Classifications

• • 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
  • H10P76/2042—Photolithographic processes using lasers
• • 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
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic 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
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
  • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
• • 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
  • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
• • 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
• • 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
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/167—Coating processes; Apparatus therefor from the gas phase, by plasma deposition
• • 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
  • G03F7/20—Exposure; Apparatus therefor
• • 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
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
• • 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
• • 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
  • G03F7/36—Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma
• • 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
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/71—Etching of wafers, substrates or parts of devices using masks for conductive or resistive materials

Definitions

• the present invention relates to a method for manufacturing a semiconductor substrate and a composition for forming a resist underlayer film.
• a resist film formed from a radiation-sensitive composition for forming a resist film is exposed to far ultraviolet rays (e.g., ArF excimer laser light, KrF excimer laser light, etc.), extreme ultraviolet rays ( Electromagnetic waves such as EUV) or charged particle beams such as electron beams are used to generate acid in the exposed areas.
• far ultraviolet rays e.g., ArF excimer laser light, KrF excimer laser light, etc.
• extreme ultraviolet rays Electromagnetic waves such as EUV
• charged particle beams such as electron beams are used to generate acid in the exposed areas.
• a chemical reaction catalyzed by this acid causes a difference in dissolution rate in the developing solution between the exposed area and the unexposed area, thereby forming a pattern on the substrate.
• the formed pattern can be used as a mask or the like in substrate processing.
• Such a pattern forming method is required to improve the resist performance along with the miniaturization of the processing technology.
• organic polymers, acid generators, and other components used in radiation-sensitive compositions for forming resist films, types of components, molecular structures, etc. have been studied, and combinations thereof have also been studied in detail ( See JP-A-2000-298347). Also, the use of metal-containing compounds instead of organic polymers has been investigated.
• the resist pattern may collapse or the pattern may trail at the bottom of the resist film.
• An object of the present invention is to provide a method for manufacturing a semiconductor substrate and a composition for forming a resist underlayer film, capable of forming a resist pattern having excellent pattern rectangularity by suppressing collapse of the resist pattern and skirting of the pattern at the bottom of the resist film. is to provide
• the present invention in one embodiment, a step of directly or indirectly applying a composition for forming a resist underlayer film onto a substrate; a step of forming a metal-containing resist film on the resist underlayer film formed by the resist underlayer film-forming composition coating step; exposing the metal-containing resist film; volatilizing part of the exposed metal-containing resist film to form a resist pattern.
• the present invention in another embodiment, a step of directly or indirectly applying a composition for forming a resist underlayer film onto a substrate; a step of forming a metal-containing resist film on the resist underlayer film formed by the resist underlayer film-forming composition coating step; exposing the metal-containing resist film;
• a composition for forming a resist underlayer film which is used in a method for manufacturing a semiconductor substrate comprising a step of volatilizing a part of the exposed metal-containing resist film to form a resist pattern, at least one selected from the group consisting of an acid-generating component, an acid-group-containing component, a photobase generator and a base-containing component;
• the present invention relates to a composition for forming a resist underlayer film containing a solvent and
• a composition for forming a resist underlayer film capable of forming a resist underlayer film having excellent resist pattern rectangularity is used, a semiconductor substrate having a favorable pattern shape can be efficiently manufactured.
• a resist underlayer film having excellent resist pattern rectangularity can be formed, so that a semiconductor substrate having a favorable pattern shape can be efficiently manufactured. Therefore, the method for producing a semiconductor substrate and the composition for forming a resist underlayer film can be suitably used for the production of semiconductor devices, which are expected to be further miniaturized in the future.
• the method for producing a semiconductor substrate includes a step of directly or indirectly applying a composition for forming a resist underlayer film onto a substrate (hereinafter also referred to as a “step of applying a composition for forming a resist underlayer film”); A step of forming a metal-containing resist film on the resist underlayer film formed by the film-forming composition coating step (hereinafter also referred to as a “metal-containing resist film forming step”), and a step of exposing the metal-containing resist film. (hereinafter also referred to as “exposure step”), and a step of volatilizing part of the exposed metal-containing resist film to form a resist pattern (hereinafter also referred to as “resist pattern forming step”).
• the resist underlayer film-forming composition is applied directly or indirectly onto the substrate.
• the method of coating the composition for forming a resist underlayer film is not particularly limited, and can be carried out by an appropriate method such as spin coating, casting coating, roll coating, or the like. Thereby, a coating film is formed, and a resist underlayer film is formed by volatilization of the solvent in the composition for forming a resist underlayer film.
• the resist underlayer film-forming composition will be described later.
• the coating film formed by the coating is heated.
• the heating of the coating promotes the formation of the resist underlayer film. More specifically, heating the coating film promotes volatilization of the solvent in the resist underlayer film-forming composition.
• the coating film may be heated in an air atmosphere or in a nitrogen atmosphere.
• the lower limit of the heating temperature is preferably 100°C, more preferably 150°C, and even more preferably 200°C.
• the upper limit of the heating temperature is preferably 400°C, more preferably 350°C, and even more preferably 280°C.
• the lower limit of the heating time is preferably 15 seconds, more preferably 30 seconds.
• the upper limit of the time is preferably 1,200 seconds, more preferably 600 seconds.
• the lower limit to the average thickness of the resist underlayer film to be formed is preferably 0.5 nm, more preferably 1 nm, and even more preferably 2 nm.
• the upper limit of the average thickness is preferably 50 nm, more preferably 20 nm, still more preferably 10 nm, and particularly preferably 7 nm.
• the method for measuring the average thickness is described in Examples.
• Metal-containing resist film forming step In this step, a metal-containing resist film is formed on the resist underlayer film formed in the resist underlayer film-forming composition coating step.
• the metal-containing resist film can be formed by depositing a metal compound on the resist underlayer film.
• Deposition of the metal compound on the resist underlayer film may be performed by vapor deposition by chemical vapor deposition (CVD) or atomic layer deposition (ALD). Deposition may be performed by plasma enhanced (PE) CVD or plasma enhanced (PE) ALD.
• CVD chemical vapor deposition
• ALD atomic layer deposition
• PE plasma enhanced
• PE plasma enhanced
• the metal atom contained in the metal-containing resist film is preferably at least one selected from the group consisting of Sn and Hf.
• metal compounds examples include metal compounds represented by the following formula (1).
• M(X) 4 (1) In formula (1), M is Sn or Hf. Each X is independently a halogen atom or an alkyl group.
• metal compounds examples include Sn(CH 3 ) 4 , Sn(Br) 4 and HfCl 4 .
• a metal compound can be used in combination of 2 or more types.
• process conditions suitable for depositing Sn(CH 3 ) 4 on the above resist underlayer film include a deposition temperature between about ⁇ 54° C. and 30° C. (eg, about 20° C.) and a reactor pressure of 20 Torr or less. (eg, pressure maintained at about 1 Torr at 20° C.).
• the deposition rate can be controlled by maintaining the Sn(CH 3 ) 4 flow rate between about 100 sccm and 1000 sccm.
• process conditions suitable for depositing HfCl 4 on the above resist underlayer film include a deposition temperature between about 0° C. and 300° C. (e.g., about 100° C.) and a reactor pressure of 10 Torr or less (e.g., 100° C. at a pressure maintained between 0.1 and 1 Torr).
• the deposition rate can be controlled by maintaining the HfCl 4 flow rate between about 10 sccm and 100 sccm.
• a film of Sn(Br) 4 can be made into a film of SnX 4 by the reaction of the following formula with a reactant X 2 (eg, where X is Cl, I, or H).
• X 2 eg, where X is Cl, I, or H.
• a film of HfCl 4 can be made into a film of HfX 4 by the reaction of the following formula with reactant X 2 (eg, where X is Br, I, or H).
• X 2 eg, where X is Br, I, or H.
• the lower limit to the average thickness of the metal-containing resist film to be formed is preferably 0.1 nm, more preferably 0.5 nm, and even more preferably 1 nm.
• the upper limit of the average thickness is preferably 50 nm, more preferably 20 nm, still more preferably 10 nm, and particularly preferably 5 nm.
• the method for measuring the average thickness is described in Examples.
• Radiation used for exposure can be appropriately selected according to the type of metal-containing resist film to be used.
• Examples thereof include electromagnetic waves such as visible light, ultraviolet rays, deep ultraviolet rays, X-rays and ⁇ -rays, and particle beams such as electron beams, molecular beams and ion beams.
• far ultraviolet rays are preferable, and KrF excimer laser light (wavelength 248 nm), ArF excimer laser light (wavelength 193 nm), F2 excimer laser light (wavelength 157 nm), Kr2 excimer laser light ( wavelength 147 nm), ArKr excimer laser.
• EUV extreme ultraviolet rays
• the exposure conditions can be appropriately determined according to the type of the metal-containing resist film to be used.
• EUV decomposes metal compounds (including the above SnX4 and HfX4 ) in exposed portions of a metal-containing resist film.
• the metal compound is Sn(Br) 4
• the decomposition reaction of the metal compound proceeds as follows. SnBr4 ⁇ Sn+ 2Br2 EUV directly decomposes SnBr4 into Sn and bromine gas ( Br2).
• resist pattern forming step In this step, part of the exposed metal-containing resist film is volatilized to form a resist pattern.
• a resist pattern can be formed by volatilizing the unexposed portion of the exposed metal-containing resist film. Volatilization of the unexposed portions of the exposed metal-containing resist film can be performed by reducing pressure, heating, or a combination thereof.
• the exposed portion becomes Sn. can be developed to form a resist pattern.
• etching is performed using the resist pattern as a mask. Etching may be performed once or multiple times, that is, etching may be performed sequentially using a pattern obtained by etching as a mask. Etching methods include dry etching, wet etching, and the like. A semiconductor substrate having a predetermined pattern is obtained by the etching.
• Dry etching can be performed using, for example, a known dry etching apparatus.
• the etching gas used for dry etching can be appropriately selected according to the mask pattern, the elemental composition of the film to be etched, etc. Examples include CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 and SF 6 .
• Fluorine-based gases chlorine-based gases such as Cl 2 and BCl 3 , oxygen-based gases such as O 2 , O 3 and H 2 O, H 2 , NH 3 , CO, CO 2 , CH 4 , C 2 H 2 , C 2H4 , C2H6 , C3H4 , C3H6 , C3H8 , HF, HI , HBr , HCl, NO, NH3 , reducing gases such as BCl3 , He, N2 , Inert gas, such as Ar, etc. are mentioned. These gases can also be mixed and used.
• composition for forming a resist underlayer film comprises a step of applying the composition for forming a resist underlayer film directly or indirectly onto a substrate, and adding a metal to the resist underlayer film formed by the step of applying the composition for forming a resist underlayer film.
• a method for manufacturing a semiconductor substrate comprising the steps of: forming a metal-containing resist film; exposing the metal-containing resist film; and volatilizing a portion of the exposed metal-containing resist film to form a resist pattern. used for For the details of each step, the steps of the method for manufacturing the semiconductor substrate can be suitably adopted.
• the composition for forming a resist underlayer film comprises at least one selected from the group consisting of [A] an acid generating component, [B] an acid group-containing component, [C1] a photobase generator and [C2] a base-containing component; [E] a solvent.
• the [A] acid-generating component includes a thermal acid generator (hereinafter also referred to as [A1] thermal acid generator), a thermal acid-generating polymer (hereinafter also referred to as [A2] thermal acid-generating polymer), and light. Acid generators (hereinafter also referred to as [A3] photoacid generators) can be mentioned. [A] Acid-generating components may be used singly or in combination of two or more.
• the thermal acid generator includes a sulfo group, a carboxyl group, a phosphono group, a phosphoric acid group, a sulfuric acid group, a sulfonamide group, a sulfonylimide group, and -CR F1 R F2 OH (R F1 is a fluorine atom or a fluorinated alkyl R F2 is a hydrogen atom, a fluorine atom, or a fluorinated alkyl group) or a combination thereof (hereinafter also referred to as "acid group (a)"). It is a component of low-molecular-weight compounds generated by
• the component generated from the thermal acid generator is preferably sulfonic acid, more preferably fluorinated alkylsulfonic acid having 1 to 10 carbon atoms and sulfonic acid having an alicyclic structure, perfluoroalkylsulfonic acid and 10- Camphorsulfonic acid is more preferred, and trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid and 10-camphorsulfonic acid are particularly preferred.
• thermal acid generators include onium salt compounds such as iodonium salt compounds, organic sulfonic acid alkyl esters, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, and 2-nitrobenzyl tosylate. etc.
• iodonium salt compounds include anions such as trifluoromethanesulfonate, nonafluoro-n-butanesulfonate, 10-camphorsulfonate, pyrenesulfonate, n-dodecylbenzenesulfonate, naphthalenesulfonate, diphenyliodonium, bis(4-t-butylphenyl ) salt compounds with iodonium cations such as iodonium.
• anions such as trifluoromethanesulfonate, nonafluoro-n-butanesulfonate, 10-camphorsulfonate, pyrenesulfonate, n-dodecylbenzenesulfonate, naphthalenesulfonate, diphenyliodonium, bis(4-t-butylphenyl ) salt compounds with iodonium cations such as iodon
• an onium salt compound is preferable, and an iodonium salt compound is more preferable. More preferred are n-butanesulfonate and bis(4-t-butylphenyl)iodonium 10-camphorsulfonate.
• the lower limit of the content of [A1] thermal acid generator in the components other than the solvent in the composition for forming underlayer film is 0. .1% by weight is preferred, 1% by weight is more preferred, and 2% by weight is even more preferred.
• the upper limit of the content ratio is preferably 20% by mass, more preferably 15% by mass, still more preferably 12% by mass, and particularly preferably 10% by mass.
• the thermal acid-generating polymer is an organic polymer that generates a component having an acid group (a) by the action of heat.
• the component generated from the thermal acid-generating polymer may be a low-molecular-weight compound having an acid group (a) or an organic polymer having an acid group (a). ) are preferred.
• the lower limit of Mw of the thermal acid-generating polymer is preferably 1,600, more preferably 2,000, and even more preferably 2,500.
• the upper limit of Mw is preferably 50,000, more preferably 30,000, and even more preferably 15,000.
• Examples of the [A2] thermal acid-generating polymer include polymers having structural units in which one or more [A1] thermal acid generators are incorporated, and structural units having an alkoxysulfonyl group are preferred.
• the alkoxysulfonyl group includes, for example, an alkoxysulfonyl group having 1 to 20 carbon atoms, and an ethoxysulfonyl group is preferred.
• a structural unit containing an alkoxysulfonyl group a styrene-based structural unit containing an aromatic ring substituted with an alkoxysulfonyl group is preferred, and a structural unit represented by the following formula is more preferred.
• the [A2] thermal acid-generating polymer may have structural units other than the structural unit in which the [A1] thermal acid generator is incorporated.
• R 1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• A is a divalent hydrocarbon group consisting of a single bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a combination thereof.
• R 2 is an alkyl group having 1 to 20 carbon atoms.
• the lower limit of the content ratio of the [A1] structural unit into which the thermal acid generator is incorporated is preferably 1 mol%, more preferably 5 mol%, in all the structural units constituting the [A2] thermal acid generating polymer.
• the upper limit of the content of the structural unit is preferably 80 mol %, more preferably 60 mol %.
• the thermal acid-generating polymer may have structural units other than the structural unit in which the [A1] thermal acid generator is incorporated.
• the structural unit is not particularly limited, and includes, for example, the same structural units as those constituting each resin in the [D1] organic polymer described later.
• the lower limit of the content of the other structural units in all structural units constituting the thermal acid-generating polymer is preferably 5 mol%, more preferably 10 mol%.
• the upper limit of the content of the structural unit is preferably 80 mol %, more preferably 50 mol %.
• the lower limit of the content ratio of the [A2] thermal acid-generating polymer among the components other than the solvent in the composition for forming the underlayer film is preferably 80% by mass, more preferably 90% by mass, even more preferably 95% by mass.
• the upper limit of the content ratio may be 100% by mass.
• photoacid generator is a component that generates an acid by the action of radiation.
• Photoacid generators may be used singly or in combination of two or more.
• the acid generated from the photoacid generator is preferably sulfonic acid, more preferably fluorinated alkylsulfonic acid having 1 to 10 carbon atoms and sulfonic acid having an alicyclic structure, perfluoroalkylsulfonic acid and 10- Camphorsulfonic acid is more preferred, and trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid and 10-camphorsulfonic acid are particularly preferred.
• Photoacid generators include, for example, onium salt compounds, N-sulfonyloxyimide compounds, halogen-containing compounds, diazoketone compounds, and the like.
• onium salt compounds include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, phosphonium salts, diazonium salts, pyridinium salts and the like.
• anion of the onium salt compound examples include anions represented by the following formula.
• Examples of the cation of the onium salt compound include cations represented by the following formula.
• onium salt compound an appropriate combination of the above anion and the above cation can be used.
• N-sulfonyloxyimide compounds include compounds represented by the following formula.
• the photoacid generator is preferably an onium salt compound, more preferably a sulfonium salt, and more preferably triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, and triphenylsulfonium camphorsulfonate.
• the lower limit of the content of the [A3] photoacid generator among the components other than the solvent in the composition for forming the underlayer film is 0. .1% by weight is preferred, 1% by weight is more preferred, and 2% by weight is even more preferred.
• the upper limit of the content ratio is preferably 20% by mass, more preferably 15% by mass, still more preferably 12% by mass, and particularly preferably 10% by mass.
• the [B] acid group-containing component is a component other than the [A] acid generating component and has an acid group (a).
• the acid group-containing component may be a low-molecular compound (hereinafter also referred to as [B1] acid group-containing compound) or an organic polymer (hereinafter also referred to as [B2] acid group-containing polymer). There may be.
• the acid group-containing component can be used singly or in combination of two or more.
• the acid group-containing compound is a low-molecular-weight compound having an acid group (a).
• Specific examples of the [B1] acid group-containing compound include, for example, the same components as those described above [A1] having an acid group (a) generated from the thermal acid generator.
• the lower limit of the content ratio of the [B1] acid group-containing compound in the components other than the solvent in the composition for forming the underlayer film is 0. .1% by weight is preferred, 1% by weight is more preferred, and 2% by weight is even more preferred.
• the upper limit of the content ratio is preferably 20% by mass, more preferably 15% by mass, still more preferably 10% by mass, and particularly preferably 8% by mass.
• the acid group-containing polymer is an organic polymer having an acid group (a).
• Examples of the acid group-containing polymer include ion exchange resins having a structural unit containing an acid group (a).
• the lower limit of the Mw of the acid group-containing polymer is preferably 1,600, more preferably 2,000, and even more preferably 2,500.
• the upper limit of Mw is preferably 50,000, more preferably 30,000, and even more preferably 15,000.
• ion exchange resins include polymers obtained by introducing acid groups (a) into organic polymers such as styrene polymers, (meth)acrylic polymers, polyester polymers, cellulose, and polytetrafluoroethylene. be done. More specifically, polymers obtained by sulfonating novolac resins, polymers obtained by sulfonating resole resins, polymers obtained by sulfonating styrene polymers crosslinked with divinylbenzene, and (meth)polymers crosslinked with divinylbenzene. Examples thereof include polymers obtained by carboxylating acrylic polymers. Examples of the novolak-based resin and resol-based resin to be sulfonated in the ion-exchange resin include those similar to the novolac-based resin and resol-based resin in the [D1] organic polymer described later.
• the structural unit containing an acid group (a) one obtained by introducing a sulfo group into a structural unit of a novolac resin is preferable.
• Examples of such structural units include structural units represented by the following formulas.
• the lower limit of the content of the structural unit containing the acid group (a) in all the structural units constituting the acid group-containing polymer is preferably 5 mol%, more preferably 10 mol%.
• the upper limit of the content of the structural unit is preferably 80 mol %, more preferably 50 mol %.
• the lower limit of the content of structural units not containing an acid group (a) in all structural units constituting the acid group-containing polymer is preferably 5 mol%, more preferably 10 mol%.
• the upper limit of the content of the structural unit is preferably 80 mol %, more preferably 50 mol %.
• the lower limit of the content ratio of the [B2] acid group-containing polymer among the components other than the solvent in the composition for forming the underlayer film is preferably 80% by mass, more preferably 90% by mass, even more preferably 95% by mass.
• the upper limit of the content ratio may be 100% by mass.
• the photobase generator is a component that generates a base by the action of radiation.
• Examples of the base generated from the photobase generator include amines such as primary amines, secondary amines and tertiary amines.
• the photobase generator may be used alone or in combination of two or more.
• photobase generators include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, ⁇ , ⁇ -dimethyl-3,5-dimethoxybenzyl carbamates, acyloxyiminos, acetophenone compounds, and the like. can be done.
• transition metal complex of cobalt examples include compounds described in paragraph [0198] of JP-A-2017-009673.
• ortho-nitrobenzyl carbamates include [[(2-nitrobenzyl)oxy]carbonyl]methylamine, [[(2-nitrobenzyl)oxy]carbonyl]propylamine, [[(2-nitrobenzyl)oxy]carbonyl ]hexylamine, [[(2-nitrobenzyl)oxy]carbonyl]cyclohexylamine, [[(2-nitrobenzyl)oxy]carbonyl]aniline, [[(2-nitrobenzyl)oxy]carbonyl]piperidine, bis[[[ (2-nitrobenzyl)oxy]carbonyl]hexamethylenediamine, bis[[(2-nitrobenzyl)oxy]carbonyl]phenylenediamine, bis[[(2-nitrobenzyl)oxy]carbonyl]toluenediamine, bis[[( 2-nitrobenzyl)oxy]carbonyl]diaminodiphenylmethane, bis[[(2-nitrobenzyl)oxy]carbonyl]piperazine, [[(2,
• Examples of ⁇ , ⁇ -dimethyl-3,5-dimethoxybenzyl carbamates include [[( ⁇ , ⁇ -dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]methylamine, [[( ⁇ , ⁇ -dimethyl- 3,5-dimethoxybenzyl)oxy]carbonyl]propylamine, [[( ⁇ , ⁇ -dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]hexylamine, [[( ⁇ , ⁇ -dimethyl-3,5- Dimethoxybenzyl)oxy]carbonyl]cyclohexylamine, [[( ⁇ , ⁇ -dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]aniline, [[( ⁇ , ⁇ -dimethyl-3,5-dimethoxybenzyl)oxy] Carbonyl]piperidine, bis[[( ⁇ , ⁇ -dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]hexamethylene
• acyloxyiminos examples include propionylacetophenone oxime, propionylbenzophenone oxime, propionylacetone oxime, butyrylacetophenone oxime, butyrylbenzophenone oxime, butyrylacetone oxime, adipoylacetophenone oxime, adipoylbenzophenone oxime, and adipoylacetone.
• acetophenone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine -4-yl-phenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and other acetophenone compounds having an ⁇ -aminoketone structure mentioned.
• Photobase generators include, in addition to the above-described compound examples, 2-nitrobenzylcyclohexylcarbamate, O-carbamoylhydroxyamide, O-carbamoylhydroxyamide, and the like.
• the photobase generator is preferably an acetophenone compound and 2-nitrobenzylcyclohexylcarbamate, more preferably an acetophenone compound having an ⁇ -aminoketone structure and 2-nitrobenzylcyclohexylcarbamate, and 2-methyl-1-[ More preferred are 4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one.
• Base-containing components include onium salt compounds that are not decomposed by the action of heat, such as sulfonium salt compounds, and amines.
• sulfonium salt compounds include compounds represented by the following formula.
• amines include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, carboxylic acid quaternary ammonium salts, and the like.
• aliphatic amines examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine and dicyclohexyl.
• Aliphatic amines such as amines and dicyclohexylmethylamine are included.
• aromatic amines examples include aniline, benzylamine, N,N-dimethylaniline, diphenylamine, and the like.
• heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine , 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine , pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo[4,3,0]-5-nonene, 1,8-diazabicyclo[5,3,0]- 7 undecene and the like.
• Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide and the like.
• Examples of the quaternary ammonium salts of carboxylic acids include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
• the resist underlayer film-forming composition contains [C1] photobase generator or [C2] base-containing component, among the components other than the solvent in the underlayer film-forming composition, [C1] photobase generator or [ C2]
• the lower limit of the content of the base-containing component is preferably 0.1% by mass, more preferably 1% by mass, and even more preferably 2% by mass.
• the upper limit of the content ratio is preferably 20% by mass, more preferably 15% by mass, still more preferably 10% by mass, and particularly preferably 8% by mass.
• the composition for forming a resist underlayer film includes [B] an organic polymer other than an acid group-containing component (hereinafter also referred to as "[D1] organic polymer”), [D2] an inorganic polymer, and [D3] containing an aromatic ring.
• [D1] organic polymer an organic polymer other than an acid group-containing component
• [D2] an inorganic polymer an inorganic polymer
• [D3] containing an aromatic ring containing an aromatic ring.
• a compound, [D4] additive, and the like may be further contained.
• organic polymer for example, those described in paragraphs [0040] to [0116] of JP-A-2016-206676 can be used.
• Novolak-based resins, resol-based resins, aromatic ring-containing vinyl-based resins, acenaphthylene-based resins, indene-based resins, polyarylene-based resins, triazine-based resins, calixarene-based resins, fullerene-based resins and pyrene-based resins are preferred, and novolak-based resins and acenaphthylene-based resins are more preferred.
• the lower limit of Mw of novolac resins, resole resins, aromatic ring-containing vinyl resins, acenaphthylene resins, indene resins, polyarylene resins, triazine resins, fullerene resins or pyrene resins is preferably 500. 1,000 is more preferred, and 2,000 is even more preferred.
• the upper limit of Mw is preferably 10,000.
• the lower limit of the ratio of Mw to Mn (Mw/Mn) of these resins is preferably 1.1.
• the upper limit of Mw/Mn is preferably 5, more preferably 3, and even more preferably 2.
• the lower limit of the molecular weight of the calixarene-based resin is preferably 500, more preferably 700, and even more preferably 1,000, from the viewpoint of improving the flatness of the resist underlayer film.
• the upper limit of the molecular weight is preferably 5,000, more preferably 3,000, and even more preferably 1,500.
• the molecular weight of the calixarene-based resin means Mw in terms of polystyrene by GPC.
• [D2] inorganic polymer examples include [D2-1] polysiloxane, a plurality of metal atoms, oxygen atoms that bridge the metal atoms (hereinafter also referred to as "bridging oxygen atoms"), and the metal atoms [D2-2] complexes (dinuclear complexes) containing polydentate ligands coordinated to , [D2-3] polycarbosilanes, and the like.
• [D2-1] Polysiloxane examples include those having a structural unit (I) represented by the following formula (I) and/or a structural unit (II) represented by the following formula (II). .
• Each structural unit in the polysiloxane can be used alone or in combination of two or more.
• R 1 X1 is a monovalent organic group having 1 to 20 carbon atoms.
• organic group refers to a group having at least one carbon atom.
• the monovalent organic group represented by R X1 includes a monovalent hydrocarbon group, a monovalent fluorinated hydrocarbon group, or a divalent heteroatom-containing group between the carbon-carbon atoms of a monovalent hydrocarbon group.
• the nitrogen-containing heterocyclic ring include an azocycloalkane ring and an isocyanuric ring.
• Structural units (I) include, for example, structural units represented by the following formula.
• the lower limit of the content of structural unit (I) in [D2-1]polysiloxane is preferably 1 mol%, more preferably 5 mol%.
• the upper limit of the content of the structural unit (I) is preferably 60 mol%, more preferably 40 mol%.
• the lower limit of the content of structural unit (II) in [D2-1]polysiloxane is preferably 40 mol%, more preferably 60 mol%.
• the upper limit of the content of the structural unit (II) is preferably 99 mol%, more preferably 95 mol%.
• the lower limit of Mw of [D2-1]polysiloxane is preferably 500, more preferably 800, and even more preferably 1,200.
• the upper limit of Mw is preferably 100,000, more preferably 30,000, still more preferably 10,000, and particularly preferably 5,000.
• titanium, tantalum, zirconium and tungsten (hereinafter also referred to as "specific metal atoms") are preferable, and titanium and zirconium are more preferable.
• specific metal atoms titanium, tantalum, zirconium and tungsten
• the [D2-2] complex can become a stable multinuclear complex by including a bridging oxygen atom.
• a plurality of bridging oxygen atoms may be bonded to one metal atom, but for some metal atoms, only one bridging oxygen atom may be bonded to one metal atom.
• the [C2-2] complex preferably mainly contains a structure in which two bridging oxygen atoms are bonded to one metal atom.
• "mainly containing" the above structure means 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably It means that two bridging oxygen atoms are bonded to each of 95 mol % or more of the metal atoms.
• the [D2-2] complex may have other bridging ligands such as peroxide ligands (-O-O-) in addition to the bridging oxygen atoms.
• bridging ligands such as peroxide ligands (-O-O-) in addition to the bridging oxygen atoms.
• the multidentate ligand in the [D2-2] complex improves the solubility of the [C2-2] complex, thereby improving the removability of the underlying film.
• polydentate ligands include hydroxy acid esters, ⁇ -diketones, ⁇ -ketoesters, malonic acid diesters in which the carbon atom at the ⁇ -position may be substituted (hereinafter also referred to as “malonic acid diesters”), and ⁇ Hydrocarbons with bonds or ligands derived from these compounds are preferred.
• These compounds usually form a multidentate ligand as an anion that gains one electron, form a multidentate ligand as an anion with a proton removed, or form a multidentate ligand with its structure as it is. Forms a dentate ligand.
• the lower limit of the molar ratio of the polydentate ligand to the metal atom in the complex is preferably 1, more preferably 1.5, and still more preferably 1.8.
• the upper limit of the above ratio is preferably 3, more preferably 2.5, and even more preferably 2.2.
• the [D2-2] complex may contain other ligands in addition to the above-described bridging ligands and polydentate ligands.
• [D2-3]polycarbosilane is a polymer having Si—C bonds in the main chain.
• [D2-3]polycarbosilane has, for example, a first structural unit represented by the following formula (i) (hereinafter also referred to as “structural unit (i)").
• [D2-3]polycarbosilane is a second structural unit represented by formula (ii) described later (hereinafter also referred to as “structural unit (ii)”) and a third structural unit represented by formula (iii). It may have a structural unit (hereinafter also referred to as “structural unit (iii)”).
• [D2-3] polycarbosilane can be used alone or in combination of two or more.
• Structural unit (i) Structural unit (i) is represented by the following formula (i).
• R 1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.
• X and Y are each independently a hydrogen atom, a hydroxy group, a halogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• R 1 in the above formula (i) includes, for example, a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent carbonized alicyclic group having 3 to 20 carbon atoms.
• a hydrogen group, a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like can be mentioned.
• the chain hydrocarbon group includes both a straight chain hydrocarbon group and a branched chain hydrocarbon group.
• Examples of the unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms include chain saturated hydrocarbon groups such as methanediyl group and ethanediyl group, and chain unsaturated hydrocarbon groups such as ethenediyl group and propenediyl group. etc.
• Examples of the unsubstituted divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a monocyclic alicyclic saturated hydrocarbon group such as cyclobutanediyl group, and a monocyclic alicyclic group such as cyclobutenediyl group.
• Formula unsaturated hydrocarbon group, polycyclic alicyclic saturated hydrocarbon group such as bicyclo[2.2.1]heptanediyl group, polycyclic alicyclic unsaturated group such as bicyclo[2.2.1]heptenediyl group A hydrocarbon group etc. are mentioned.
• Examples of the unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenylene group, a biphenylene group, a phenyleneethylene group, and a naphthylene group.
• substituents in the substituted divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 include a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkoxy group, an acyl group, an acyloxy group, and the like. mentioned.
• R 1 is preferably an unsubstituted chain saturated hydrocarbon group, more preferably a methanediyl group or an ethanediyl group.
• the monovalent organic group having 1 to 20 carbon atoms represented by X or Y in the above formula (i) includes, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a carbon-carbon a monovalent group having a divalent heteroatom-containing group, the above hydrocarbon group or a group containing a divalent heteroatom-containing group in which some or all of the hydrogen atoms of the group are substituted with a monovalent heteroatom-containing group and the like.
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent linear hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a 6 to 20 monovalent aromatic hydrocarbon groups and the like are included.
• Examples of monovalent chain hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl group and ethyl group, alkenyl groups such as ethenyl group, and alkynyl groups such as ethynyl group.
• Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include monovalent monocyclic saturated alicyclic hydrocarbon groups such as cyclopentyl group and cyclohexyl group, cyclopentenyl group, cyclohexenyl group and the like. Monovalent monocyclic alicyclic unsaturated hydrocarbon groups, norbornyl groups, monovalent polycyclic saturated alicyclic hydrocarbon groups such as adamantyl groups, norbornenyl groups, monovalent monovalent groups such as tricyclodecenyl groups Examples include polycyclic alicyclic unsaturated hydrocarbon groups.
• Examples of monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, xylyl, naphthyl, methylnaphthyl and anthryl, benzyl, naphthylmethyl and anthryl. and aralkyl groups such as methyl group.
• heteroatom constituting the divalent or monovalent heteroatom-containing group examples include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a halogen atom and the like.
• Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
• divalent heteroatom-containing groups examples include -O-, -CO-, -S-, -CS-, -NR'-, and groups in which two or more of these are combined.
• R' is a hydrogen atom or a monovalent hydrocarbon group.
• monovalent heteroatom-containing groups include halogen atoms such as fluorine, chlorine, bromine and iodine atoms, hydroxy, carboxy, cyano, amino and sulfanyl groups.
• the monovalent organic group having 1 to 20 carbon atoms represented by X or Y is preferably a monovalent hydrocarbon group, more preferably a monovalent linear hydrocarbon group or a monovalent aromatic hydrocarbon group. , an alkyl group or an aryl group are more preferred.
• the number of carbon atoms in the monovalent organic group represented by X or Y is preferably 1-10, more preferably 1-6.
• the halogen atom represented by X or Y includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. As this halogen atom, a chlorine atom or a bromine atom is preferable.
• the lower limit of the content of the structural unit (i) with respect to the total structural units constituting the [D2-3]polycarbosilane is 5 mol%.
• 30 mol % is more preferable, 60 mol % is even more preferable, and 80 mol % is particularly preferable.
• the upper limit of the content of structural unit (i) may be 100 mol %.
• Structural unit (ii) is an arbitrary structural unit that [D2-3]polycarbosilane may have, and is represented by the following formula (ii).
• the lower limit of the content ratio of the structural unit (ii) to the total structural units constituting the [D2-3]polycarbosilane is 0.1 mol. % is preferred, 1 mol % is more preferred, and 5 mol % is even more preferred.
• the upper limit of the content of the structural unit (ii) is preferably 50 mol%, more preferably 40 mol%, still more preferably 30 mol%, and particularly preferably 20 mol%.
• Structural unit (iii) Structural unit (iii) is an arbitrary structural unit that [D2-3]polycarbosilane may have, and is represented by the following formula (iii).
• R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• c is 1 or 2; When c is 2, two R 2 are the same or different.
• R 2 examples include the same groups as the monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified for X and Y in formula (i) above.
• substituents for the monovalent hydrocarbon group having 1 to 20 carbon atoms include the same monovalent heteroatom-containing groups exemplified for X and Y in formula (i) above.
• R 2 is preferably a substituted or unsubstituted monovalent chain hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, more preferably an alkyl group or an aryl group, and a methyl group or a phenyl group. More preferred.
• the lower limit of the content ratio of the structural unit (iii) to the total structural units constituting the [D2-3]polycarbosilane is 0.1 mol. % is preferred, 1 mol % is more preferred, and 5 mol % is even more preferred.
• the upper limit of the content of the structural unit (iii) is preferably 50 mol%, more preferably 40 mol%, still more preferably 30 mol%, and particularly preferably 20 mol%.
• Aromatic ring-containing compound is a compound having an aromatic ring and having a molecular weight of 600 or more and 3,000 or less (excluding [D1] organic polymer and [D2] inorganic polymer).
• the molecular weight of the [D3] aromatic ring-containing compound means, for example, the polystyrene-equivalent weight average molecular weight (Mw) by GPC.
• the heat resistance and etching resistance of the underlayer film can be improved in the same manner as in the case of containing the [D1] organic polymer having an aromatic ring.
• Specific examples of the aromatic ring-containing compound include compounds described in paragraphs [0117] to [0179] of JP-A-2016-206676.
• Additives include [D4-1] cross-linking agent, [D4-2] cross-linking accelerator, surfactant and the like.
• the composition for forming a resist underlayer film preferably further contains [D4-1] cross-linking agent and/or [D4-2] cross-linking accelerator.
• the [D4-1] cross-linking agent is a component that forms a cross-linked bond between the [D1] organic polymers by the action of heat or the like.
• the hardness of the underlayer film can be improved.
• Examples of [D4-1] cross-linking agents include compounds having an alkoxyalkylated amino group, hydroxymethyl group-substituted phenol compounds, and the like.
• hydroxymethyl group-substituted phenol compounds include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene [2,6-bis (hydroxymethyl)-p-cresol], 4,4′-(1-(4-(1-(4-hydroxy-3,5-bis(methoxymethyl)phenyl)-1-methylethyl)phenyl)ethylidene) bis(2,6-bis(methoxymethyl)phenol), 5,5′-(1-methylethylidene)bis(2-hydroxy-1,3-benzenedimethanol) and the like.
• Examples of compounds having an alkoxyalkylated amino group include (poly)methylolated melamine, (poly)methylolated glycoluril, (poly)methylolated benzoguanamine, (poly)methylolated urea, and the like.
• Examples of the nitrogen-containing compound having an active methylol group include compounds obtained by substituting at least part of the hydrogen atoms of the hydroxy groups in the methylol group with alkyl groups such as methyl groups and butyl groups.
• the compound having an alkoxyalkylated amino group may be a mixture of a plurality of substituted compounds, or may contain an oligomer component partially self-condensed.
• cross-linking agent in addition to the compounds described above, for example, polyfunctional (meth)acrylate compounds, epoxy compounds, hydroxymethyl group-substituted phenol compounds, alkoxyalkyl group-containing phenol compounds, etc. can also be used. Specific examples of these compounds include compounds described in paragraphs [0203] to [0207] of JP-A-2016-206676.
• cross-linking agent a hydroxymethyl group-substituted phenol compound and a compound having an alkoxyalkylated amino group are preferable, and 5,5′-(1-methylethylidene)bis(2-hydroxy-1,3 -benzenedimethanol) and 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine are more preferred.
• the lower limit of the content of the [D4-1] cross-linking agent in the components other than the solvent in the underlayer film-forming composition is 0. .1% by weight is preferred, 1% by weight is more preferred, and 2% by weight is even more preferred.
• the upper limit of the content ratio is preferably 20% by mass, more preferably 15% by mass, still more preferably 10% by mass, and particularly preferably 8% by mass.
• the [D4-2] cross-linking accelerator is used for the formation of cross-linked bonds by the [D4-1] cross-linking agent, and hydrolytic condensation by the hydrolyzable groups remaining in [D2-1] polysiloxane and [D2-2] complexes. etc.
• a nitrogen-containing compound having an acid-dissociable group can be used as the cross-linking accelerator.
• Nitrogen-containing compounds having an acid-labile group include, for example, Nt-butoxycarbonylpiperidine, Nt-butoxycarbonylimidazole, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole. , N-(t-butoxycarbonyl)di-n-octylamine, N-(t-butoxycarbonyl)diethanolamine, N-(t-butoxycarbonyl)dicyclohexylamine, N-(t-butoxycarbonyl)diphenylamine, Nt -butoxycarbonyl-4-hydroxypiperidine, Nt-amyloxycarbonyl-4-hydroxypiperidine and the like.
• the lower limit of the content of the [D4-2] cross-linking accelerator among the components other than the solvent in the composition for forming the underlayer film is preferably 0.1% by mass, more preferably 1% by mass, and even more preferably 2% by mass.
• the upper limit of the content ratio is preferably 20% by mass, more preferably 15% by mass, still more preferably 10% by mass, and particularly preferably 8% by mass.
• the surfactant improves the coating surface uniformity of the formed underlayer film and suppresses the occurrence of coating spots.
• Specific examples of the surfactant include those described in paragraph [0216] of JP-A-2016-206676.
• Solvents include, for example, hydrocarbon solvents, ester solvents, alcohol solvents, ketone solvents, ether solvents, and nitrogen-containing solvents. [E] Solvents may be used alone or in combination of two or more.
• hydrocarbon solvents examples include aliphatic hydrocarbon solvents such as n-pentane, n-hexane and cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene and xylene.
• ester solvents include carbonate solvents such as diethyl carbonate, acetic acid monoester solvents such as methyl acetate and ethyl acetate, lactone solvents such as ⁇ -butyrolactone, diethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate.
• carbonate solvents such as diethyl carbonate
• acetic acid monoester solvents such as methyl acetate and ethyl acetate
• lactone solvents such as ⁇ -butyrolactone
• diethylene glycol monomethyl ether acetate diethylene glycol monomethyl ether acetate
• propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate.
• Valued alcohol partial ether carboxylate solvents such as methyl lactate and ethyl lactate, and the like are included.
• alcohol solvents examples include monoalcohol solvents such as methanol, ethanol, n-propanol and 4-methyl-2-pentanol, and polyhydric alcohol solvents such as ethylene glycol and 1,2-propylene glycol. .
• ketone solvents examples include chain ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and cyclic ketone solvents such as cyclohexanone.
• ether solvents examples include linear ether solvents such as n-butyl ether, polyhydric alcohol ether solvents such as cyclic ether solvents such as tetrahydrofuran, and polyhydric alcohol partial ether solvents such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether. Solvents and the like are included.
• nitrogen-containing solvents examples include linear nitrogen-containing solvents such as N,N-dimethylacetamide and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.
• the solvent is preferably an alcohol solvent, an ether solvent or an ester solvent, more preferably a monoalcohol solvent, a polyhydric alcohol partial ether solvent or a polyhydric alcohol partial ether carboxylate solvent, and 4-methyl -2-Pentanol, propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate are more preferred.
• the lower limit of the [E] solvent content in the composition for forming a resist underlayer film is preferably 50% by mass, more preferably 60% by mass, and even more preferably 70% by mass.
• the upper limit of the content ratio is preferably 99.9% by mass, more preferably 99% by mass, and even more preferably 95% by mass.
• the composition for forming a resist underlayer film comprises at least one selected from the group consisting of [A] an acid generating component, [B] an acid group-containing component, [C1] a photobase generator and [C2] a base-containing component; [E] It can be prepared by mixing a solvent and, if necessary, optional components in a predetermined ratio, and preferably filtering the resulting mixture through a membrane filter or the like having a pore size of 0.5 ⁇ m or less.
• Mw Weight average molecular weight
• Average thickness of film The average thickness of the film is measured using a spectroscopic ellipsometer ("M2000D" by JA WOOLLAM) at arbitrary 9 points at 5 cm intervals including the center of the resist underlayer film and the metal-containing resist film. Then, the average value of those film thicknesses was obtained as a calculated value.
• A-1 A compound represented by the following formula (a-1)
• A-2 A compound represented by the following formula (a-2)
• A-3 A compound represented by the following formula (a-3)
• A- 4 Resin represented by the following formula (a-4) (Mw: 3,000)
• A-5 A compound represented by the following formula (a-5)
• A-6 A compound represented by the following formula (a-6)
• B-1 Acid group-containing polymer represented by the following formula (b-1) (Mw: 3,000)
• C1-1 compound represented by the following formula (c1-1)
• C1-2 compound represented by the following formula (c1-2)
• C1-3 compound represented by the following formula (c1-3)
• D1-1 an organic polymer represented by the following formula (c-1) (Mw: 2,000)
• D1-2 an organic polymer represented by the following formula (c-2) (Mw: 1,100)
• D1-3 an organic polymer represented by the following formula (c-3) (Mw: 2,000)
• D1-4 an organic polymer represented by the following formula (c-4)
• D1-5 an organic polymer represented by the following formula (c-5)
• D1-6 an organic polymer represented by the following formula (c-6) (Mw: 2,000)
• D2-1-1 an inorganic polymer represented by the following formula (c-7) (Mw: 1,500)
• D2-1-2 an inorganic polymer (Mw: 2,000) represented by the following formula (c-8)
• D2-1-3 an inorganic polymer (Mw: 2,000) represented by the following formula (c-9)
• D2-1-4 an inorganic polymer (Mw: 3,000) represented by the following formula (c-10)
• the inside of the reaction vessel was set to 20° C., and the above monomer solution was added dropwise over 1 hour while stirring.
• the end of the dropwise addition was defined as the start time of the reaction, and the polymerization reaction was carried out at 40° C. for 1 hour and then at 60° C. for 3 hours.
• tetrahydrofuran (213 parts by mass) was added, and the polymerization solution was ice-cooled to 10° C. or lower.
• triethylamine 150 mol %) was added to the cooled polymerization solution, methanol (150 mol %) was added dropwise from the dropping funnel over 10 minutes while stirring.
• the end of the dropwise addition was defined as the start time of the reaction, and the reaction was carried out at 20° C.
• polycarbosilane (D2- A propylene glycol monomethyl ether solution of 3-1) was obtained.
• concentration of this polycarbosilane (D2-3-1) in the propylene glycol monomethyl ether acetate solution was 5% by mass.
• Mw of polycarbosilane (D2-3-1) was 2,500.
• Mw of polycarbosilane (D2-3-2) is 1,800
• Mw of polycarbosilane (D2-3-3) is 2,100
• Mw of polycarbosilane (D2-3-4) is 1,300
• Mw of polycarbosilane (D2-3-5) was 1,800.
• D2-3-1 Polycarbosilane synthesized above (D2-3-1) (Mw: 2,500)
• D2-3-2 Polycarbosilane synthesized above (D2-3-2) (Mw: 1,800)
• D2-3-3 Polycarbosilane synthesized above (D2-3-3) (Mw: 2,100)
• D2-3-4 Polycarbosilane synthesized above (D2-3-4) (Mw: 1,300)
• D2-3-5 Polycarbosilane synthesized above (D2-3-5) (Mw: 1,800)
• Example 1 0.3 parts by mass of the thermal acid generator (A-1) and 2.7 parts by mass of the organic polymer (D1-2) were dissolved in 97.0 parts by mass of the solvent (E-1). This solution was filtered through a membrane filter with a pore size of 0.45 ⁇ m to prepare a composition for forming a resist underlayer film (J-1).
• Example 2 to 43 Compositions (J-2) to (J-43) for resist underlayer film formation were prepared in the same manner as in Example 1, except that the types and contents of the components shown in Table 2 were used. "-" in Table 2 indicates that the corresponding component was not used.
• a substrate (S-1) was prepared by forming a silicon dioxide film with a thickness of 20 nm on a 12-inch silicon wafer.
• a substrate (S-2) was prepared by forming a silicon carbide film with a thickness of 20 nm on a 12-inch silicon wafer.
• Sn(CH 3 ) 4 was added to the surface of the substrate (S-1), substrate (S-2) or substrate (S-3) prepared above by a CVD apparatus at 20° C. under a pressure of about 1 Torr. deposited to form a metal-containing resist film with a thickness of 2 nm.
• Pattern rectangularity was evaluated according to the following method. The evaluation results are shown in Table 3 below. "-" in Table 3 indicates that the composition for forming a resist underlayer film was not applied.
• Pattern rectangularity A scanning electron microscope (“SU8220” manufactured by Hitachi High-Technologies Corporation) was used to measure and observe the resist pattern of the evaluation substrate. The pattern rectangularity was rated as "A” (good) when the cross-sectional shape of the pattern was rectangular, “B1” (bad) when the pattern cross-section had footing, and “B1” (poor) when the resist pattern collapsed. B2” (defective).
• a composition for forming a resist underlayer film having excellent pattern rectangularity is used, so that a semiconductor substrate having a favorable pattern shape can be efficiently manufactured. Therefore, the method for manufacturing a semiconductor substrate can be suitably used for manufacturing semiconductor devices which are expected to be further miniaturized in the future.

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