8. The use according to claim 5, wherein the organic film impregnated with the metal compound has a metal diffusion amount of 10 atm% or less at a depth of 30 nm from the surface of the lower layer film.

9. A base layer film-forming composition used for manufacturing a substrate according to claim 1, wherein the polymer contained in the composition is of the following formula (I): 【Transformation 3】 [In formula (I), R １ represents a hydrogen atom or a methyl group. L １ represents a single bond, a -COO- group, a -CONH- group, or a linear or branched alkylene group having 1 to 5 carbon atoms. A represents a linear or branched hydroxyalkyl group having 1 to 20 carbon atoms. A base film-forming composition comprising a repeating unit structure represented by .

10. The underlayer film-forming composition according to claim 9, wherein the polymer contains 20 mol% to 90 mol% of the repeating unit structure represented by formula (I) relative to the entire polymer.

11. The polymer is of the following formula (II): 【Chemistry 4】 [In formula (II), T １ This represents an alkyl group having 1 to 10 carbon atoms, which may be substituted with a hydrogen atom or a halogen group. L ２ represents a single bond, a -COO- group, a -CONH- group, or a linear or branched alkylene group having 1 to 5 carbon atoms, R １ This represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halogen group. r1 represents an integer between 0 and 3. n1 represents an integer between 0 and 2. 'a' represents an integer between 0 and 6. The underlayer film-forming composition according to claim 9, comprising a repeating unit structure represented by [the specified unit].

12. The underlayer film-forming composition according to claim 11, wherein the polymer contains 10 mol% to 100 mol% of the repeating unit structure represented by formula (II) relative to the entire polymer.

13. The underlying film-forming composition according to claim 9, further comprising a solvent.

14. The underlayer film-forming composition according to claim 9, further comprising a crosslinking agent and / or an acid catalyst.

15. A lower layer film characterized by being a fired product of a coated film made from the lower layer film forming composition described in any one of claims 9 to 14.

16. An underlayer film used to form a composite film mask pattern on a semiconductor substrate in which a patterned organic film is impregnated with a metal compound containing aluminum, in a method for manufacturing a substrate according to claim 1 or 2, the underlayer film containing 22% by mass or less of carbonyl groups.

17. A base layer film-forming composition used for manufacturing a semiconductor device according to claim 3, wherein the polymer contained in the composition is of the following formula (I): 【Transformation 5】 [In formula (I), R １ represents a hydrogen atom or a methyl group. L １ represents a single bond, a -COO- group, a -CONH- group, or a linear or branched alkylene group having 1 to 5 carbon atoms. A represents a linear or branched hydroxyalkyl group having 1 to 20 carbon atoms. A base film-forming composition comprising a repeating unit structure represented by .

18. The underlayer film-forming composition according to claim 17, wherein the polymer contains 20 mol% to 90 mol% of the repeating unit structure represented by formula (I) relative to the entire polymer.

19. The polymer is of the following formula (II): 【Transformation 6】 [In formula (II), T １ This represents an alkyl group having 1 to 10 carbon atoms, which may be substituted with a hydrogen atom or a halogen group. L ２ represents a single bond, a -COO- group, a -CONH- group, or a linear or branched alkylene group having 1 to 5 carbon atoms. R １ This represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halogen group. r1 represents an integer between 0 and 3. n1 represents an integer between 0 and 2. 'a' represents an integer between 0 and 6. The underlayer film-forming composition according to claim 17, comprising a repeating unit structure represented by [the specified unit].

20. The underlayer film-forming composition according to claim 19, wherein the polymer contains 10 mol% to 100 mol% of the repeating unit structure represented by formula (II) relative to the entire polymer.

21. The underlying film-forming composition according to claim 17, further comprising a solvent.

22. The underlayer film-forming composition according to claim 17, further comprising a crosslinking agent and / or an acid catalyst.

23. A lower layer film characterized by being a fired product of a coated film made from the lower layer film forming composition described in any one of claims 17 to 22.

24. An underlayer film used to form a composite film mask pattern on a semiconductor substrate in which a patterned organic film is impregnated with a metal compound containing aluminum, in a method for manufacturing a semiconductor device according to claim 3 or 4, the underlayer film containing 22% by mass or less of carbonyl groups.

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