Coating composition for uneven substrates containing a compound having a curable functional group

Abstract

Coating composition for uneven substrates that forms a coating film with pattern filling and planarizing properties [Solution] The main agent comprises (A): a partial structure of formula (A-1) or formula (A-2), and (B): a specific olefin, acetylene, or azide partial structure, and is cured by light irradiation or by heating at 30°C to 300°C during or after light irradiation. The content of the main agent in the solid content is 95% by mass to 100% by mass. TIFF2023072048000032.tif65133

Description

[Technical field]

[0001] The present invention relates to a coating composition for uneven substrates for forming a planarized film on a substrate having steps by photocrosslinking, and a method for producing a planarized laminated substrate using the coating composition for uneven substrates. [Background technology]

[0002] In recent years, semiconductor integrated circuit devices have been fabricated to meet increasingly fine design rules, and in order to form finer resist patterns using photolithography technology, it is necessary to shorten the exposure wavelength.

[0003] However, as the exposure wavelength becomes shorter, the depth of focus decreases, making it necessary to improve the planarization of the coating formed on the substrate. In other words, the planarization technology on the substrate is becoming important for manufacturing semiconductor devices with fine design rules.

[0004] As a method for forming a planarizing film, for example, a method for forming a resist underlayer film by photocuring the resist underlayer film has been disclosed.

[0005] A resist underlayer film-forming composition containing a polymer having an epoxy group or an oxetane group in a side chain and a photocationic polymerization initiator, or a resist underlayer film-forming composition containing a polymer having a radically polymerizable ethylenically unsaturated bond and a photoradical polymerization initiator has been disclosed (see Patent Document 1).

[0006] In addition, a resist underlayer film-forming composition has been disclosed that contains a silicon-based compound having a cationic polymerizable reactive group such as an epoxy group or a vinyl group, a photocationic polymerization initiator, and a photoradical polymerization initiator (see Patent Document 2).

[0007] Also disclosed is a method for manufacturing a semiconductor device using a resist underlayer film containing a polymer having a crosslinkable functional group (such as a hydroxyl group) in the side chain, a crosslinking agent, and a photoacid generator (see Patent Document 3).

[0008] Further, although they are not photocrosslinkable resist underlayer films, resist underlayer films having unsaturated bonds in the main chain or side chain have been disclosed (see Patent Documents 4 and 5). [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication Pamphlet WO2006 / 115044 [Patent Document 2] International Publication Pamphlet WO2007 / 066597 [Patent Document 3] International Publication Pamphlet WO2008 / 047638 [Patent Document 4] International Publication Pamphlet WO2009 / 008446 [Patent Document 5] Special table 2004-533637 Summary of the Invention [Problem to be solved by the invention]

[0010] In conventional photocrosslinking materials, for example, in a resist underlayer film forming composition containing a polymer having a thermal crosslinking functional group such as a hydroxyl group, a crosslinking agent, and an acid catalyst (acid generator), when the composition is heated to fill a pattern (e.g., a hole or trench structure) formed on a substrate, a crosslinking reaction proceeds and viscosity increases, resulting in a problem of insufficient filling of the pattern. Furthermore, there is a problem of loss of flatness due to thermal shrinkage caused by degassing.

[0011] In addition, in a resist underlayer film-forming composition containing a polymer having a cationic polymerizable reactive group such as an epoxy group or a vinyl group and an acid generator, light irradiation and heating are performed. In this case, if the content of the acid generator is high, heat shrinkage due to degassing occurs, which causes a problem in flatness.

[0012] Therefore, an object of the present invention is to provide a coating composition for coating an uneven substrate, which is capable of forming a coating having planarizing properties on a substrate, which has high pattern filling properties and is capable of forming a coating film without causing degassing or thermal shrinkage. [Means for solving the problem]

[0013] In a first aspect, the present invention provides a composition comprising a base material comprising the following compound (A), compound (B), or a mixture thereof, and compound (A) is represented by the following formula (A-1) or formula (A-2): [ka] (wherein n is an integer of 1 or 2, the dashed line indicates a bond to an aromatic ring, and the aromatic ring is an aromatic ring constituting a polymer skeleton or an aromatic ring constituting a monomer), Compound (B) contains at least one partial structure selected from the group consisting of partial structures represented by the following formulas (B-1) to (B-5), or a partial structure represented by formula (B-6): and A compound including a partial structure formed by combining with a partial structure represented by formula (B-8), [ka] (In the formula, R 1 , R 1a , R 3 , R 5 , R 5a , and R 6a each independently represents a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, a nitrogen atom, an amide group, an amino group, or a group consisting of a combination thereof; R 2 、 R 4 , and R 6 each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms, an oxygen atom, a carbonyl group, an amide group, an amino group, or a group consisting of a combination thereof; R 2 、 R 4 , R6 represents a monovalent group, R 1 , R 1a , R 3 , R 5a , and R 6a represents a divalent group, R 5 represents a trivalent group, n represents the number of repeating units from 1 to 10, and the dotted lines represent chemical bonds with adjacent atoms. A coating composition for uneven substrates comprising a base material containing compound (A), compound (B), or a mixture thereof, and a solvent, When the base agent is used, the composition is cured by light irradiation or by heating at 30° C. to 300° C. during or after light irradiation, When a base agent containing the compound (B) is used, the composition is cured by heating at 30° C. to 300° C. during or after light irradiation, the composition for covering an uneven substrate, wherein the content of the main agent in the solid content of the composition is 95% by mass to 100% by mass; As a second aspect, the composition for covering a substrate with differences in height according to the first aspect, wherein the aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring; As a third aspect, the polymer containing an aromatic ring contains a hydroxyaryl novolac structure. P The composition for covering a stepped substrate according to the first or second aspect, which is a polymer in which a hydroxyl group of the polymer is substituted with an organic group of formula (A-1) or formula (A-2); As a fourth aspect, the composition for covering a substrate with differences in level according to the first or second aspect, wherein the aromatic ring-containing monomer is a monomer in which a hydroxyl group of the aromatic ring is substituted with an organic group of formula (A-1) or formula (A-2). As a fifth aspect, when the base material is a mixture of the compound (A) and the compound (B), the molar ratio of the epoxy group to the vinyl group is 100:1 to 1:100. The step-covered substrate covering composition according to any one of the preceding claims, as a sixth aspect, the composition for covering a substrate with differences in height according to any one of the first to fifth aspects, further comprising an acid generator; as a seventh aspect, the composition for covering a substrate with differences in height according to any one of the first to sixth aspects, further comprising a surfactant; As an eighth aspect, a method for producing a coated substrate, the method comprising: a step (i) of applying the stepped substrate covering composition according to any one of the first to seventh aspects to a substrate having a step; and a step (ii) of exposing the composition applied in the step (i) to light or heating it during or after exposure. As a ninth aspect, the method for producing a coated substrate according to the eighth aspect further comprises a step (ia) of heating the step-changed substrate coating composition at a temperature of 70° C. to 400° C. for 10 seconds to 5 minutes after applying the step (i). As a tenth aspect, the method for producing a coated substrate according to the eighth or ninth aspect, wherein the light wavelength used for exposure in the step (ii) is 150 nm to 248 nm; According to an eleventh aspect, the amount of exposure light in the step (ii) is 10 mJ / cm 2 ~5000mJ / cm 2 The method for producing a coated substrate according to any one of the eighth to tenth aspects, As a twelfth aspect, the method for producing a coated substrate according to any one of the eighth to eleventh aspects, in which the substrate has an open area (non-pattern area) and a pattern area of ​​DENCE (dense) and ISO (sparse), and the aspect ratio of the pattern is 0.1 to 100; As a thirteenth aspect, the method for producing a coated substrate according to any one of the eighth to twelfth aspects, in which a bias (a coating step) between the open area and the pattern area is 1 nm to 50 nm; As a fourteenth aspect, a method for producing a semiconductor device, comprising the steps of forming an underlayer film on a substrate having a step using the uneven substrate coating composition according to any one of the first to seventh aspects, forming a resist film thereon, irradiating the resist film with light or an electron beam, or heating the resist film during or after the irradiation with light or an electron beam, and then developing the resist film to form a resist pattern, etching the underlayer film with the formed resist pattern, and processing a semiconductor substrate with the patterned underlayer film; As a fifteenth aspect, the method for manufacturing a semiconductor device according to the fourteenth aspect, wherein the substrate having the step has an open area (non-pattern area) and a pattern area of ​​DENCE (dense) and ISO (sparse), and the aspect ratio of the pattern is 0.1 to 100; As a sixteenth aspect, a step of forming an underlayer film from a step substrate covering composition is provided. a method for producing a semiconductor device according to a fourteenth aspect, comprising: a step (i) of applying the stepped substrate covering composition according to any one of the first to seventh aspects to a substrate having a step; and a step (ii) of exposing the composition applied in the step (i) to light or heating it during or after exposure; As a seventeenth aspect, the method for producing a semiconductor device according to the sixteenth aspect further comprises a step (ia) of heating the step-like substrate covering composition at a temperature of 70° C. to 400° C. for 10 seconds to 5 minutes after applying the step (i). As an eighteenth aspect, the method for producing a semiconductor device according to the sixteenth aspect or the seventeenth aspect, wherein a wavelength of light used for exposure in the step (ii) is 150 nm to 248 nm; According to a nineteenth aspect, the amount of exposure light in the step (ii) is 10 mJ / cm 2 ~5000mJ / cm 2 A method for manufacturing a semiconductor device according to any one of sixteenth to eighteenth aspects, As a twentieth aspect, the method for producing a semiconductor device according to the fourteenth aspect, wherein an underlayer film obtained from the uneven substrate coating composition has a coating step of 1 nm to 50 nm; As a twenty-first aspect, a method for producing a substrate having a step, comprising the steps of forming an underlayer film on a substrate having a step using the stepped substrate coating composition according to any one of the first to seventh aspects, forming a hard mask thereon, forming a resist film thereon, irradiating the resist film with light or an electron beam, or heating the resist film during or after the irradiation with light or an electron beam, and then developing the resist film to form a resist pattern, etching the hard mask with the resist pattern thus formed, etching the underlayer film with the patterned hard mask, and etching the resist film with the patterned hard mask. a manufacturing method of a semiconductor device, the manufacturing method including a step of processing a semiconductor substrate by using the underlying film; As a 22nd aspect, the method for manufacturing a semiconductor device according to the 21st aspect, wherein the substrate having the step has an open area (non-pattern area) and a pattern area of ​​DENCE (dense) and ISO (sparse), and the aspect ratio of the pattern is 0.1 to 100; As a 23rd aspect, a step of forming an underlayer film from a step substrate covering composition a method for producing a semiconductor device according to a twenty-first aspect, comprising: a step (i) of applying the stepped substrate covering composition according to any one of the first to seventh aspects to a substrate having a step; and a step (ii) of exposing the composition applied in the step (i) to light or heating it during or after exposure; As a 24th aspect, the method for producing a semiconductor device according to the 23rd aspect further comprises a step (ia) of heating the stepped substrate covering composition at a temperature of 70° C. to 400° C. for 10 seconds to 5 minutes after applying the stepped substrate covering composition in the step (i); As a 25th aspect, the method for producing a semiconductor device according to the 23rd aspect or the 24th aspect, wherein a wavelength of light used for exposure in the step (ii) is 150 nm to 248 nm; According to a twenty-sixth aspect, the amount of exposure light in the step (ii) is 10 mJ / cm 2 ~5000mJ / cm 2 A method for manufacturing a semiconductor device according to any one of the twenty-third to twenty-fifth aspects, According to a twenty-seventh aspect, there is provided a method for producing a semiconductor device as set forth in the twenty-first aspect, wherein an underlayer film obtained from the uneven substrate covering composition has a coating step of 1 nm to 50 nm. Effect of the Invention

[0014] The stepped substrate coating composition is applied onto the stepped substrate, and in some cases, the pattern is filled by further reflowing by heating. Since the stepped substrate coating composition of the present invention does not have a thermal crosslinking site, there is no increase in viscosity during use, and a flat film can be formed regardless of the open area (non-pattern area) on the stepped substrate, or the pattern area of ​​DENCE (dense) or ISO (sparse). In the stepped substrate coating composition of the present invention, the epoxy group-containing compound contained therein is polymerized by heating during or after light irradiation, and a crosslinked structure of epoxy groups or unsaturated bonds is formed by cationic species or radical species by light irradiation. That is, the stepped substrate coating composition of the present invention can crosslink the stepped substrate coating film (flattening film) formed by applying the stepped substrate coating composition by reaction of double bonds or triple bonds derived from epoxy groups or unsaturated groups.

[0015] Therefore, the uneven substrate coating film (flattening film) formed by the uneven substrate coating composition of the present invention does not undergo a crosslinking reaction due to a crosslinking agent and an acid catalyst during thermal reflow, and the subsequent photocrosslinking is a photoreaction that does not involve degassing, so no thermal shrinkage occurs. Therefore, the uneven substrate coating composition of the present invention can provide an excellent flattening film that simultaneously satisfies both good filling properties into a pattern and flatness after filling.

[0016] In the present invention, if the film of the uneven substrate coating composition is photocurable and photocuring is not completed sufficiently down to the bottom of the applied film, when the film of the uneven substrate coating composition is post-heated after light irradiation or when a hard mask or resist is applied on top, the uncured portions may flow, resulting in a deterioration in the planarization of the film of the uneven substrate coating composition of the present application.

[0017] It is believed that the crosslinked structure based on epoxy groups forms a stronger crosslinked structure than the crosslinked structure based on unsaturated bonds, thereby preventing the flow of uncured parts, and since there is less film shrinkage, deterioration of planarization after application of the silicon-containing hard mask forming composition that is coated on the upper layer can be suppressed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention relates to a composition comprising a base material containing the following compound (A), compound (B), or a mixture thereof, and compound (A) is a compound containing a partial structure represented by the following formula (A-1) or formula (A-2): [ka] Compound (B) contains at least one partial structure selected from the group consisting of partial structures represented by the following formulas (B-1) to (B-5), or a partial structure represented by formula (B-6): and A compound including a partial structure formed by combining with a partial structure represented by formula (B-8), [ka] A coating composition for uneven substrates comprising the base material and a solvent, When a base material containing the compound (A) or the compound (A) and the compound (B) is used, the composition is cured by light irradiation or by heating at 30° C. to 300° C. during or after light irradiation, When a base agent containing the compound (B) is used, the composition is cured by heating at 30° C. to 300° C. during or after light irradiation, In the composition for covering an uneven substrate, the content of the main agent in the solid content of the composition is 95% by mass to 100% by mass.

[0019] In formula (A-1), n ​​represents an integer of 1 or 2, the dashed line represents a bond to an aromatic ring, and the aromatic The rings may be aromatic rings constituting the polymer backbone or may be aromatic rings constituting the monomer.

[0020] In formulas (B-1) to (B-8), R 1 , R 1a , R 3 , R 5 , R 5a , and R 6aeach independently represents a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, a nitrogen atom, an amide group, an amino group, or a group consisting of a combination thereof; R 2 、 R 4 , and R 6 each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms, an oxygen atom, a carbonyl group, an amide group, an amino group, or a group consisting of a combination thereof; R 2 、 R 4 , R 6 represents a monovalent group, R 1 , R 1a , R 3 , R 5a , and R 6a represents a divalent group, R 5 represents a trivalent group, n represents the number of repeating units from 1 to 10, and the dotted lines represent chemical bonds with adjacent atoms.

[0021] The solid content of the uneven substrate coating composition is 0.1 to 70% by mass, or 0.1 to 60% by mass, or 0.2 to 30% by mass, or 0.3 to 15% by mass. The solid content is the content of all components excluding the solvent in the uneven substrate coating composition.

[0022] The aromatic ring can be a benzene ring, a naphthalene ring, or an anthracene ring.

[0023] The polymer containing aromatic rings contains a hydroxyaryl novolac structure. P The hydroxyl group of the polymer may be substituted with an organic group of the formula (A-1) or an organic group of the formula (A-2). These aryl groups may be aromatic groups derived from benzene or naphthalene.

[0024] [ka]

[0025] [ka]

[0026] [ka]

[0027] [ka]

[0028] The polymer of formula (a-1) is available from DIC Corporation under the trade names HP-5000 and HP-5000L. The polymer of formula (a-2) is available from DIC Corporation under the trade name HP-7200. The polymer of formula (a-3) is available from Nippon Kayaku Co., Ltd. under the trade name NC-2000-L. The polymer of formula (a-4) is available from Nippon Kayaku Co., Ltd. under the trade name NC-3000-L. The polymer of formula (a-5) is available from Nippon Kayaku Co., Ltd. under the trade name NC-7000L. The polymer of formula (a-6) is available from Nippon Kayaku Co., Ltd. under the trade name EPPN-201. The polymer of formula (a-7) is available from Nippon Kayaku Co., Ltd. under the trade name NC-7300L. The polymer of formula (a-8) is available from Nippon Kayaku Co., Ltd. under the trade name NC-3500. The polymer of formula (a-9) is available from Nippon Kayaku Co., Ltd. under the trade name EPPN-501H. The polymer of formula (a-10) is available from Nippon Kayaku Co., Ltd. under the trade name FAE-2500. The polymer of formula (a-11) is available from Mitsubishi Chemical Corporation under the trade name Multifunctional Epoxy Resin 157. The polymer of formula (a-12) is available from Mitsubishi Chemical Corporation under the trade name Multifunctional Epoxy Resin 1032.

[0029] The weight average molecular weight of the polymer is from 600 to 1,000,000, or from 600 to 200,000, or from 1,500 to 15,000.

[0030] In the present invention, the monomer containing an aromatic ring may be a monomer in which the hydroxyl group of the aromatic ring is substituted with an organic group of formula (A-1) or an organic group of formula (A-2).

[0031] Examples of the hydroxyl group on the aromatic ring include the hydroxyl groups of phenol and naphthol.

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] The monomer compound of formula (aa-1) is available from DIC Corporation under the trade names HP4700 and HP4710. The monomer compound of formula (aa-2) is available from DIC Corporation under the trade name HP4770. The monomer compound of formula (aa-3) is available from AOC Corporation under the trade name TEP-G. The monomer compound of formula (aa-4) is available from Nippon Kayaku Co., Ltd. under the trade name NC-6000. The monomer compound of formula (aa-5) is available from Nippon Kayaku Co., Ltd. under the trade name RE-810NM. The monomer compound of formula (aa-6) is available from Mitsubishi Chemical Corporation under the trade name Liquid Epoxy Bis-A Type. The monomer compound of formula (aa-7) is available from Mitsubishi Chemical Corporation under the trade name Liquid Epoxy Bis-F Type. The monomer compound of formula (aa-8) is available from Mitsubishi Chemical Corporation under the trade name Multifunctional Epoxy 1031S. The monomer compound of formula (aa-9) is available from Mitsubishi Chemical Corporation under the trade name Multifunctional Epoxy 604. The monomer compound of formula (aa-10) is available from Adeka Resin Co., Ltd. under the trade name EP-3950S / L. The monomer compound of formula (aa-11) is available from Mitsubishi Chemical Corporation under the trade name YX4000. The monomer compound of formula (aa-12) is available from Mitsubishi Chemical Corporation under the trade name YL6121H. The monomer compound of formula (aa-13) is available from Osaka Gas Chemicals Co., Ltd. under the trade name OGSOL-EG-200. The monomer compound of formula (aa-14) is available from DIC Corporation under the trade name EXA-1514. The monomer compound of formula (aa-15) is available from Osaka Gas Chemicals Co., Ltd. under the trade name PG-100. The monomer compound of formula (aa-16) is available as 2,2'-diglycidyloxy-1,1'-binaphthalene. The monomer compound of formula (aa-17) is available from DIC Corporation under the trade name HP-4770. The monomer compound of formula (aa-18) is available from Mitsubishi Chemical Corporation under the trade name YX-8800.

[0037] Furthermore, a product name HP-6000 manufactured by DIC Corporation can also be used.

[0038] The above-mentioned aromatic ring-containing monomers may have a molecular weight in the range of 200 to 10,000, or 200 to 2,000, or 200 to 1,000.

[0039] The compound (A) can be used with an epoxy value in the range of 150 to 350, or 150 to 300. An epoxy compound with a softening point in the range of 120° C. or lower can be used.

[0040] In the present invention, when the base resin is a mixture of compound (A) and compound (B), the molar ratio of epoxy groups to vinyl groups is 100:1 to 1:100, or 30:1 to 1:30, or 20:1 to 1:1, and compound (B) contains at least one partial structure selected from the group consisting of partial structures represented by formulas (B-1) to (B-5), or a partial structure represented by formula (B-6): and It is possible to obtain a compound containing a partial structure formed by combining with the partial structure represented by formula (B-8).

[0041] In formulas (B-1) to (B-8), R 1 , R 1a , R 3 , R 5 , R 5a , and R 6a each represents a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, a nitrogen atom, an amide group, an amino group, or a group consisting of a combination thereof; R 2 、 R 4 , and R 6 each represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms, an oxygen atom, a carbonyl group, an amide group, an amino group, or a group consisting of a combination thereof; R 2 、 R 4 , R 6 represents a monovalent group, R 1 , R 1a , R 3 , R 5a , and R 6a represents a divalent group, R 5represents a trivalent group, n represents the number of repeating units from 1 to 10, and the dotted lines represent chemical bonds with adjacent atoms.

[0042] The saturated hydrocarbon group having 1 to 10 carbon atoms may be an alkyl group having 1 to 10 carbon atoms, and examples of such groups include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, a 1-methyl- Cyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 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, 2,3-dimethyl-cyclobutyl, 2,4- Examples of such cyclopropyl groups include 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.

[0043] The saturated hydrocarbon group having 1 to 10 carbon atoms also includes a divalent alkylene group derived from the above alkyl group.

[0044] Examples of the unsaturated hydrocarbon group having 2 to 10 carbon atoms include alkenyl groups or alkynyl groups corresponding to the alkyl groups having 2 or more carbon atoms.

[0045] The aromatic hydrocarbon group having 6 to 40 carbon atoms may be a divalent arylene group having 6 to 40 carbon atoms, such as a phenylene group, a biphenylene group, a terphenylene group, a fluorenylene group, a naphthylene group, an anthrylene group, a pyrenylene group, or a carbazolylene group.

[0046] Examples of the compound (B) used in the present invention include the following. [ka]

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] The compound of the above formula (b-1) can be obtained by reacting HP-4700 (trade name, manufactured by DIC Corporation) with acrylic acid. The compound of the above formula (b-2) can be obtained by reacting HP-5000 (trade name, manufactured by DIC Corporation) with acrylic acid. The compound of the above formula (b-3) can be obtained by reacting EPPN-501H (trade name, manufactured by Nippon Kayaku Co., Ltd.) with acrylic acid. The compound of the above formula (b-4) can be obtained by reacting acrylic acid with NC-7000L (trade name, manufactured by Nippon Kayaku Co., Ltd.). The compound of the above formula (b-5) can be obtained by reacting acrylic acid with Nippon Kayaku Co., Ltd.'s product name NC-3500. The compound of the above formula (b-6) can be obtained by reacting HP-4700 (trade name, manufactured by DIC Corporation) with methacrylic acid. The compound of the above formula (b-7) is monoitaconate (manufactured by DIC Corporation, trade name HP-4700). It is obtained by reacting with methyl. The compound of the above formula (b-8) can be obtained by reacting HP-4700 (trade name, manufactured by DIC Corporation) with diallylisocyanuric acid. The compound of the above formula (b-9) can be obtained by reacting HP-4700 (trade name, manufactured by DIC Corporation) with sorbic acid. The compound of the above formula (b-10) can be obtained by reacting 4-vinylbenzoic acid with HP-4700 (trade name, manufactured by DIC Corporation). The compound of the above formula (b-11) can be obtained by reacting HP-4700 (trade name, manufactured by DIC Corporation) with N-(4-hydroxyphenyl)methacrylamide. The compound of the above formula (b-12) can be obtained by reacting TEPC-BIP-A (manufactured by Asahi Organic Chemicals Co., Ltd.) with glycidyl methacrylate. The compound of the above formula (b-13) can be obtained by reacting TEP-BOCP, manufactured by Asahi Organic Chemicals Co., Ltd., with glycidyl methacrylate. The compound of the above formula (b-14) can be obtained by reacting the reaction product of 2,2'-biphenol and 2-ethylhexylaldehyde with glycidyl methacrylate. The compound of the above formula (b-15) can be obtained by reacting monoallyldiglycidylisocyanuric acid with 2,2-dimethylsuccinic acid. The compound of the above formula (b-16) can be obtained by reacting triglycidyl isocyanurate with acrylic acid. The compound of the above formula (b-17) can be obtained by reacting bisphenol A diallyl with glycidyl acrylate. The compound of the above formula (b-18) can be obtained by reacting monoallyldiglycidylisocyanuric acid, 2,2-dimethylsuccinic acid, and monoallylisocyanuric acid. The compound of the above formula (b-19) can be obtained by reacting HP-4700 (trade name, manufactured by DIC Corporation) with propargylic acid. The compound of the above formula (b-20) can be obtained by reacting acrylic acid and 5-hexinoic acid with HP-4700 (trade name, manufactured by DIC Corporation). The compound of the above formula (b-21) can be obtained by reacting 4-azidobenzoic acid and 5-hexinoic acid with HP-4700 (trade name, manufactured by DIC Corporation). The compound of the above formula (b-22) can be obtained by reacting monoallyl diglycidyl isocyanuric acid with 3,3'-dithiopropionic acid, and then reacting with 2-isocyanatoethyl acrylate. The compound of the above formula (b-23) can be obtained by reacting diglycidyl terephthalic acid with dimethylsuccinic acid, and then reacting with 2-isocyanatoethyl acrylate.

[0055] The present invention can contain an acid generator. As the acid generator, a photoacid generator can be used. Examples of the photoacid generator include onium salt-based photoacid generators such as bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate and triphenylsulfonium trifluoromethanesulfonate, halogen-containing compound-based photoacid generators such as phenyl-bis(trichloromethyl)-s-triazine, and sulfonic acid-based photoacid generators such as benzoin tosylate and N-hydroxysuccinimide trifluoromethanesulfonate. The amount of the photoacid generator is 0.2 to 5% by mass, or 0.4 to 5% by mass, or 0.4 to 4.9% by mass, or 0.4 to 4.8% by mass, based on the total solid content.

[0056] The step-like substrate coating composition of the present invention may contain a surfactant. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene-polyoxypropylene block copolymers, sol. nonionic surfactants such as sorbitan fatty acid esters, such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; and EFTOP (registered trademark) EF30. Fluorine-based surfactants such as EF303, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Megafac (registered trademark) F171, F173, R30, R-30N, R-40, R-40LM (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). One type selected from these surfactants may be added, or two or more types may be added in combination. The content of the surfactant is, for example, 0.01 to 5% by mass, or 0.01 to 2% by mass, or 0.01 to 0.2% by mass, or 0.01 to 0.1% by mass, or 0.01 to 0.09% by mass, based on the solid content excluding the solvent described below from the stepped substrate covering composition of the present invention.

[0057] In the present invention, examples of the solvent for dissolving compound (A), compound (B), or compound (A) and compound (B) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol dimethyl ether, toluene, xylene, styrene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone, acetone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl normal butyl ketone, isopropyl acetate ketone, normal propyl acetate, isobutyl acetate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, normal propanol, 2-methyl-2-butanol, isobutanol, normal butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, isopropyl ether, 1,4-dioxane, N,N-dimethyltetramamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N-cyclo, hexyl-2-pyrrolidinone, etc. These organic solvents may be used alone or in combination of two or more.

[0058] Next, the method for forming a planarizing film using the uneven substrate coating composition of the present invention will be described. The uneven substrate coating composition is applied to a substrate (e.g., transparent substrate such as silicon / silicon dioxide coating, glass substrate, ITO substrate, etc.) used in the manufacture of precision integrated circuit elements by a suitable coating method such as a spinner or coater, and then baked (heated) and exposed to light to form a coating film. That is, the coated substrate is manufactured by including a step (i) of applying the uneven substrate coating composition to a substrate having steps, and a step (ii) of exposing the composition applied in step (i) or heating it to 30°C to 300°C, or 100°C to 300°C during or after exposure.

[0059] When coating is carried out using a spinner, coating can be carried out, for example, at a rotation speed of 100 to 5,000 for 10 to 180 seconds.

[0060] The substrate may have an open area (non-patterned area) and patterned areas of DENCE (dense) and ISO (coarse), with the aspect ratio of the pattern being 0.1 to 10, or 0.1 to 100.

[0061] A non-patterned area refers to a portion of the substrate that does not have a pattern (e.g., a hole or trench structure), a DENCE (dense) area refers to a portion of the substrate where patterns are densely packed, and an ISO (coarse) area refers to a portion of the substrate where patterns are widely spaced and scattered. The aspect ratio of a pattern is the ratio of the pattern depth to the pattern width. The pattern depth is usually several hundred nm (e.g., about 100 to 300 nm), and a DENCE (dense) area is an area where patterns of several tens of nm (e.g., 30 to 80 nm) are densely packed at intervals of about 100 nm. An ISO (coarse) area is an area where patterns of several hundred nm (e.g., about 200 to 1000 nm) are scattered.

[0062] Here, the thickness of the uneven substrate coating film (flattening film) is preferably 0.01 μm to 3.0 μm. In step (ia), the coating may be heated at 70° C. to 400° C., or 100° C. to 250° C. for 10 seconds to 5 minutes, or 30 seconds to 2 minutes. This heating causes the uneven substrate coating composition to reflow, forming a flat uneven substrate coating film (flattening film).

[0063] In step (ii), the exposure light is actinic radiation such as near ultraviolet light, far ultraviolet light, or extreme ultraviolet light (e.g., EUV, wavelength 13.5 nm), and light having a wavelength of, for example, 248 nm (KrF laser light), 193 nm (ArF laser light), 172 nm (xenon excimer light), 157 nm (F2 laser light), etc. The exposure wavelength may be ultraviolet light having a wavelength of 150 nm to 248 nm, and preferably a wavelength of 172 nm.

[0064] This exposure causes crosslinking of the film covering the stepped substrate (flattening film). In step (ii), the exposure dose is 10 mJ / cm 2 ~3000mJ / cm 2 , or 10 mJ / cm 2 ~5000mJ / cm 2 When the amount of exposure light falls within this range, a photoreaction occurs, crosslinking is formed, and solvent resistance is imparted.

[0065] The stepped substrate coating film (flattening film) thus formed preferably has zero bias (coating step) between the open area and the pattern area, but can be flattened to a range of 1 nm to 50 nm, or 1 nm to 25 nm. The bias between the open area and the DENCE area is about 15 nm to 20 nm, and the bias between the open area and the ISO area is about 1 nm to 10 nm.

[0066] The uneven substrate coating film (flattening film) obtained by the present invention can be coated with a resist film, and the resist film can be exposed and developed by lithography to form a resist pattern, and a substrate can be processed according to the resist pattern. In this case, the uneven substrate coating film (flattening film) is a resist underlayer film, and the uneven substrate coating composition is also a resist underlayer film-forming composition.

[0067] A good resist pattern can be obtained by applying a resist onto the resist underlayer film, irradiating the resist with light or electron beams through a specified mask, developing, rinsing, and drying. If necessary, post-exposure baking (PEB) after irradiation with light or electron beams can also be performed. Then, the resist underlayer film in the portion where the resist film has been developed and removed in the above process is removed by dry etching, and a desired pattern can be formed on the substrate.

[0068] The resist used in the present invention is a photoresist or an electron beam resist.

[0069] The photoresist to be applied on the upper part of the resist underlayer film for lithography in the present invention may be either a negative type or a positive type, and examples thereof include a positive type photoresist consisting of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; a chemically amplified photoresist consisting of a binder having a group that is decomposed by acid to increase the alkaline dissolution rate and a photoacid generator; a chemically amplified photoresist consisting of an alkali-soluble binder, a low molecular weight compound that is decomposed by acid to increase the alkaline dissolution rate of the photoresist and a photoacid generator; a chemically amplified photoresist consisting of a binder having a group that is decomposed by acid to increase the alkaline dissolution rate and a low molecular weight compound that is decomposed by acid to increase the alkaline dissolution rate of the photoresist and a photoacid generator; a photoresist having a Si atom in the skeleton, and examples thereof include APEX-E, a product of Rohm and Haas Company.

[0070] Examples of the electron beam resist to be applied on the upper side of the resist underlayer film for lithography in the present invention include a composition consisting of a resin containing a Si-Si bond in the main chain and an aromatic ring at the end and an acid generator that generates an acid when irradiated with an electron beam, or a composition consisting of poly(p-hydroxystyrene) in which a hydroxyl group is substituted with an organic group containing N-carboxyamine and an acid generator that generates an acid when irradiated with an electron beam. In the latter electron beam resist composition, the acid generated from the acid generator by irradiation with an electron beam reacts with the N-carboxyaminooxy group in the polymer side chain, and the polymer side chain decomposes into a hydroxyl group, exhibits alkali solubility, and dissolves in an alkaline developer to form a resist pattern. Acid generators that generate acid upon irradiation with an electron beam include halogenated organic compounds such as 1,1-bis[p-chlorophenyl]-2,2,2-trichloroethane, 1,1-bis[p-methoxyphenyl]-2,2,2-trichloroethane, 1,1-bis[p-chlorophenyl]-2,2-dichloroethane, and 2-chloro-6-(trichloromethyl)pyridine; onium salts such as triphenylsulfonium salts and diphenyliodonium salts; and sulfonic acid esters such as nitrobenzyl tosylate and dinitrobenzyl tosylate.

[0071] The exposure light for the photoresist is actinic radiation such as near ultraviolet light, far ultraviolet light, or extreme ultraviolet light (e.g., EUV, wavelength 13.5 nm), and light with wavelengths of, for example, 248 nm (KrF laser light), 193 nm (ArF laser light), 172 nm, etc. For the light irradiation, any method can be used without particular limitation as long as it can generate acid from the photoacid generator in the resist film, and the exposure light amount is 1 to 5000 mJ / cm. 2 , or 10 to 5000 mJ / cm 2 , or 10 to 1000 mJ / cm 2 by.

[0072] The electron beam resist can be irradiated with an electron beam using, for example, an electron beam irradiation device.

[0073] As the developer for the resist film having the resist underlayer film formed using the resist underlayer film forming composition for lithography of the present invention, aqueous solutions of alkalis such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and cyclic amines such as pyrrole and piperidine can be used. Furthermore, an appropriate amount of alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants can be added to the aqueous solutions of the above alkalis. Among these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline.

[0074] In addition, an organic solvent can be used as the developer. For example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, propylene glycol monoethyl ether acetate, 2-ethoxybutyl ... dibutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, charcoal Examples of the alkyl esters include ethyl acetate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate.Furthermore, a surfactant may be added to these developers. The development conditions are appropriately selected from a temperature of 5 to 50° C. and a time of 10 to 600 seconds.

[0075] In the present invention, a semiconductor device can be manufactured through a process of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film-forming composition, forming a resist film thereon, subsequently forming a resist pattern by irradiating the resist underlayer film with light or an electron beam and developing it, etching the resist underlayer film with the resist pattern, and processing a semiconductor substrate with the patterned resist underlayer film.

[0076] In the future, as resist patterns become finer, problems such as resolution problems and the resist pattern collapsing after development will arise, and there will be a demand for thinner resists. It is difficult to obtain a resist pattern film thickness sufficient for the above purpose, and a process has become necessary in which not only the resist pattern but also the resist underlayer film formed between the resist film and the semiconductor substrate to be processed functions as a mask during substrate processing. As resist underlayer films for such processes, unlike conventional high etch rate resist underlayer films, resist underlayer films for lithography having a selectivity of dry etching rate close to that of resist films, resist underlayer films for lithography having a selectivity of dry etching rate smaller than that of resist films, and resist underlayer films for lithography having a selectivity of dry etching rate smaller than that of semiconductor substrates are required. In addition, such resist underlayer films can be provided with antireflection properties, and can also have the functions of conventional antireflection films.

[0077] On the other hand, in order to obtain a fine resist pattern, a process has begun to be used in which the resist pattern and the resist underlayer film are narrower than the pattern width at the time of resist development during dry etching of the resist underlayer film. As a resist underlayer film for such a process, unlike conventional high etch rate antireflective films, a resist underlayer film having a selectivity ratio of dry etching rate close to that of the resist film is required. In addition, such a resist underlayer film can be provided with antireflective properties, and can also have the functions of conventional antireflective films.

[0078] In the present invention, after forming the resist underlayer film of the present invention on a substrate, a resist can be applied directly onto the resist underlayer film, or after forming one or several layers of a coating material on the resist underlayer film as necessary. This narrows the pattern width of the resist film, and even if the resist film is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas.

[0079] That is, a semiconductor device can be manufactured through the steps of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition, forming thereon a hard mask using a coating material containing a silicon component or the like or a hard mask by vapor deposition (e.g., silicon oxynitride), forming a resist film on top of that, forming a resist pattern by irradiation with light or an electron beam and development, etching the hard mask using the resist pattern with a halogen-based gas, etching the resist underlayer film using the patterned hard mask with an oxygen-based gas or a hydrogen-based gas, and processing the semiconductor substrate with a halogen-based gas using the patterned resist underlayer film.

[0080] In terms of its effect as an antireflective film, the resist underlayer film-forming composition for lithography of the present invention has a light-absorbing moiety incorporated into the skeleton, so that no diffusion occurs into the photoresist during drying by heating, and the light-absorbing moiety has sufficiently large light-absorbing performance, so that the composition has a high antireflective effect.

[0081] The resist underlayer film forming composition for lithography of the present invention has high thermal stability, can prevent contamination of the upper layer film by decomposition products during baking, and can provide a large temperature margin for the baking step.

[0082] Furthermore, the resist underlayer film forming composition for lithography of the present invention can be used as a film having a function of preventing light reflection, depending on process conditions, and further a function of preventing interaction between a substrate and a photoresist, or a function of preventing adverse effects on a substrate of materials used in a photoresist or substances generated during exposure of the photoresist. EXAMPLES

[0083] (Synthesis Example 1) In a two-neck flask, 6.84 g of diphenylamine (Kanto Chemical Co., Ltd.) and 3-hydroxy 7.49g of diphenylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.36g of ethylhexylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 25.0g of propylene glycol monomethyl ether acetate, and 0.31g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was then heated to 120°C and refluxed and stirred for about 5 hours. After the reaction was completed, the mixture was diluted with 20g of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), and the polymer solution was dropped into a mixed solvent of methanol (manufactured by Kanto Chemical Co., Ltd.), ultrapure water, and 30% aqueous ammonia (manufactured by Kanto Chemical Co., Ltd.) to cause reprecipitation. The precipitate obtained was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. Then, 23.8g of compound 13 resin was obtained. The obtained polymer corresponded to formula (C-1). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 10,200.

[0084] [ka]

[0085] (Synthesis Example 2) 10.00 g of an epoxy group-containing benzene condensed ring compound (product name: EPICLON HP-4700, epoxy value: 165 g / eq., manufactured by DIC Corporation, formula (aa-1)), 4.37 g of acrylic acid, 0.56 g of ethyltriphenylphosphonium bromide, and 0.03 g of hydroquinone were added to 34.91 g of propylene glycol monomethyl ether, and the mixture was heated and stirred at 100° C. for 21 hours under a nitrogen atmosphere. 15 g of a cation exchange resin (product name: Dowex (registered trademark) 550A, manufactured by Muromachi Technos Co., Ltd.) and 15 g of an anion exchange resin (product name: Amberlite (registered trademark) 15JWET, manufactured by Organo Corporation) were added to the resulting solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of compound (E) was obtained. The obtained compound (B) corresponds to the formula (b-1), and had a weight average molecular weight Mw of 1,400 as measured by GPC in terms of polystyrene.

[0086] (Synthesis Example 3) 14.00 g of an epoxy group-containing benzene condensed ring compound (product name: EPICLON HP-6000, epoxy value: 239 g / eq., manufactured by DIC Corporation), 4.24 g of acrylic acid, 0.54 g of ethyltriphenylphosphonium bromide, and 0.03 g of hydroquinone were added to 43.89 g of propylene glycol monomethyl ether, and the mixture was heated and stirred at 100° C. for 22 hours under a nitrogen atmosphere. 19 g of a cation exchange resin (product name: Dowex [registered trademark] 550A, manufactured by Muromachi Technos Co., Ltd.) and 19 g of an anion exchange resin (product name: Amberlite [registered trademark] 15JWET, manufactured by Organo Corporation) were added to the resulting solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution corresponding to compound (B) was obtained. The weight average molecular weight Mw of the resulting compound measured in terms of polystyrene by GPC was 800.

[0087] (Synthesis Example 4) Epoxy group-containing benzene condensed ring compound (product name: EPICLON HP-4700, epoxy value: 162 g / eq., manufactured by DIC Corporation, formula (aa-1) 9.00 g, N-(4 45.22 g of propylene glycol monomethyl ether was added to 9.84 g of (hydroxyphenyl) methacrylamide, 1.04 g of ethyl triphenylphosphonium bromide, and 0.02 g of hydroquinone, and the mixture was heated and stirred at 100° C. for 25 hours under a nitrogen atmosphere. 20 g of cation exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Techno Co., Ltd.) and 20 g of anion exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the obtained solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a compound (A) solution was obtained. The obtained compound (B) corresponds to the formula (b-11), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 1900. No residual epoxy groups were present.

[0088] (Synthesis Example 5) 44.77 g of propylene glycol monomethyl ether was added to 14.00 g of an epoxy group-containing benzene condensed ring compound (product name: RE-810NM, epoxy value: 221 g / eq., Nippon Kayaku Co., Ltd., formula (aa-5)), 4.56 g of acrylic acid, 0.59 g of ethyltriphenylphosphonium bromide, and 0.03 g of hydroquinone, and the mixture was heated and stirred at 100°C for 22 hours under a nitrogen atmosphere. The resulting solution was added to a cation exchange resin (product name: Dowex The mixture was added with 19 g of ion exchange resin (product name: Amberlite (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 19 g of anion exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Co., Ltd.), and subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of compound (B) was obtained. The obtained compound (B) corresponds to formula (b-17), and the weight average molecular weight Mw measured in terms of polystyrene by GPC was 900. No residual epoxy groups were present.

[0089] Example 1 2 g of EPPN-201 (manufactured by Nippon Kayaku Co., Ltd., formula (a-6)) was dissolved in 18 g of cycloxanone, and then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0090] Example 2 2 g of EPPN-501H (manufactured by Nippon Kayaku Co., Ltd., formula (a-9)) was dissolved in 18 g of propylene glycol monomethyl ether acetate. The solution was then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0091] Example 3 2 g of 1032H60 (manufactured by Mitsubishi Chemical Corporation, formula (a-12)) was dissolved in 18 g of propylene glycol monomethyl ether acetate, and then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0092] Example 4 2 g of 157S70 (manufactured by Mitsubishi Chemical Corporation, formula (a-11)) was dissolved in 18 g of propylene glycol monomethyl ether acetate, and then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0093] Example 5 2 g of HP-4700 (DIC Corporation, formula (aa-1)) was dissolved in 18 g of propylene glycol monomethyl ether acetate, and then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0094] Example 6 2 g of HP-7200HHH (DIC Corporation, formula (a-2)) was dissolved in 18 g of propylene glycol monomethyl ether acetate, and then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0095] Example 7 2 g of NC-3000-L (manufactured by Nippon Kayaku Co., Ltd., formula (a-4)) was dissolved in 18 g of propylene glycol monomethyl ether acetate. The solution was then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0096] Example 8 2 g of NC3500 (manufactured by Nippon Kayaku Co., Ltd., formula (a-8)) was dissolved in 18 g of propylene glycol monomethyl ether acetate, and then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0097] Example 9 2 g of NC-6000 (manufactured by Nippon Kayaku Co., Ltd., formula (aa-4)) was dissolved in 18 g of propylene glycol monomethyl ether acetate, and then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0098] Example 10 2 g of NC-7300L (manufactured by Nippon Kayaku Co., Ltd., formula (a-7)) was dissolved in 18 g of propylene glycol monomethyl ether acetate. The solution was then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0099] Example 11 2 g of 1031S (manufactured by Mitsubishi Chemical Corporation, formula (aa-8)) was dissolved in 18 g of propylene glycol monomethyl ether acetate, and then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0100] Example 12 2 g of NC-7000L (manufactured by Nippon Kayaku Co., Ltd., formula (a-5)) was dissolved in 18 g of propylene glycol monomethyl ether acetate. The solution was then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0101] (Example 13) 3.72 g of propylene glycol monomethyl ether acetate containing 22.82 mass% of HP-4700 (manufactured by DIC Corporation, formula (aa-1)), 2.14 g of propylene glycol monomethyl ether containing 2 mass% of TPS-TF (manufactured by Toyo Gosei Co., Ltd., photoacid generator), 0.08 g of propylene glycol monomethyl ether acetate solution containing 1 weight % of a surfactant (manufactured by DIC Corporation, product name: Megafac [product name] R-40, fluorosurfactant), 3.38 g of propylene glycol monomethyl ether acetate, 0.63 g of propylene glycol monomethyl ether was mixed in. Thereafter, the mixture was filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0102] Example 14 3.81 g of propylene glycol monomethyl ether acetate containing 22.45 mass% of product name NC-7300-L (manufactured by Nippon Kayaku Co., Ltd., formula (a-7)), 2.14 g of propylene glycol monomethyl ether containing 2 mass% of TPS-TF (manufactured by Toyo Gosei Co., Ltd., photoacid generator), 0.08 g of propylene glycol monomethyl ether acetate solution containing 1 wt% of surfactant (manufactured by DIC Corporation, product name: Megafac [product name] R-40, fluorine-based surfactant), 3.33 g of propylene glycol monomethyl ether acetate, and 0.63 g of propylene glycol monomethyl ether were mixed. Then, the mixture was filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0103] Example 15 0.59 g of propylene glycol monomethyl ether acetate containing 29.78 mass% of product name 1031S (manufactured by Mitsubishi Chemical Corporation, formula (aa-8)), 2.10 g of the resin solution obtained in Synthesis Example 2 (solid content is 25.02 mass%), 0.03 g of a propylene glycol monomethyl ether acetate solution containing 1 wt% of a surfactant (manufactured by DIC Corporation, product name: Megafac [product name] R-40, fluorine-based surfactant), 3.96 g of propylene glycol monomethyl ether acetate, and 0.32 g of propylene glycol monomethyl ether were mixed. Thereafter, the mixture was filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0104] (Example 16) 1.17 g of propylene glycol monomethyl ether acetate containing 29.78 mass% of product name 1031S (manufactured by Mitsubishi Chemical Corporation, formula (aa-8)), 1.40 g of the resin solution obtained in Synthesis Example 2 (solid content is 25.02 mass%), 0.07 g of a propylene glycol monomethyl ether acetate solution containing 1 wt% of a surfactant (manufactured by DIC Corporation, product name: Megafac [product name] R-40, fluorine-based surfactant), 3.52 g of propylene glycol monomethyl ether acetate, and 0.84 g of propylene glycol monomethyl ether were mixed. Then, the mixture was filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0105] (Example 17) 2.34 g of propylene glycol monomethyl ether acetate containing 29.83 mass% of product name 157S70 (manufactured by Mitsubishi Chemical Corporation, formula (a-11)), 0.93 g of the resin solution obtained in Synthesis Example 2 (solid content is 25.02 mass%), 0.14 g of a propylene glycol monomethyl ether acetate solution containing 1 wt% of a surfactant (manufactured by DIC Corporation, product name: Megafac [product name] R-40, fluorine-based surfactant), 2.63 g of propylene glycol monomethyl ether acetate, and 1.19 g of propylene glycol monomethyl ether were mixed. Then, the mixture was filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0106] (Example 18) 2.35 g of propylene glycol monomethyl ether acetate containing 29.78 mass% of product name 1031S (manufactured by Mitsubishi Chemical Corporation, formula (aa-8)), 0.93 g of the resin solution obtained in Synthesis Example 2 (solid content 25.02 mass%), and propylene glycol containing 1 wt% of a surfactant (manufactured by DIC Corporation, product name: Megafac [product name] R-40, a fluorosurfactant) were mixed. 0.14 g of a solution of propylene glycol monomethyl ether acetate, 2.62 g of propylene glycol monomethyl ether acetate, and 1.20 g of propylene glycol monomethyl ether were mixed together, and then filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0107] (Example 19) To 2.94 g of the resin solution (formula b-11) obtained in Synthesis Example 4 (solid content: 23.75% by mass) and 3.07 g of the resin solution (formula b-17) obtained in Synthesis Example 5 (solid content: 22.81% by mass), 0.001 g of a surfactant (manufactured by DIC Corporation, product name: Megafac [product name] R-40, fluorine-based surfactant), 8.41 g of propylene glycol monomethyl ether, and 5.58 g of propylene glycol monomethyl ether acetate were added to prepare a solution of an organic underlayer film-forming composition for covering a stepped substrate.

[0108] Comparative Example 1 The resin obtained in Synthesis Example 1 was dissolved in propylene glycol monomethyl ether acetate, and then ion-exchanged to obtain a resin solution (solid content 30.1% by mass). 0.04 g of propylene glycol monomethyl ether acetate containing 1% by mass of surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.32 g of propylene glycol monomethyl ether containing 2% by mass of pyridinium p-hydroxybenzenesulfonate, 3.48 g of propylene glycol monomethyl ether acetate, and 1.62 g of propylene glycol monomethyl ether were added to 1.41 g of this resin solution, and the mixture was filtered through a polytetrafluoroethylene microfilter having a diameter of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0109] Comparative Example 2 To 4.19 g of the resin solution obtained in Synthesis Example 2 (solid content: 25.02 mass%), 0.001 g of a surfactant (manufactured by DIC Corporation, product name: Megafac [product name] R-40, fluorine-based surfactant), 6.62 g of propylene glycol monomethyl ether, and 4.19 g of propylene glycol monomethyl ether acetate were added, and the mixture was filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0110] Comparative Example 3 To 8.13 g of the resin solution (solid content: 25.80 mass%) obtained in Synthesis Example 3, 0.002 g of a surfactant (manufactured by DIC Corporation, product name: Megafac [product name] R-40, fluorine-based surfactant), 13.50 g of propylene glycol monomethyl ether, and 8.37 g of propylene glycol monomethyl ether acetate were added, and the mixture was filtered through a polytetrafluoroethylene microfilter having an aperture of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0111] (Solvent resistance test) The resist underlayer film forming compositions prepared in Comparative Examples 2 to 3 and Examples 1 to 19 were each applied onto a silicon wafer using a spin coater. The composition was heated on a hot plate at 100°C to 240°C for 60 seconds or 90 seconds to form a resist underlayer film having a thickness of 150 nm. The solvent resistance was evaluated by immersing the baked coating film in a 7:3 mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate for 1 minute, spin drying, and baking at 100°C for 60 seconds, and measuring the film thickness to calculate the remaining film ratio (Table 1).

[0112] [Table 1]

[0113] From the above results, it was confirmed that solvent resistance cannot be obtained by simply applying heat. Therefore, sufficient fluidity and flattening properties can be ensured when heat is applied after pattern coating.

[0114] (Photocuring test) The resist underlayer film forming compositions prepared in Comparative Examples 2 to 3 and Examples 1 to 19 were each applied onto a silicon wafer using a spin coater. The wafer was heated on a hot plate at 100°C to 240°C for 60 seconds or 90 seconds to form a resist underlayer film having a thickness of 150 nm. This resist underlayer film was then irradiated with 500 mJ / cm2 of ultraviolet light using a UV irradiation unit (wavelength 172 nm) manufactured by Ushio Inc. 2 The coating film was irradiated with ultraviolet light for 10 min to confirm its solvent resistance under light irradiation (UV irradiation). The solvent resistance was evaluated by immersing the coating film after UV irradiation in a 7:3 mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate for 1 minute, spin drying, and baking at 100°C for 1 minute, and measuring the film thickness. The film shrinkage rate before and after light irradiation was also calculated at the same time (Table 2). Note that NG is a sample where film roughness occurred after light irradiation, making it impossible to measure the film thickness accurately.

[0115] [Table 2]

[0116] From the above results, it was confirmed that the materials that could not be cured by heat alone could be cured by light irradiation. It was also confirmed that in Examples 13 and 14, the materials could not be cured by baking alone or by light irradiation alone.

[0117] In order to improve the photocurability of Examples 5, 7, 10, and 12, for which sufficient photocurability could not be confirmed by the above method, the photocurability was confirmed by increasing the amount of light irradiated during light irradiation and by adding heat during light irradiation using a similar experimental method (Table 3). In Examples 5, 7, 10, and 12, the amount of light irradiated and the temperature during light irradiation of those compositions were changed.

[0118] [Table 3]

[0119] From the above results, it is possible to increase the sensitivity of a material that has low sensitivity to light by increasing the amount of light irradiated during light irradiation or by applying heat during light irradiation, thereby enabling the material to exhibit photocurability.

[0120] Examples 13 and 14 were irradiated with light at 172 nm and then baked at 120° C. for 90 seconds to confirm their curability.

[0121] [Table 4]

[0122] From the above results, it can be seen that for materials with low sensitivity to light, a photoacid generator is used to generate acid, and then low-temperature baking can be performed to compensate for the hardening of materials that are not sufficiently hardened by light hardening.

[0123] (Evaluation of flattening and embedding properties on uneven substrates-1) To evaluate the planarization ability on a stepped substrate, a comparison was made between the coating thickness of a dense pattern area (DENSE) with a trench width of 50 nm and a pitch of 100 nm and an open area (OPEN) where no pattern was formed on a 200 nm-thick SiO2 substrate. In addition, the embedding ability was evaluated by observing the DENSE area. The resist underlayer film-forming compositions prepared in Comparative Examples 1 to 3 and Examples 2 to 18 were applied onto the above substrate, and then heated at 100°C for 60 seconds or The resist underlayer film was baked at 240°C for 90 seconds to form a resist underlayer film of about 150 nm. This resist underlayer film was irradiated with 500 mJ / cm2 of ultraviolet light using a UV irradiation unit (wavelength 172 nm) manufactured by Ushio Inc. 2 or 1000mJ / cm 2 The substrate was irradiated with ultraviolet light for 100 s, and heat was applied during or after the irradiation as necessary. The planarization of the substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the planarization was evaluated by measuring the difference in film thickness between the dense area (patterned area) and the open area (no patterned area) of the stepped substrate (the difference in coating step between the dense area and the open area, called the bias). Here, planarization means that the difference in film thickness (iso-dense bias) of the coating material present on the upper part of the area where the pattern exists (dense area (patterned area)) and the area where the pattern does not exist (open area (no patterned area)) is small (Table 5).

[0124] [Table 5]

[0125] (Evaluation of flattening and embedding properties on uneven substrates-2) To evaluate the planarization ability on a stepped substrate, a comparison was made between the coating thickness of a dense pattern area (DENSE) with a trench width of 50 nm and a pitch of 100 nm and an open area (OPEN) where no pattern was formed on a 200 nm thick SiO2 substrate. In addition, the embedding ability was evaluated by observing the DENSE area. The resist underlayer film forming composition prepared in Example 19 was applied onto the above substrate, and then baked at 170°C for 60 seconds or at 240°C for 90 seconds to form a resist underlayer film of about 150 nm. This resist underlayer film was exposed to 500 mJ / cm2 of UV irradiation using a UV irradiation unit (wavelength 172 nm) manufactured by Ushio Inc. 2 or 1000mJ / cm 2 The planarization of the substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the planarization was evaluated by measuring the film thickness difference between the dense area (patterned area) and the open area (no patterned area) of the stepped substrate (the coating step between the dense area and the open area, which is called the bias). Here, planarization means that the difference in thickness (iso-dense bias) of the coating material present on the upper portion between the portion where the pattern exists (dense area (pattern portion)) and the portion where the pattern does not exist (open area (no pattern portion)) is small (Table 5-1).

[0126] [Table 6]

[0127] (Evaluation of flattening and filling properties when applying upper layer film-1) To evaluate the planarization property when applying the upper layer film, the coating film thickness was compared between an 800 nm trench area (TRENCH) and an open area (OPEN) where no pattern was formed, using a 200 nm thick SiO2 substrate. In addition, embedding property was confirmed in a dense pattern area (DENSE) with a trench width of 50 nm and a pitch of 100 nm. The resist underlayer film forming compositions prepared in Comparative Examples 2 to 3 and Examples 2, 3, 4, 8, 11, and 13 to 18 were applied onto the above substrate, and then baked at 240°C for 90 seconds to form a resist underlayer film of about 150 nm. This resist underlayer film was exposed to 500 mJ / cm 2 of UV irradiation using an ultraviolet irradiation device using a UV irradiation unit (wavelength 172 nm) manufactured by Ushio Inc. 2 The substrate was then irradiated with ultraviolet light. A coating type silicon material was then spin-coated on the top layer and baked at 215°C for 60 seconds to form an inorganic film of about 30 nm. The planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the planarization was evaluated by measuring the film thickness difference between the trench area (patterned portion) and the open area (no patterned portion) of the stepped substrate (the coating step between the trench area and the open area, which is called the bias). Here, the planarization means that the film thickness difference (Iso-dense bias: coating step nm) of the coating material present on the upper portion between the portion where the pattern exists (trench area (patterned portion)) and the portion where the pattern does not exist (open area (no patterned portion)) is small (Table 6). The embeddability was evaluated as (◯) when the embedding was successful without voids, and as (×) when voids were generated.

[0128] [Table 7]

[0129] (Evaluation of flattening and filling properties when applying upper layer film-2) To evaluate the planarization when applying the top layer film, a comparison was made between the coating thickness of an 800 nm trench area (TRENCH) and an open area (OPEN) where no pattern was formed on a 200 nm thick SiO2 substrate. In addition, the embedding property was confirmed in a dense pattern area (DENSE) with a trench width of 50 nm and a pitch of 100 nm. The resist underlayer film forming compositions prepared in Comparative Example 4 and Example 19 were applied onto the above substrate, and then baked at 240°C for 90 seconds to form a resist underlayer film of about 150 nm. This resist underlayer film was heated at the following light irradiation temperature and irradiated with 500 mJ / cm using an ultraviolet irradiation device using a UV irradiation unit (wavelength 172 nm) manufactured by Ushio Inc. 2 The substrate was then irradiated with ultraviolet light for 1000 s. A coating type silicon material was then spin-coated on the top layer and baked at 215°C for 60 seconds to form an inorganic film of about 30 nm. The planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the planarization was evaluated by measuring the film thickness difference between the trench area (patterned portion) and the open area (no patterned portion) of the stepped substrate (the coating step between the trench area and the open area, which is called the bias). Here, the planarization means that the film thickness difference (Iso-dense bias: coating step nm) of the coating material present on the upper portion between the portion where the pattern exists (trench area (patterned portion)) and the portion where the pattern does not exist (open area (no patterned portion)) is small (Table 6-1). The embeddability was evaluated as (◯) when the embedding was successful without voids, and as (×) when voids were generated. In Comparative Example 4, Comparative Example 5, and Example 19-1, the composition used in Example 19 was irradiated with light at different temperatures.

[0130] [Table 8]

[0131] The coating step difference (nm) between the trench area and the open area, and the coating step difference (nm) between the dense area and the open area is preferably less than 50 nm, or preferably 40 nm or less, or 30 nm or less.

[0132] When heating is performed during or after light irradiation, this applies to heating during light irradiation and heating after light irradiation (for example, when a silicon-based inorganic film is overcoated on a resist underlayer film), but it is preferable that the heating is performed within the range throughout the steps during or after light irradiation. [Industrial Applicability]

[0133] The composition can be used as a coating composition for coating uneven substrates to form a coating film on a substrate that has high pattern filling properties, is capable of forming a coating film without causing outgassing or thermal shrinkage, and has planarizing properties.

Claims

1. 1. A stepped substrate comprising a stepped substrate coating composition, The step-fixed substrate coating composition includes a base material and a solvent, The base agent contains the following compound (A) or a mixture of the following compound (A) and the following compound (B), and compound (A) is represented by the following formula (A-1): 【Chemistry 1】 (wherein n is an integer of 1 or 2, the dashed line indicates a bond to an aromatic ring, and the aromatic ring is an aromatic ring constituting a polymer skeleton or an aromatic ring constituting a monomer), the aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring, the polymer containing the aromatic ring is a polymer having a hydroxyl group of a polymer containing a hydroxyaryl novolak structure substituted with an organic group represented by formula (A-1), and the monomer containing the aromatic ring is a monomer having a hydroxyl group of an aromatic ring substituted with an organic group represented by formula (A-1), The compound (A) is a polymer represented by the following formulae (a-1) to (a-5), a polymer represented by the following formulae (a-7) to (a-12), or a compound represented by the following formulae (aa-1) to (aa-18), 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 Compound (B) is a compound containing at least one partial structure selected from the group consisting of partial structures represented by the following formulas (B-1) to (B-5), or containing a partial structure consisting of a combination of a partial structure represented by formula (B-6) and a partial structure represented by formula (B-8), 【Chemistry 10】 (In the formula, R １ , R １ａ , R ３ , R ５ , R ５ａ , and R ６ａ are each independently the number of carbon atoms R represents a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, a nitrogen atom, an amide group, an amino group, or a group consisting of a combination thereof; ２ , R ４ , and R ６ each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms, an oxygen atom, a carbonyl group, an amide group, an amino group, or a group consisting of a combination thereof; R ２ , R ４ , R ６ represents a monovalent group, R １ , R １ａ , R ３ , R ５ａ , and R ６ａ represents a divalent group, R ５ represents a trivalent group, n represents the number of repeating units from 1 to 10, and the dotted lines represent chemical bonds with adjacent atoms. When the compound (A) or the base material containing the compound (A) and the compound (B) is used, the step substrate covering composition is cured by light irradiation or cured by heating at 30° C. to 300° C. during or after light irradiation, A stepped substrate, wherein the content of the main component in the solid content of the composition is 95% by mass to 100% by mass.

2. 2. The stepped substrate according to claim 1, wherein when the base material is a mixture of the compound (A) and the compound (B), the molar ratio of epoxy groups to vinyl groups is 100:1 to 1:

100.

3. The stepped substrate according to claim 1 or 2, further comprising an acid generator.

4. The stepped substrate according to claim 1 , further comprising a surfactant.

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