Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F138/00—Homopolymers of compounds having one or more carbon-to-carbon triple bonds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/38—Treatment before imagewise removal, e.g. prebaking
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
  • H10P14/6326—Deposition processes
  • H10P14/6342—Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/66—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials
  • H10P14/668—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/68—Organic materials, e.g. photoresists
  • H10P14/683—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
  • H10P50/286—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials
  • H10P50/287—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials by chemical means
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes
  • H10P76/2043—Photolithographic processes using an anti-reflective coating
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/73—Etching of wafers, substrates or parts of devices using masks for insulating materials

Definitions

• the present invention relates to a stepped substrate coating composition for forming a flattening film by being cured by heating on a substrate having a step, and a method for manufacturing a flattened laminated substrate using the stepped substrate coating composition.
• 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 containing a polymer having a radically polymerizable ethylenically unsaturated bond and a photoradical polymerization initiator.
• the underlayer film forming composition is disclosed (see Patent Document 1).
• a resist underlayer film forming composition containing a silicon-based compound having a cationically polymerizable reactive group such as an epoxy group and a vinyl group, and a photocationic polymerization initiator and a photoradical polymerization initiator is disclosed (Patent).
• Patent Document 3 a method for manufacturing a semiconductor device using a resist underlayer film containing a polymer having a crosslinkable functional group (for example, a hydroxy group) in a side chain, a crosslinking agent and a photoacid generator is disclosed (see Patent Document 3). .. Further, a photocrosslinking resist underlayer film into which a propargyl group has been introduced is disclosed. (See Patent Document 4)
• the conventional stepped substrate coating composition is heated and then further irradiated with light to form a flattening film, so that the manufacturing process is complicated and time-consuming. Further, in the case of light irradiation, the exposure wavelength and the exposure amount must be adjusted according to the type and properties of the stepped substrate coating composition, so that the production efficiency of the flattening film having the light irradiation step requiring adjustment work is poor. There was a problem that the production cost was high.
• the subject of the present invention is a stepped substrate coating composition for forming a flattening film on a substrate, which can form a coating film having a high filling property in an open area and a pattern area by a heating-only process. Is to provide.
• the present invention is a stepped substrate coating composition containing a main agent compound (A), a cross-linking agent, and a solvent.
• the compound (A) has the following formula (A-1). (In the formula, the broken line indicates the bond with the aromatic ring, the aromatic ring is an aromatic ring constituting a polymer skeleton or an aromatic ring constituting a monomer, and n indicates an integer of 1 to 4. .)
• Stepped substrate coating composition which is a compound containing a partial structure represented by As a second aspect, the stepped substrate coating composition according to the first aspect, wherein the aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring.
• the polymer containing the aromatic ring is a polymer containing a hydroxyaryl novolak structure, and the hydroxyl group thereof is substituted with a partial structure of the formula (A-1).
• the stepped substrate coating composition according to the second aspect As a fourth aspect, the monomer containing the aromatic ring is a monomer in which the hydroxyl group of the aromatic ring is substituted with the partial structure of the formula (A-1), and the stepped substrate coating according to the first aspect or the second aspect.
• Composition As a fifth aspect, the stepped substrate coating composition according to any one of the first aspect to the fourth aspect, further comprising an acid generator.
• the stepped substrate coating composition according to any one of the first aspect to the fifth aspect further comprising a surfactant.
• a method for manufacturing a coated substrate which includes a heating step (ii).
• the method for manufacturing a coated substrate according to the seventh aspect which is heated at a temperature of 100 ° C. to 500 ° C. in the above step (ii).
• the substrate having the step has an open area (non-pattern area) and a pattern area composed of DENCE (dense) and ISO (coarse), and the aspect ratio of the pattern is 0.1 to 100.
• the method for manufacturing a coated substrate according to the seventh aspect or the eighth aspect As a tenth viewpoint, the substrate having the step has an open area (non-pattern area) and a pattern area composed of DENCE (dense) and ISO (coarse), and Bias (coating step) between the open area and the pattern area.
• this is irradiated with light or an electron beam, or heated during or after irradiation with light or an electron beam, and a step of forming a resist pattern by subsequent development, a step of etching the underlayer film with the formed resist pattern, and a step of etching the underlayer film.
• a method for manufacturing a semiconductor device which includes a step of processing a semiconductor substrate with a patterned underlayer film.
• the method for manufacturing a semiconductor device according to the eleventh aspect which comprises the step (ii) of heating the composition applied in i).
• the method for manufacturing a semiconductor device according to the twelfth aspect wherein the semiconductor device is heated at a temperature of 100 ° C. to 500 ° C. in the above step (ii).
• the substrate having the step has an open area (non-pattern area) and a pattern area composed of DENCE (dense) and ISO (coarse), and the aspect ratio of the pattern is 0.1 to 100.
• the substrate having the step has an open area (non-pattern area) and a pattern area composed of DENCE (dense) and ISO (coarse), and the underlayer film obtained from the step substrate coating composition.
• the method for manufacturing a semiconductor device according to any one of the eleventh aspect to the fourteenth aspect, wherein the semiconductor device has a bias (coating step) between an open area of 1 nm to 50 nm and a pattern area.
• a step of forming a resist film on the resist film then a step of irradiating the resist film with light or an electron beam, or a step of heating the resist film during or after irradiation with light or an electron beam, and then developing the resist pattern to form a resist pattern.
• a method for manufacturing a semiconductor device which includes a step of etching a hard mask with a pattern, a step of etching the underlayer with a patterned hard mask, and a step of processing a semiconductor substrate with the patterned underlayer.
• the method for manufacturing a semiconductor device according to the sixteenth aspect which comprises the step (ii) of heating the composition applied in i).
• the method for manufacturing a semiconductor device according to the seventeenth aspect wherein the semiconductor device is heated at a temperature of 100 ° C. to 500 ° C. in the above step (ii).
• the substrate having the step has an open area (non-pattern area) and a pattern area composed of DENCE (dense) and ISO (coarse), and the aspect ratio of the pattern is 0.1 to 100.
• the lower layer film obtained from the stepped substrate coating composition has an open area of 1 nm to 50 nm and a Bias (coating step) between the pattern area and the pattern area.
• the stepped substrate coating composition of the present invention can be cured only by heating, the process for producing the resist underlayer film is simple, and the production efficiency of the resist underlayer film and the coated substrate can be improved. Further, in the stepped substrate coating composition of the present invention, a flat film is formed on the stepped substrate regardless of the open area (non-pattern area) on the stepped substrate or the pattern area composed of DENCE (dense) and ISO (coarse). Can be formed. That is, the stepped substrate coating composition of the present invention can provide an excellent flattening film in which good filling performance for open areas and pattern areas and flattening performance after filling are simultaneously satisfied.
• the present invention is a stepped substrate coating composition containing a main agent compound (A), a cross-linking agent, and a solvent, wherein the compound (A) has the following formula (A-1).
• a stepped substrate coating composition which is a compound containing a partial structure represented by.
• n represents an integer of 1 to 4
• a broken line indicates a bond with an aromatic ring
• the aromatic ring is an aromatic ring constituting a polymer skeleton or an aromatic constituting a monomer. It is a tribal ring.
• the aromatic ring can be a benzene ring, a naphthalene ring, or an anthracene ring.
• the polymer containing an aromatic ring can be a polymer containing a hydroxyaryl novolak structure, and the hydroxyl group thereof can be a polymer substituted with a partial structure of the formula (A-1).
• aryl groups aromatic groups derived from benzene and naphthalene can be used.
• the polymers of the formulas (a-1) to (a-13) are synthesized by, for example, a condensation reaction of the epoxy group of the precursor polymer with propiolic acid according to a known method, although the production method is not limited.
• the weight average molecular weight of the polymer is 600 to 1,000,000, 600 to 200,000, or 1500 to 15,000.
• the monomer containing an aromatic ring can be a monomer in which the glycidyl ether group of the aromatic ring is substituted with the partial structure of the formula (A-1).
• the epoxy group of the precursor monomer is replaced by condensation with propiolic acid. It is synthesized.
• the monomer containing the aromatic ring can be used in the range of molecular weight of 200 to 10000, 200 to 2000, or 200 to 1000.
• the polymer or monomer containing the aromatic ring can also be mixed with any other aromatic carboxylic acid when reacted with propiolic acid.
• aromatic carboxylic acid include benzoic acid, naphthalenecarboxylic acid, anthracenecarboxylic acid, pyrenecarboxylic acid and the like, and these carboxylic acids have one or more hydroxyl groups, aldehyde groups, methoxymethyl groups and aminos on the benzene ring.
• the group may be substituted with a methylol group, an allyl group, an ethynyl group, or a propargyl group.
• the ratio of propiolic acid to aromatic carboxylic acid is about 0.1 to 50 mol, preferably about 0.1 to 10 mol, preferably 0.1 to 2 mol with respect to 1 mol of propiolic acid. More preferred.
• Examples of polymers or monomers obtained when propiolic acid and aromatic carboxylic acid are mixed and reacted include the following.
• R in the structural formula is an aromatic ring or HCC-group derived from the aromatic carboxylic acid, and at least one or more is an HCC- group.
• the stepped substrate coating composition of the present invention can contain a cross-linking agent.
• the cross-linking agent include melamine-based, substituted urea-based, and polymers thereof.
• it is a cross-linking agent having at least two cross-linking substituents, such as methoxymethylated glycol uryl (eg, tetramethoxymethyl glycol uryl), butoxymethylated glycol uryl, methoxymethylated melamine, butoxymethylated melamine, methoxy.
• a cross-linking agent having high heat resistance can be used.
• a compound containing a cross-linking substituent having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule can be preferably used.
• Examples of this compound include a compound having a partial structure of the following formula (4) and a polymer or oligomer having a repeating unit of the following formula (5).
• the above R 11 , R 12 , R 13 and R 14 are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and these alkyl groups can use the above-mentioned examples.
• the above compounds can be obtained as products of Asahi Organic Materials Industry Co., Ltd. and Honshu Chemical Industry Co., Ltd.
• the compound of the formula (4-23) is Honshu Chemical Industry Co., Ltd., trade name TMOM-BP
• the compound of the formula (4-24) is Asahi Organic Material Industry Co., Ltd., trade name TM. -Available as BIP-A.
• the amount of the cross-linking agent added varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001% by mass or more and 0.01 with respect to the total solid content.
• Mass% or more 0.05 mass% or more, 0.5 mass% or more, or 1.0 mass% or more, 80 mass% or less, 50 mass% or less, 40 mass% or less, 20 mass% or less, or 10 It is less than mass%.
• These cross-linking agents may cause a cross-linking reaction by self-condensation, but if cross-linking substituents are present in the polymer of the present invention, they can cause a cross-linking reaction with those cross-linking substituents.
• solvent for dissolving the compound (A) in the present invention examples 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, and methyl.
• the stepped substrate coating composition of the present invention can contain an acid and / or an acid generator.
• the acid include p-toluene sulfonic acid, trifluoromethane sulfonic acid, pyridinium p-toluene sulfonic acid, pyridinium phenol sulfonic acid, salicyl acid, 5-sulfosalicylic acid, 4-phenol sulfonic acid, camphor sulfonic acid, 4-chlorobenzene sulfonic acid.
• Benzindisulfonic acid 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid and the like. Only one type of acid can be used, or two or more types can be used in combination.
• the blending amount is usually 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass with respect to the total solid content.
• the acid generator examples include a thermal acid generator.
• the thermoacid generator examples include 2,4,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, K-PURE® CXC-1612, CXC-1614, and TAG. -2172, TAG-2179, TAG-2678, TAG2689, TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 ( Sanshin Chemical Industry Co., Ltd.) Other organic sulfonic acid alkyl esters and the like can be mentioned.
• the ratio thereof is 0.01 to 10 parts by mass, 0.1 to 8 parts by mass, or 0. to 100 parts by mass with respect to 100 parts by mass of the solid content of the resist underlayer film forming composition. It is 5 to 5 parts by mass.
• the stepped substrate coating composition of the present invention can contain a surfactant.
• the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxy.
• Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Solbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.
• Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, Ftop [registered trademarks] EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics Chemicals Co., Ltd.), Megafuck [registered trademarks] F171, F173, R30, R-30N, R-40, R-40LM (manufactured by DIC Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard [registered trademark] AG710, Surfron [registered trademark] ] S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and other fluorosurfactants, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) Can be mentioned.
• Ftop EF301,
• the content ratio of the surfactant is, for example, 0.01% by mass to 5% by mass, or 0.01% by mass to 2% by mass, based on the solid content of the stepped substrate coating composition of the present invention excluding the solvent described later. %, 0.01% by mass to 0.2% by mass, or 0.01% by mass to 0.1% by mass, or 0.01% by mass to 0.09% by mass.
• a transparent substrate such as a substrate used for manufacturing a precision integrated circuit element (for example, silicon / silicon dioxide coating, glass substrate, ITO substrate, etc.)
• a film is formed by baking (heating). That is, the coated substrate is manufactured including a step (i) of applying the stepped substrate coating composition to the substrate having a step and a step (ii) of heating the composition applied in the step (i).
• the application can be performed at a rotation speed of 100 to 5000 for 10 to 180 seconds.
• the substrate has an open area (non-pattern area) and a pattern area composed of DENCE (dense) and ISO (coarse), and the aspect ratio of the pattern is 0.1 to 10 or 0.1 to 100. Can be used.
• the non-pattern area indicates a portion on the substrate without a pattern (for example, a hole or trench structure), DENCE (dense) indicates a portion where patterns are dense on the substrate, and ISO (coarse) indicates a pattern on the substrate.
• the part where the pattern is scattered is shown.
• the aspect ratio of the pattern is the ratio of the pattern depth to the width of the pattern.
• the pattern depth is usually several hundred nm (for example, about 100 to 300 nm)
• DENCE (dense) is a place where patterns of several tens of nm (for example, about 30 to 80 nm) are densely packed at intervals of about 100 nm. ..
• ISO (coarse) is a place where patterns having a pattern of several hundred nm (for example, about 200 to 1000 nm) are scattered.
• the film thickness of the stepped substrate coating film is preferably 0.01 ⁇ m to 3.0 ⁇ m.
• the heating is preferably at a temperature of 100 ° C to 500 ° C, or 200 ° C to 400 ° C. At temperatures in this range, acid is generated and a curing reaction occurs, resulting in solvent resistance.
• the Bias (coating step) between the open area and the pattern area is zero, but it is in the range of 1 nm to 50 nm or 1 nm to 25 nm. It can be flattened so as to be.
• the bias of the open area and the DENCE area is about 15 nm to 20 nm, and the bias of the open area and the ISO area is about 1 nm to 10 nm.
• the stepped substrate coating film (flattening film) obtained by the present invention is coated with a resist film on it, and the resist film is exposed and developed by lithography by lithography to form a resist pattern, and the substrate is processed according to the resist pattern. It can be carried out.
• the stepped substrate coating film (flattening film) is a resist underlayer film
• the stepped substrate coating composition is also a resist underlayer film forming composition.
• a good resist pattern can be obtained by applying a resist on the resist underlayer film, irradiating it with light or an electron beam through a predetermined mask, developing, rinsing, and drying. If necessary, heating (PEB: Post Exposure Bake) can be performed during or after irradiation with light or an electron beam. Then, the resist underlayer film of the portion where the resist film is developed and removed by the above step can be removed by dry etching to form a desired pattern on the substrate.
• PEB Post Exposure Bake
• the resist used in the present invention is a photoresist or an electron beam resist.
• Either a negative type or a positive type can be used as the photoresist applied to the upper part of the photoresist underlayer film for lithography in the present invention, and a positive type photoresist composed of a novolak resin and a 1,2-naphthoquinonediazide sulfonic acid ester and an acid are used.
• a chemically amplified photoresist consisting of a binder having a group that decomposes to increase the alkali dissolution rate and a photoacid generator, a low molecular weight compound and photoacid that decomposes with an alkali-soluble binder and acid to increase the alkali dissolution rate of the photoresist.
• It consists of a chemically amplified photoresist made of a generator, a binder having a group that decomposes with an acid to increase the alkali dissolution rate, a low molecular weight compound that decomposes with an acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator.
• a chemically amplified photoresist made of a generator, a binder having a group that decomposes with an acid to increase the alkali dissolution rate, a low molecular weight compound that decomposes with an acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator.
• an acid is generated by irradiation with a resin containing a Si—Si bond in the main chain and an aromatic ring at the end and an electron beam.
• a resin containing a Si—Si bond in the main chain and an aromatic ring at the end and an electron beam examples thereof include a composition composed of an acid generator, or a composition composed of a 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 by irradiation with an electron beam. Be done.
• the acid generated from the acid generator by electron beam irradiation reacts with the N-carboxyaminoxy group of the polymer side chain, the polymer side chain is decomposed into hydroxyl groups, and the polymer side chain shows alkali solubility and is an alkali developing solution. It dissolves in and forms a resist pattern.
• the acid generators that generate acid by irradiation with this electron beam are 1,1-bis [p-chlorophenyl] -2,2,2-trichloroethane and 1,1-bis [p-methoxyphenyl] -2,2,2.
• the exposure light of the photoresist is a chemical ray such as near ultraviolet rays, far ultraviolet rays, or extreme ultraviolet rays (for example, EUV, wavelength 13.5 nm), for example, 248 nm (KrF laser light), 193 nm (ArF laser light), 172 nm. Light of the same wavelength is used.
• EUV extreme ultraviolet rays
• any method that can generate acid from the photoacid generator in the resist film can be used without particular limitation, 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 .
• the electron beam irradiation of the electron beam resist can be performed using, for example, an electron beam irradiation device.
• Examples of the developing solution of the resist film having the resist underlayer film formed by using the stepped substrate coating composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia and the like.
• Inorganic alkalis primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, triethanolamine and the like.
• Alkaline amines such as alcohol amines, tetramethylammonium hydroxides, tetraethylammonium hydroxides, quaternary ammonium salts such as choline, cyclic amines such as pyrrole and piperidine, and the like can be used.
• an alcohol such as isopropyl alcohol and a surfactant such as a nonionic surfactant can be added to the aqueous solution of the alkalis in an appropriate amount for use.
• the preferred developer is a quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline.
• an organic solvent can be used as the developing solution.
• an organic solvent can be used as the developing solution.
• a step of forming the resist underlayer film on the semiconductor substrate with the resist underlayer film forming composition a step of forming the resist film on the resist film, and then a step of forming the resist pattern by light or electron beam irradiation and development.
• the semiconductor device can be manufactured through a step of etching the resist underlayer film with a resist pattern and a step of processing a semiconductor substrate with the patterned resist underlayer film.
• the resist underlayer film for such a process has a selective ratio of dry etching rate close to that of the resist film, and the dry etching rate is smaller than that of the resist underlayer film for lithography and the resist film.
• a process of making the resist pattern and the resist underlayer film thinner than the pattern width at the time of resist development during dry etching of the resist underlayer film has also begun to be used.
• a resist underlayer film for such a process unlike a conventional high etching rate antireflection film, a resist underlayer film having a selection ratio of a dry etching rate close to that of a resist film is required. Further, it is possible to impart an antireflection ability to such a resist underlayer film, and it is possible to have the function of a conventional antireflection film.
• the substrate after forming the resist underlayer film of the present invention on the substrate, directly on the resist underlayer film, or if necessary, one or several layers of the coating material are formed on the resist underlayer film, and then the film is formed.
• a resist can be applied.
• the pattern width of the resist film is narrowed, and even when the resist film is thinly coated to prevent the pattern from collapsing, the substrate can be processed by selecting an appropriate etching gas.
• a step of forming the resist underlayer film on the semiconductor substrate with the resist underlayer film forming composition and forming a hard mask with a coating material containing a silicon component or the like or a hard mask by vapor deposition (for example, silicon nitride) on the step.
• a step of forming a resist film on the resist film a step of forming a resist pattern by irradiation and development of light or an electron beam, a step of etching a hard mask with a halogen-based gas by a resist pattern, and a patterned hard mask.
• the stepped substrate coating composition of the present invention when the effect as an antireflection film is taken into consideration, since the light absorption portion is incorporated into the skeleton, there is no diffuser in the photoresist during heating and drying, and light Since the absorption site has a sufficiently large absorption performance, it has a high antireflection effect.
• the stepped substrate coating composition of the present invention has high thermal stability, can prevent contamination of the upper layer film by decomposition products during firing, and can provide a margin in the temperature margin of the firing process.
• the stepped substrate coating composition of the present invention has a function of preventing light reflection and further preventing interaction between the substrate and the photoresist, or a material or photoresist used for the photoresist, depending on the process conditions. It can be used as a film having a function of preventing adverse effects of substances generated during exposure on a substrate.
• the mixture was heated to 140 ° C. and refluxed and stirred under a nitrogen atmosphere for about 24 hours. Then, the mixture was cooled to room temperature, 1.951 g of propiolic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter abbreviated as PA) was added, and the mixture was refluxed and stirred at 60 ° C. under a nitrogen atmosphere for about 36 hours.
• PA propiolic acid
• anion exchange resin product name: Dawex [registered trademark] 550A, Muromachi Technos Co., Ltd.
• cation exchange resin product name: Amberlite [registered trademark] 15JWET, organo (product name: Amberlite [registered trademark] 15JWET) Co., Ltd.) 12.315 g was added and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of compound formula (1-1) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,570.
• anion exchange resin product name: Dawex [registered trademark] 550A, Muromachi Technos Co., Ltd.
• cation exchange resin product name: Amberlite [registered trademark] 15JWET, organo (product name: Amberlite [registered trademark] 15JWET) Co., Ltd.) 14.779 g was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of compound formula (1-2) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 2,620.
• anion exchange resin product name: Dawex [registered trademark] 550A, Muromachi Technos Co., Ltd.
• cation exchange resin product name: Amberlite [registered trademark] 15JWET, organo (product name: Amberlite [registered trademark] 15JWET) Co., Ltd.) 14.465 g was added and treated with an ion exchange at room temperature for 4 hours. After separating the ion exchange resin, a solution of compound formula (1-3) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 750.
• Anion exchange resin product name: Dawex [registered trademark] 550A, Muromachi Technos Co., Ltd.
• 11 g was added and ion exchange treatment was performed at room temperature for 4 hours.
• a solution of compound formula (1-4) was obtained.
• the obtained compound had a weight average molecular weight Mw measured by GPC in terms of polystyrene and was 4,100.
• TMOM-BP Propylene glycol containing 0.166 g, 1% surfactant (manufactured by DIC Co., Ltd., product name: Megafuck [trade name] R-40, fluorine-based surfactant), manufactured by Honshu Chemical Industry Co., Ltd. 0.166 g of monomethyl ether acetate, 2.822 g of propylene glycol monomethyl ether, and 4.266 g of propylene glycol monomethyl ether acetate were mixed. Then, the mixture was filtered through a polytetrafluoroethylene microfilter having a diameter of 0.1 ⁇ m to prepare a solution of the resist underlayer film forming composition.
• TMOM-BP Propylene glycol containing 0.166 g, 1% surfactant (manufactured by DIC Co., Ltd., product name: Megafuck [trade name] R-40, fluorine-based surfactant), manufactured by Honshu Chemical Industry Co., Ltd. 0.166 g of monomethyl ether acetate, 0.260 g of propylene glycol monomethyl ether, and 7.522 g of propylene glycol monomethyl ether acetate were mixed. Then, the mixture was filtered through a polytetrafluoroethylene microfilter having a diameter of 0.1 ⁇ m to prepare a solution of the resist underlayer film forming composition.
• Example 3 Propylene glycol monomethyl ether 0.497 g containing 5% TAG2689 (King Industries, Inc., thermal acid generator) in 4.239 g of the resin solution (solid content 19.53%) obtained in Synthesis Example 3, TMOM-BP ( Propylene glycol containing 0.1656 g of Honshu Chemical Industry Co., Ltd., 1% surfactant (DIC Co., Ltd., product name: Megafuck [trade name] R-40, fluorine-based surfactant) 0.166 g of monomethyl ether acetate, 2.822 g of propylene glycol monomethyl ether, and 4.11 g of propylene glycol monomethyl ether acetate were mixed. Then, the mixture was filtered through a polytetrafluoroethylene microfilter having a diameter of 0.1 ⁇ m to prepare a solution of the resist underlayer film forming composition.
• Example 3 a curing reaction occurs due to a reaction with a cross-linking material to obtain solvent resistance and a residual film ratio of 100%, whereas in Comparative Example 1, it is not sufficiently cured by heat alone and solvent resistance is obtained. There wasn't.
• the flatness of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the film thickness of the dense area (pattern portion) and the open area (non-pattern portion) of the stepped substrate was observed.
• the flatness was evaluated by measuring the difference (the coating step between the dense area and the open area, which is called the bias).
• the flattening property is a portion where the pattern exists (dense area (pattern portion)) and a portion where the pattern does not exist (open area (non-pattern portion)), and the coated coating film existing on the upper portion thereof. It means that the film thickness difference (Iso-dense bias) of the object is small.
• Example 1-3 since the cross-linking start temperature of the cross-linking group contained in the polymer can be raised, sufficient reflowability can be obtained and good flattening property can be obtained.
• Comparative Example 2 the cross-linking start temperature of the cross-linking agent is low, and sufficient reflowability cannot be obtained, so that the flattening property is low.
• the stepped substrate coating composition of the present invention has high filling property into a pattern and can be used as a stepped substrate coating composition for forming a film having flattening property on a substrate.

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