US20230250238A9 - Silicon-containing composition and method of producing semiconductor substrate - Google Patents

Silicon-containing composition and method of producing semiconductor substrate Download PDF

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US20230250238A9
US20230250238A9 US17/887,670 US202217887670A US2023250238A9 US 20230250238 A9 US20230250238 A9 US 20230250238A9 US 202217887670 A US202217887670 A US 202217887670A US 2023250238 A9 US2023250238 A9 US 2023250238A9
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silicon
group
formula
carbon atoms
structural unit
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US20220403116A1 (en
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Ryuichi Serizawa
Kengo HIRASAWA
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JSR Corp
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JSR Corp
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    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N 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
    • G03F7/09—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
    • G03F7/004—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
    • G03F7/20—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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/325—Non-aqueous compositions
    • G03F7/327—Non-aqueous alkaline compositions, e.g. anhydrous quaternary ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to a silicon-containing composition and a method of producing a semiconductor substrate.
  • a multilayer resist process which includes: exposing and developing a resist film laminated via an organic underlayer film, a silicon-containing film, and the like on a substrate; and using as a mask, a resist pattern thus obtained to carry out etching, whereby a substrate is formed having a pattern formed thereon (see PCT International Publication No. 2012/039337).
  • a silicon-containing composition includes a polysiloxane compound and solvent.
  • the polysiloxane compound includes a fluorine atom and a group including an ester bond.
  • a method of producing a semiconductor substrate includes applying a silicon-containing composition directly or indirectly on a substrate to form a silicon-containing film.
  • a composition for resist film formation is applied directly or indirectly on the silicon-containing film to form a resist film.
  • the resist film is exposed to a radioactive ray.
  • the resist film exposed is developed with an organic solvent.
  • the silicon-containing composition includes a polysiloxane compound and solvent.
  • the polysiloxane compound includes a fluorine atom and a group including an ester bond.
  • the words “a” and “an” and the like carry the meaning of “one or more.”
  • an amount, concentration, or other value or parameter is given as a range, and/or its description includes a list of upper and lower values, this is to be understood as specifically disclosing all integers and fractions within the given range, and all ranges formed from any pair of any upper and lower values, regardless of whether subranges are separately disclosed.
  • a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, as well as all integers and fractions within the range.
  • a stated range of 1-10 fully describes and includes the independent subrange 3.4-7.2 as does the following list of values: 1, 4, 6, 10.
  • a silicon-containing film is removed by using a removing liquid. In this procedure, easily removing the silicon-containing film while preventing damage on the substrate is demanded.
  • a silicon-containing composition is to be used in forming an underlayer film of a resist film to be subjected to development with an organic solvent, and contains: a polysiloxane compound (hereinafter, may be also referred to as “(A) compound” or “compound (A)”) including a fluorine atom and a group including an ester bond; and a solvent (hereinafter, may be also referred to as “(B) solvent” or “solvent (B)”).
  • a polysiloxane compound hereinafter, may be also referred to as “(A) compound” or “compound (A)”
  • solvent hereinafter, may be also referred to as “(B) solvent” or “solvent (B)”.
  • An other embodiment of the invention is a method of producing a semiconductor substrate, the method including: applying a silicon-containing composition directly or indirectly on a substrate; applying a composition for resist film formation directly or indirectly on a silicon-containing film formed by the applying of the silicon-containing composition; applying a composition for resist film formation directly or indirectly on a silicon-containing film formed by the applying of the silicon-containing composition; exposing to a radioactive ray, a resist film formed by the applying of the composition for resist film formation; and developing with an organic solvent, the resist film exposed.
  • the silicon-containing composition and the method of producing a semiconductor substrate of the embodiments of the present invention enable forming, on a silicon-containing film, a resist pattern that is superior in terms of rectangularity of a cross-sectional shape.
  • the silicon-containing composition and method of producing a semiconductor substrate of the other embodiment of the present invention enable forming a silicon-containing film that is superior in terms of removability of a silicon-containing film with a removing liquid containing a base (hereinafter, may be also referred to as “film removability”). Therefore, these can be suitably used in production of a semiconductor substrate, and the like.
  • the silicon-containing composition of one embodiment of the present invention contains the compound (A) and the solvent (B).
  • the composition may contain, within a range not leading to impairment of the effects of the present invention, other optional component(s) (hereinafter, may be merely referred to as “optional component(s)”).
  • the silicon-containing composition Due to containing the compound (A) and the solvent (B), the silicon-containing composition enables forming a resist pattern that is superior in terms of rectangularity of a cross-sectional shape, in forming the resist pattern on a silicon-containing film by development with an organic solvent. Furthermore, the silicon-containing film formed from the silicon-containing composition is superior in terms of removability of a silicon-containing film (film removability) with a removing liquid containing a base.
  • the silicon-containing composition can be suitably used as a composition for forming a silicon-containing film (i.e., composition for silicon-containing film formation).
  • a development procedure of a resist film is classified broadly into: development with an organic solvent, in which an organic solvent is used as a developer solution; and development with an alkali, in which an alkaline solution is used as a developer solution, and the silicon-containing composition is suitably used for forming an underlayer film of the resist film to be subjected to the development with an organic solvent.
  • the silicon-containing composition is used for forming an underlayer film of a resist film to be subjected to development with an organic solvent
  • development with an organic solvent is carried out after the forming and exposing of the resist film, only a light-exposed region of the resist film is dissolved, while the silicon-containing film, being the underlayer film of the resist film, is not dissolved, thereby enabling forming a resist pattern that is superior in terms of rectangularity of a cross-sectional shape.
  • the resist film to be subjected to development with an organic solvent is preferably a negative tone resist film in particular, and more preferably a negative tone resist film for exposure to an ArF excimer laser beam (for ArF exposure), described later.
  • the silicon-containing composition may be suitably used in forming an underlayer film of a resist film for ArF exposure, to be subjected to development with an organic solvent.
  • the compound (A) is a polysiloxane compound including a fluorine atom and a group including an ester bond.
  • the “ester bond” means a —C( ⁇ O)—O— bond or an —O—C( ⁇ O)— bond
  • the “group including an ester bond” may be exemplified by not only an ester group (—C( ⁇ O)—O—R) and an acyloxy group (—O—C( ⁇ O)—R), but also groups including a lactone structure, groups including a carbonate bond (—O—C( ⁇ O)—O—), and the like.
  • the “lactone structure” means a structure having at least one ring (lactone ring) including an ester bond.
  • the “polysiloxane compound” means a compound including a siloxane bond (—Si—O—Si—).
  • the compound (A) having the group including an ester bond Due to the compound (A) having the group including an ester bond, forming a silicon-containing film that is superior in terms of film removability is enabled. In addition, due to the compound (A) having a fluorine atom, forming a resist pattern that is superior in terms of rectangularity of a cross-sectional shape is enabled in forming the resist pattern on a silicon-containing film by development with an organic solvent.
  • the silicon-containing composition may contain one, or two or more types of the compound (A).
  • the fluorine atom and the group including an ester bond may be included in one type of a functional group, or these may be each included in different functional groups.
  • the group including an ester bond may be bonded directly to a silicon atom, or may be bonded to a silicon atom via another group.
  • the group including an ester bond is not particularly limited as long as it includes an ester bond, and is exemplified by an ester group, an acyloxy group, a group including a lactone structure, a group including a cyclic carbonate structure, and the like. Of these, in light of further improving the film removability, the ester group is preferred.
  • the compound (A) may have one, or two or more types of the group including an ester bond.
  • the “cyclic carbonate structure” means a structure including a ring (cyclic carbonate ring) which includes a carbonate bond (—O—C( ⁇ O)—O—).
  • the fluorine atom may be bonded directly to a silicon atom, or may be bonded to a silicon atom via another group.
  • the fluorine atom is preferably bonded to the silicon atom via another group.
  • the fluorine atom, in the compound (A) is preferably bonded to the silicon atom as a group including a fluorine atom.
  • the group including a fluorine atom is exemplified by groups obtained by substituting with a fluorine atom, at least one hydrogen atom included in an organic group, and the like.
  • groups obtained by substituting with a fluorine atom, at least one hydrogen atom included in an organic group, and the like are preferred.
  • the compound (A) is preferably a compound having a first structural unit (hereinafter, may be also referred to as “structural unit (I)”) represented by the following formula (1) described later, and a second structural unit (hereinafter, may be also referred to as “structural unit (II)”) represented by following formula (2) described later.
  • the compound (A) may have, within a range not leading to impairment of the effects of the present invention, other structural unit(s) (hereinafter, may be merely referred to as “other structural unit”) aside from the structural unit (I) and the structural unit (II).
  • the structural unit (I) is a structural unit represented by the following formula (1).
  • the compound (A) may have one, or two or more types of the structural unit (I).
  • the structural unit (I) includes a monovalent organic group having 1 to 20 carbon atoms (hereinafter, may be also referred to as “fluorine atom-containing group (X)”) which includes a fluorine atom represented by X in the following formula (1), a resist pattern having more superior rectangularity of a cross-sectional shape can be formed, in forming a resist pattern on the silicon-containing film by development with an organic solvent.
  • X represents a monovalent organic group having 1 to 20 carbon atoms and including a fluorine atom
  • a is an integer of 1 to 3, wherein in a case in which a is no less than 2, a plurality of Xs are identical or different from each other
  • R 1 represents a halogen atom, a hydroxy group, or a monovalent organic group having 1 to 20 carbon atoms
  • b is an integer of 0 to 2, wherein in a case in which b is 2, two R 1 s are identical or different from each other, and wherein a sum of a and b is no greater than 3.
  • the “organic group” means a group having at least one carbon atom, and the number of “carbon atoms” means the number of carbon atom(s) constituting a group.
  • the monovalent organic group having 1 to 20 carbon atoms in the fluorine atom-containing group (X) is exemplified by: a monovalent hydrocarbon group having 1 to 20 carbon atoms; a group (hereinafter, may be also referred to as “group ( ⁇ )”) that contains a divalent heteroatom-containing group between two adjacent carbon atoms of the monovalent hydrocarbon group; a group (hereinafter, may be also referred to as “group ( ⁇ )”) obtained by substituting with a monovalent heteroatom-containing group, a part or all of hydrogen atoms included in the monovalent hydrocarbon group or the group ( ⁇ ); a group (hereinafter, may be also referred to as “group ( ⁇ )”) obtained by combining the monovalent hydrocarbon group, the group ( ⁇ ), or the group ( ⁇ ) with a divalent heteroatom-containing group; and the like.
  • the “hydrocarbon group” may be exemplified by a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • the “hydrocarbon group” may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • the “chain hydrocarbon group” as referred to herein means a hydrocarbon group not including a ring structure but being constituted with only a chain structure, and may be exemplified by both a linear hydrocarbon group and a branched hydrocarbon group.
  • the “alicyclic hydrocarbon group” as referred to herein means a hydrocarbon group including, as a ring structure, not an aromatic ring structure but an alicyclic structure alone, and may be exemplified by both a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic hydrocarbon group. With regard to this, it is not necessary for the alicyclic hydrocarbon group to be constituted with only an alicyclic structure; and it may include a chain structure in a part thereof.
  • the “aromatic hydrocarbon group” as referred to herein means a hydrocarbon group including an aromatic ring structure as a ring structure. With regard to this, it is not necessary for the aromatic hydrocarbon group to be constituted with only an aromatic ring structure; it may include a chain structure or an alicyclic structure in a part thereof.
  • the monovalent hydrocarbon group having 1 to 20 carbon atoms is exemplified by a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
  • Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include: alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, an iso-butyl group, and a tert-butyl group; alkenyl groups such as an ethenyl group, a propenyl group, and a butenyl group; alkynyl groups such as an ethynyl group, a propynyl group, and a butynyl group; and the like.
  • Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include: monocyclic alicyclic saturated hydrocarbon groups such as a cyclopentyl group and a cyclohexyl group; polycyclic alicyclic saturated hydrocarbon groups such as a norbornyl group, an adamantyl group, a tricyclodecyl group, and a tetracyclododecyl group; monocyclic alicyclic unsaturated hydrocarbon groups such as a cyclopentenyl group and a cyclohexenyl group; polycyclic alicyclic unsaturated hydrocarbon groups such as a norbornenyl group, a tricyclodecenyl group, and a tetracyclododecenyl group; and the like.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include: aryl groups such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthryl group; aralkyl groups such as a benzyl group, a phenethyl group, a naphthylmethyl group, and an anthrylmethyl group; and the like.
  • heteroatoms which may constitute the divalent or monovalent heteroatom-containing group include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a halogen atom, and the like.
  • halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • Examples of the divalent heteroatom-containing group include —O—, —C( ⁇ O)—, —S—, —C( ⁇ S)—, —NR′—, groups obtained by combination of at least two of these, and the like.
  • R 1 represents a hydrogen atom or a monovalent hydrocarbon group.
  • Examples of the monovalent heteroatom-containing group include a halogen atom, a hydroxy group, a carboxy group, a cyano group, an amino group, a sulfanyl group, and the like.
  • the fluorine atom-containing group (X) is exemplified by organic groups having a substituent that contains a fluorine atom. Of these, hydrocarbon groups having a substituent that contains a fluorine atom are preferred, aromatic hydrocarbon groups having a substituent that contains a fluorine atom are more preferred, and aromatic hydrocarbon groups having a fluorine atom as a substituent are still more preferred.
  • the substituent that contains a fluorine atom is exemplified by a fluorine atom, groups obtained by substituting with a fluorine atom, at least one hydrogen atom included in a hydrocarbon group having 1 to 10 carbon atoms, and the like.
  • the aromatic hydrocarbon group having a substituent that contains a fluorine atom is preferably a fluorophenyl group or a pentafluorophenyl group.
  • a is preferably 1 or 2, and more preferably 1.
  • the monovalent organic group having 1 to 20 carbon atoms which may be represented by R 1 is exemplified by groups similar to the groups exemplified as the monovalent organic group having 1 to 20 carbon atoms in the aforementioned fluorine atom-containing group (X), and the like.
  • halogen atom which may be represented by R 1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 1 represents preferably the monovalent chain hydrocarbon group or a monovalent group obtained by substituting with a monovalent heteroatom-containing group, a part or all of hydrogen atoms included in the monovalent aromatic hydrocarbon group or the monovalent hydrocarbon group, more preferably the alkyl group or the aryl group, and still more preferably a methyl group, an ethyl group, or a phenyl group.
  • b is preferably 0 or 1, and more preferably 0.
  • structural unit (I) examples include structural units (hereinafter, may be also referred to as “structural units (I-1) to (I-3)”) derived from compounds represented by the following formulae (1-1) to (1-3), and the like.
  • the structural unit (I) in light of enabling forming a resist pattern having more superior rectangularity of a cross-sectional shape in forming the resist pattern on the silicon-containing film by development with an organic solvent, the structural unit (I-1) or (I-2) is preferred.
  • the lower limit of a proportion of the structural unit (I) contained in the compound (A) with respect to the total structural units constituting the compound (A) is preferably 1 mol %, more preferably 5 mol %, still more preferably 10 mol %, and particularly preferably 15 mol %.
  • the upper limit of the proportion of the structural unit (I) is preferably 50 mol %, more preferably 40 mol %, still more preferably 35 mol %, and particularly preferably 30 mol %.
  • the structural unit (II) is a structural unit represented by the following formula (2).
  • the compound (A) may have one, or two or more types of the structural unit (II).
  • the structural unit (II) enables forming a silicon-containing film that is more superior in the film removability, due to having a monovalent organic group (hereinafter, may be also referred to as “ester bond-containing group (Y)”) having 1 to 20 carbon atoms and including an ester bond represented by Y in the following formula (2).
  • Y represents a monovalent organic group having 1 to 20 carbon atoms and including an ester bond
  • c is an integer of 1 to 3, wherein in a case in which c is no less than 2, a plurality of Ys are identical or different from each other
  • R 2 represents a halogen atom, a hydroxy group, or a monovalent organic group having 1 to 20 carbon atoms
  • d is an integer of 0 to 2, wherein in a case in which d is 2, two R 2 s are identical or different from each other, and wherein a sum of c and d is no greater than 3.
  • the monovalent organic group having 1 to 20 carbon atoms in the ester bond-containing group (Y) is exemplified by groups similar to the groups exemplified as the monovalent organic group having 1 to 20 carbon atoms in the fluorine atom-containing group (X) in the above formula (1), and the like.
  • the ester bond-containing group (Y) is exemplified by a group including an ester group, a group including an acyloxy group, a group including a lactone structure, a group including a cyclic carbonate structure, and the like.
  • ester bond-containing group (Y-1) represented by the following formula (3-1), and the like.
  • L 1 represents a single bond or a divalent linking group
  • R 3 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms
  • * denotes a site bonding to the silicon atom in the above formula (2).
  • the divalent linking group which may be represented by L 1 is exemplified by a divalent organic group having 1 to 10 carbon atoms, and the like.
  • Exemplary divalent organic groups having 1 to 10 carbon atoms include groups obtained by removing one hydrogen atom from the monovalent organic group having 1 to 10 carbon atoms, among the groups exemplified as the monovalent organic group having 1 to 20 carbon atoms in the fluorine atom-containing group (X) in the above formula (1), and the like.
  • L 1 represents preferably a single bond, the divalent hydrocarbon group having 1 to 10 carbon atoms, or a group including a divalent heteroatom-containing group between adjacent carbon atoms of the divalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a single bond, an alkylene group, or a group including —S— between adjacent carbon atoms of an alkenylene group or an alkylene group.
  • Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 3 include the monovalent hydrocarbon groups having 1 to 10 carbon atoms, among the groups exemplified as the monovalent hydrocarbon group having 1 to 20 carbon atoms in the fluorine atom-containing group (X) in the above formula (1), and the like.
  • R 3 represents preferably the monovalent chain hydrocarbon group or the monovalent alicyclic hydrocarbon group. Furthermore, R 3 represents preferably a group that is capable of bonding to an ethereal oxygen atom of a carbonyloxy group at the tertiary carbon atom. Examples of such a group include a tert-butyl group, a 1-methylcyclopentan-1-yl group, and the like.
  • the group including an acyloxy group is exemplified by a group (hereinafter, may be also referred to as “ester bond-containing group (Y-2)”) represented by the following formula (3-2), and the like.
  • L 2 represents a single bond or a divalent linking group
  • R 4 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms
  • * denotes a site bonding to the silicon atom in the above formula (2).
  • the divalent linking group which may be represented by L 2 is exemplified by groups similar to the groups exemplified as L 1 in the above formula (3-1), and the like.
  • L 2 represents preferably a single bond, a methylene group, or a divalent alkylene group having 2 to 10 carbon atoms, and more preferably a methylene group.
  • the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 4 is exemplified by groups similar to the groups exemplified as R 3 in the above formula (3-1), and the like.
  • R 4 represents preferably the monovalent chain hydrocarbon group.
  • the group including a lactone structure is exemplified by a group (hereinafter, may be also referred to as “ester bond-containing group (Y-3)”) represented by the following formula (3-3), and the like.
  • L 3 represents a single bond or a divalent linking group
  • R 5 represents a monovalent group having a lactone structure
  • * denotes a site bonding to the silicon atom in the above formula (2).
  • the divalent linking group which may be represented by L 3 is exemplified by groups similar to the groups exemplified as L 1 in the above formula (3-1), and the like.
  • L 3 represents preferably a single bond.
  • Examples of the lactone structure in R 5 include: monocyclic lactone structures such as a propiolactone structure, a butyrolactone structure, a valerolactone structure, and a caprolactone structure; polycyclic lactone structures such as a cyclopentanelactone structure, a cyclohexanelactone structure, a norbornanelactone structure, a benzobutyrolactone structure, and a benzovalerolactone structure; and the like. Of these, the monocyclic lactone structures are preferred, and a butyrolactone structure is more preferred.
  • the group including a cyclic carbonate structure is exemplified by a group (hereinafter, may be also referred to as “ester bond-containing group (Y-4)”) represented by the following formula (3-4), and the like.
  • L 4 represents a single bond or a divalent linking group
  • R 6 represents a monovalent group having a cyclic carbonate structure
  • * denotes a site bonding to the silicon atom in the above formula (2).
  • the divalent linking group which may be represented by L 4 is exemplified by groups similar to the groups exemplified as L 1 in the above formula (3-1), and the like.
  • L 4 represents preferably the divalent alkylene group having 2 to 10 carbon atoms.
  • Examples of the cyclic carbonate structure in R 6 include: monocyclic cyclic carbonate structures such as an ethylene carbonate structure, a trimethylene carbonate structure, and a tetramethylene carbonate structure; polycyclic carbonate structures such as a cyclopentylene carbonate structure, a cyclohexylene carbonate structure, a norbomylene carbonate structure, a phenylene carbonate structure, and a naphthylene carbonate structure; and the like.
  • monocyclic cyclic carbonate structures such as an ethylene carbonate structure, a trimethylene carbonate structure, and a tetramethylene carbonate structure
  • polycyclic carbonate structures such as a cyclopentylene carbonate structure, a cyclohexylene carbonate structure, a norbomylene carbonate structure, a phenylene carbonate structure, and a naphthylene carbonate structure
  • the monocyclic cyclic carbonate structures are preferred, and the ethylene carbonate structure is more
  • the ester bond-containing group (Y) is, in light of further improving the film removability, preferably the ester bond-containing group (Y-1).
  • c is preferably 1 or 2, and more preferably 1.
  • the monovalent organic group having 1 to 20 carbon atoms which may be represented by R 2 is exemplified by groups similar to the groups exemplified as the monovalent organic group having 1 to 20 carbon atoms in the fluorine atom-containing group (X) in the above formula (1), and the like.
  • halogen atom which may be represented by R 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 2 represents preferably the monovalent chain hydrocarbon group, the monovalent aromatic hydrocarbon group, or the monovalent group obtained by substituting with the monovalent heteroatom-containing group, a part or all of hydrogen atoms included in the monovalent hydrocarbon group, more preferably the alkyl group or the aryl group, and still more preferably a methyl group, an ethyl group, or a phenyl group.
  • d is preferably 0 or 1, and more preferably 0.
  • structural unit (II) examples include structural units (hereinafter, may be also referred to as “structural units (II-1) to (II-8)”) derived from compounds represented by the following formulae (2-1) to (2-8), and the like.
  • the structural unit (II) is, in light of further improving the film removability, preferably one of the structural units (II-1) to (II-4) and (II-6), and more preferably one of the structural units (II-1) to (II-4).
  • the lower limit of a proportion of the structural unit (II) contained in the compound (A) with respect to the total structural units constituting the compound (A) is preferably 0.5 mol %, more preferably 1 mol %, and still more preferably 2 mol %. Furthermore, the upper limit of the proportion of the structural unit (II) is preferably 30 mol %, more preferably 25 mol %, and still more preferably 20 mol %. When the proportion of the structural unit (II) falls within the above range, the silicon-containing film can be formed being more superior in the film removability.
  • Structural unit (III) a Structural Unit represented by the following formula (4)
  • structural unit (IV) a structural unit represented by the following formula (5) described later, and the like.
  • structural unit (III) storage stability and coating characteristics of the silicon-containing composition can be improved.
  • structural unit (IV) resistance to etching with oxygen gas of the silicon-containing film formed from the silicon-containing composition can be improved.
  • R 7 represents a halogen atom, a hydroxy group, or a monovalent organic group having 1 to 20 carbon atoms; and e is an integer of 1 to 3, wherein in a case in which e is no less than 2, a plurality of R 7 s are identical or different from each other.
  • the monovalent organic group having 1 to 20 carbon atoms which may be represented by R 7 is exemplified by groups similar to the groups exemplified as the monovalent organic group having 1 to 20 carbon atoms in the fluorine atom-containing group (X) in the above formula (1), and the like.
  • halogen atom which may be represented by R 7 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 7 represents preferably the monovalent aromatic hydrocarbon group, more preferably the aryl group, and still more preferably a phenyl group.
  • e is preferably 1.
  • the lower limit of a proportion of the structural unit (III) with respect to the total structural units constituting the compound (A) is preferably 1 mol %, more preferably 5 mol %, and still more preferably 10 mol %.
  • the upper limit of the proportion is preferably 40 mol %, more preferably 30 mol %, and still more preferably 25 mol %.
  • the lower limit of a proportion of the structural unit (IV) with respect to the total structural units constituting the compound (A) is preferably 30 mol %, more preferably 40 mol %, and still more preferably 50 mol %.
  • the upper limit of the proportion is preferably 95 mol %, more preferably 90 mol %, and still more preferably 85 mol %.
  • the lower limit of a proportion of the compound (A) contained in the silicon-containing composition with respect to total components contained in the silicon-containing composition is preferably 0.1% by mass, more preferably 0.5% by mass, and still more preferably 1% by mass.
  • the upper limit of the proportion is preferably 10% by mass, more preferably 7.5% by mass, and still more preferably 5% by mass.
  • the compound (A) preferably has a form of a polymer.
  • a “polymer” as referred to herein means a compound having no less than two structural units; in a case in which an identical structural unit repeats twice or more, this structural unit may be also referred to as a “repeating unit.”
  • the lower limit of a polystyrene equivalent weight average molecular weight (Mw) of the compound (A) as determined by gel permeation chromatography is preferably 1,000, more preferably 1,200, still more preferably 1,500, and particularly preferably 1,600.
  • the upper limit of the Mw is preferably 10,000, more preferably 5,000, still more preferably 3,000, and particularly preferably 2,500.
  • the Mw of the compound (A) is a value measured by gel permeation chromatography (GPC) using GPC columns available from Tosoh Corporation (“G2000 HXL” ⁇ 2, “G3000 HXL” ⁇ 1, and “G4000 HXL” ⁇ 1) under the following conditions.
  • the compound (A) can be synthesized by using a monomer that gives each structural unit according to a common procedure.
  • the compound (A) can be obtained by: carrying out hydrolytic condensation with a monomer that gives the structural unit (I) and a monomer that gives the structural unit (II), as well as, as necessary, monomer(s) that give(s) the other structural unit(s), in a solvent in the presence of water and a catalyst such as oxalic acid; and preferably subjecting a solution including a thus generated hydrolytic condensation product to purification by solvent substitution or the like in the presence of a dehydrating agent such as orthoformic acid trimethyl ester.
  • a dehydrating agent such as orthoformic acid trimethyl ester.
  • the solvent (B) is not particularly limited and is exemplified by an alcohol solvent, a ketone solvent, an ether solvent, an ester solvent, a nitrogen-containing solvent, water, and the like.
  • the silicon-containing composition may contain one, or two or more types of the solvent (B).
  • the alcohol solvent examples include: monohydric alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, and iso-butanol; polyhydric alcohol solvents such as ethylene glycol, 1,2-propylene glycol, diethylene glycol, and dipropylene glycol; and the like.
  • ketone solvent examples include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl iso-butyl ketone, cyclohexanone, and the like.
  • ether solvent examples include ethyl ether, isopropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, tetrahydrofuran, and the like.
  • ester solvent examples include ethyl acetate, ⁇ -butyrolactone, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethyl propionate, n-butyl propionate, methyl lactate, ethyl lactate, and the like.
  • nitrogen-containing solvent examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.
  • the ether solvent or the ester solvent is preferred, and due to superiority in film formability, the ether solvent having a glycol structure or the ester solvent having a glycol structure is more preferred.
  • Examples of the ether solvent having a glycol structure and the ester solvent having a glycol structure include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like. Of these, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether are preferred, and propylene glycol monomethyl ether is more preferred.
  • the lower limit of a proportion of the solvent (B) contained in the silicon-containing composition with respect to total components contained in the silicon-containing composition is preferably 90% by mass, more preferably 92.5% by mass, and still more preferably 95% by mass.
  • the upper limit of the proportion is preferably 99.9% by mass, more preferably 99.5% by mass, and still more preferably 99% by mass.
  • the optional component(s) is/are exemplified by an acid generating agent, a basic compound (including a base generating agent), a radical generating agent, a surfactant, colloidal silica, colloidal alumina, an organic polymer, and the like.
  • the silicon-containing composition may contain one, or two or more types of the optional component.
  • the proportion of the optional component(s) contained in the silicon-containing composition may be appropriately determined in accordance with the type of the optional component(s) used, and to fall within a range not leading to impairment of the effects of the present invention.
  • a procedure of preparing the silicon-containing composition is not particularly limited, and the silicon-containing composition may be prepared according to a common procedure.
  • the silicon-containing composition may be prepared by, for example: mixing at a predetermined ratio, a solution of the compound (A), the solvent (B), and as needed, the optional component(s); and preferably filtering a resulting mixture through a filter, etc. having a pore size of no greater than 0.2 ⁇ m.
  • the method of producing a semiconductor substrate of the other embodiment of the present invention includes: a step (hereinafter, may be also referred to as “applying step of a silicon-containing composition”) of applying a silicon-containing composition directly or indirectly on a substrate; a step (hereinafter, may be also referred to as “applying step of a composition for resist film formation”) of applying a composition for resist film formation directly or indirectly on a silicon-containing film formed by the applying of a silicon-containing composition; a step (hereinafter, may be also referred to as “exposing step”) of exposing to a radioactive ray, a resist film formed by the applying step of a composition for resist film formation; and a step (hereinafter, may be also referred to as “development step with an organic solvent”) of developing with an organic solvent, the resist film exposed.
  • the silicon-containing composition is used as the silicon-containing composition.
  • the method of producing a semiconductor substrate may further include, as needed, a step (hereinafter, may be also referred to as “forming step of an organic underlayer film”) of forming an organic underlayer film directly or indirectly on the substrate, before the applying step of a silicon-containing composition.
  • a step hereinafter, may be also referred to as “forming step of an organic underlayer film” of forming an organic underlayer film directly or indirectly on the substrate, before the applying step of a silicon-containing composition.
  • the method of producing a semiconductor substrate may further include, as needed, a step (hereinafter, may be also referred to as “removing step”) of removing the silicon-containing film with a removing liquid containing a base, after the applying step of a silicon-containing composition.
  • a step hereinafter, may be also referred to as “removing step” of removing the silicon-containing film with a removing liquid containing a base, after the applying step of a silicon-containing composition.
  • the silicon-containing composition of the aforementioned one embodiment being used as the silicon-containing composition in the applying step of a silicon-containing composition, forming a resist pattern that is superior in terms of rectangularity of a cross-sectional shape on the silicon-containing film is enabled.
  • the silicon-containing film formed by the applying step of a silicon-containing composition can be removed with a removing liquid containing a base, due to the silicon-containing being superior in film removability.
  • the silicon-containing composition is applied directly or indirectly on a substrate.
  • a coating film of the silicon-containing composition is formed directly or indirectly on the substrate and the silicon-containing film is formed by, e.g., subjecting the coating film to, typically, heating, thereby allowing for hardening.
  • the silicon-containing composition described above is used as the silicon-containing composition.
  • the substrate is exemplified by insulating films of silicon oxide, silicon nitride, a silicon oxynitride, a polysiloxane, or the like; resin substrates; and the like. Furthermore, as the substrate, a substrate having a pattern formed thereon with wiring grooves (trenches), plug grooves (vias), or the like may be used.
  • a procedure for applying the composition for silicon-containing film formation is not particularly limited, and for example, spin-coating or the like may be exemplified.
  • the case of applying the composition for silicon-containing film formation indirectly on the substrate may be exemplified by a case in which the silicon-containing composition is applied on an other film formed on the substrate, and the like.
  • the other film formed on the substrate is exemplified by an organic underlayer film, an antireflective film, or a low-dielectric insulating film formed by the forming step of an organic underlayer film, to be described later, and the like.
  • the atmosphere thereof is not particularly limited, and may be, for example, an ambient air, a nitrogen atmosphere, or the like.
  • the coating film is subjected to heating in the ambient air.
  • Various conditions such as a heating temperature and a heating time period in subjecting the coating film to heating may be predetermined appropriately.
  • the lower limit of the heating temperature is preferably 90° C., more preferably 150° C., and still more preferably 200° C.
  • the upper limit of the heating temperature is preferably 550° C., more preferably 450° C., and still more preferably 300° C.
  • the lower limit of the heating time period is preferably 15 sec, and more preferably 30 sec.
  • the upper limit of the heating time period is preferably 1,200 sec, and more preferably 600 sec.
  • the composition for silicon-containing film formation contains the acid generating agent and the acid generating agent is a radiation-sensitive acid generating agent
  • formation of the silicon-containing film may be further promoted through a combination of an exposure and heating.
  • the radioactive ray which can be used for the exposure include radioactive rays similar to those exemplified in connection with the exposing step described later.
  • the lower limit of an average thickness of the silicon-containing film to be formed by this step is preferably 1 nm, more preferably 3 nm, and still more preferably 5 nm.
  • the upper limit of the average thickness is preferably 500 nm, more preferably 300 nm, and still more preferably 200 nm. It is to be noted that the average thickness of the silicon-containing film is a value measured by using a spectroscopic ellipsometer (“M2000D,” available from J.A. Woollam Co.).
  • a composition for resist film formation is applied directly or indirectly on the silicon-containing film formed by the applying step of a silicon-containing composition.
  • the resist film is directly or indirectly formed on the silicon-containing film.
  • a procedure for applying the composition for resist film formation is not particularly limited, and for example, spin-coating or the like may be exemplified.
  • the resist film is formed by: applying the resist composition such that a resultant resist film has a predetermined thickness; and thereafter subjecting the resist composition to prebaking (hereinafter, may be also referred to as “PB”) to evaporate the solvent in the coating film.
  • prebaking hereinafter, may be also referred to as “PB”
  • a PB temperature and a PB time period of may be appropriately predetermined in accordance with the type and the like the composition for resist film formation employed.
  • the lower limit of the PB temperature is preferably 30° C., and more preferably 50° C.
  • the upper limit of the PB temperature is preferably 200° C., and more preferably 150° C.
  • the lower limit of the PB time period is preferably 10 sec, and more preferably 30 sec.
  • the upper limit of the PB time period is preferably 600 sec, and more preferably 300 sec.
  • development procedures of a resist film are classified broadly into development with an organic solvent in which an organic solvent is used as a developer solution, and development with an alkali in which an alkaline solution is used as a developer solution.
  • the composition for resist film formation used in this applying step is limited to a composition for resist film formation that enables forming a resist film to be subjected to development with an organic solvent.
  • the reason for this limitation is that in the case in which a composition for resist film formation that enables forming a resist film to be subjected to development with an alkali, not only a light-exposed region of the resist film but also the silicon-containing film situated on or above the underlayer of the resist film formed by the applying step of a silicon-containing composition is dissolved in the alkaline developer solution, in a development step with an alkali.
  • the composition for resist film formation used in this step is not particularly limited as long as it enables forming a resist film to be subjected to development with an organic solvent, and a well-known composition for resist film formation can be used.
  • a composition for negative tone resist film formation containing a radiation-sensitive acid generating agent, or the like may be employed.
  • a composition for negative tone resist film formation, for use in exposure to an ArF excimer laser beam (for ArF exposure), described later, is preferred.
  • the resist film formed by the applying step of a composition for resist film formation is exposed to a radioactive ray.
  • a difference in solubility in an organic solvent as a developer solution is created between the light-exposed regions and light-unexposed regions of the resist film.
  • the solubility in an organic solvent of the light-exposed regions of the resist film is decreased.
  • the radioactive ray used in the exposure may be appropriately selected in accordance with the type, etc., of the composition for resist film formation used.
  • the radioactive ray include: electromagnetic waves such as visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, and ⁇ -rays; and particle rays such as electron beams, molecular beams, and ion beams.
  • a KrF excimer laser beam (wavelength: 248 nm), an ArF excimer laser beam (wavelength: 193 nm), an F 2 excimer laser beam (wavelength: 157 nm), a Kr 2 excimer laser beam (wavelength: 147 nm), an ArKr excimer laser beam (wavelength: 134 nm), or an extreme ultraviolet ray (wavelength: 13.5 nm, etc.; may be also referred to as “EUV”) is more preferred, and an ArF excimer laser beam is still more preferred.
  • the exposure conditions may be appropriately predetermined in accordance with the type, etc., of the composition for resist film formation used.
  • PEB post exposure baking
  • a PEB temperature and a PEB time period may be appropriately predetermined in accordance with the type and the like of the composition for resist film formation employed.
  • the lower limit of the PEB temperature is preferably 50° C., and more preferably 70° C.
  • the upper limit of the PEB temperature is preferably 200° C., and more preferably 150° C.
  • the lower limit of the PEB time period is preferably 10 sec, and more preferably 30 sec.
  • the upper limit of the PEB time period is preferably 600 sec, and more preferably 300 sec.
  • the resist film exposed is developed with an organic solvent. Since the difference in solubility in an organic solvent as a developer solution is created between the light-exposed regions and light-unexposed regions of the resist film by the exposing step, carrying out the development with an organic solvent enables forming a resist pattern by removing portions having relatively higher solubility in the organic solvent.
  • the resist pattern is formed by removing regions unexposed with light, which have relatively higher solubility in the organic solvent, through carrying out the development with the organic solvent.
  • the developer solution used in the development with an organic solvent is not particularly limited as long as the developer solution is for use in development with an organic solvent, and any well-known developer solution may be used.
  • a developer solution similar to those exemplified as the solvent (B) in the silicon-containing composition, described above, or the like may be employed.
  • washing and/or drying may be carried out.
  • an organic underlayer film is formed directly or indirectly on the substrate.
  • This step is an arbitrary step.
  • the organic underlayer film is formed directly or indirectly on the substrate.
  • the expression “before the applying step of a silicon-containing composition” as referred to herein means not only immediately before the applying step of a silicon-containing composition, but means any time point upstream of the applying step of a silicon-containing composition. Therefore, other arbitrary step(s) may be included between this forming step and the applying step of a silicon-containing composition.
  • the organic underlayer film can be formed by applying a composition for organic underlayer film formation, or the like.
  • a procedure of forming the organic underlayer film by applying the composition for organic underlayer film formation is exemplified by a procedure of applying the composition for silicon-containing film formation directly or indirectly on the substrate to form a coating film; and hardening the coating film by subjecting the coating film to an exposure and/or heating.
  • the composition for organic underlayer film formation include “HM8006,” available from JSR Corporation, and the like. Conditions for the heating and/or the exposure may be appropriately predetermined in accordance with the type, etc., of the composition for organic underlayer film formation used.
  • the case of forming the organic underlayer film indirectly on the substrate may be exemplified by a case of forming the organic underlayer film on a low-dielectric insulating film formed on the substrate, and the like.
  • the silicon-containing film is removed with a removing liquid containing a base (hereinafter, may be also referred to as “base-containing removing liquid”).
  • base-containing removing liquid a removing liquid containing a base
  • This step is an arbitrary step.
  • the silicon-containing film is removed from the substrate.
  • the expression “after the applying step of a silicon-containing composition” as referred to means not only immediately after the applying step of a silicon-containing composition, but means any time point downstream of the applying step of the silicon-containing composition. Therefore, the expression “after the applying step of a silicon-containing composition” may involve being after the applying step of a silicon-containing composition, and not only before the applying step of a composition for resist film formation, but also, for example, after the development step with an organic solvent.
  • the silicon-containing film can be easily removed as a rework step when defects and/or the like are detected on the silicon-containing film before the applying step of a composition for resist film formation.
  • residues of the silicon-containing film after the etching can be removed.
  • the base-containing removing liquid is not particularly limited, as long as it is a basic solution containing a base.
  • the base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (hereinafter, may be also referred to as “TMAH”), tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, and the like.
  • TMAH tetramethylammonium hydroxide
  • the base-containing removing liquid in light of further improving removability of the silicon-containing film, a liquid containing the base and water, or a liquid containing a base, hydrogen peroxide, and water is preferred.
  • a procedure of removing the silicon-containing film is not particularly limited as long as the procedure enables bringing the silicon-containing film to be in contact with the base-containing removing liquid, and the procedure is exemplified by: immersing the substrate in the base-containing removing liquid; spraying the base-containing removing liquid; applying the base-containing removing liquid; and the like.
  • various conditions such as a temperature and a time period are not particularly limited, and may be appropriately predetermined in accordance with a film thickness of the silicon-containing film, the type of the base-containing removing liquid used, and the like.
  • the lower limit of the temperature is preferably 20° C., more preferably 40° C., and still more preferably 50° C.
  • the upper limit of the temperature is preferably 300° C., and more preferably 100° C.
  • the lower limit of the time period is preferably 5 sec, and more preferably 30 sec.
  • the upper limit of the time period is preferably 10 min, and more preferably 180 sec.
  • washing and/or drying may be carried out.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the concentration (unit: % by mass) of the compound (A) in the solution was determined by: baking 0.5 g of the solution of the compound (A) at 250° C. for 30 min; measuring a mass of a residue thus obtained; and dividing the mass of the residue by the mass of the solution of the compound (A).
  • the average thickness of the film was measured by using a spectroscopic ellipsometer (“M2000D,” available from J.A. Woollam Co.).
  • Monomers (hereinafter, may be also referred to as “monomers (M-1) to (M-13)”) used for synthesis in Examples 1-1 to 1-21 and Comparative Examples 1-1 and 1-2 are presented below. Furthermore, in the following Examples 1-1 to 1-21 and Comparative Examples 1-1 and 1-2, the term “mol %” means a value, provided that the total mol number of the monomers (M-1) to (M-13) used was 100 mol %.
  • a monomer solution was prepared by dissolving in 62 parts by mass of propylene glycol monoethyl ether, the compound (M-1), the compound (M-3), and the compound (M-6) such that the molar ratio became 84/15/1 (by mol %).
  • the internal temperature of the reaction vessel was adjusted to 60° C., and 40 parts by mass of a 9.1% by mass aqueous oxalic acid solution were added dropwise over 20 min with stirring. A time point of starting the dropwise addition was defined as a start time of the reaction, and the reaction was performed for 4 hrs. After completion of the reaction, the internal temperature of the reaction vessel was lowered to no greater than 30° C.
  • Examples 1-2 to 1-21, and Comparative Examples 1-1 and 1-2 Synthesis of Compounds (A-2) to (A-21), (AJ-1), and (AJ-2)
  • each silicon-containing composition is shown below. It is to be noted that in Examples 2-1 to 2-21 and Comparative Examples 2-1 and 2-2 below, unless otherwise specified particularly, the term “parts by mass” means a value, provided that the total mass of the components used was 100 parts by mass.
  • Silicon-containing composition (J-1) was prepared by: mixing 1 part by mass (not including the solvent) of (A-1) as the compound (A), and 99 parts by mass (including the solvent contained in the solution of the compound (A)) of (B-1) as the solvent (B); and filtering a resulting solution through a polytetrafluoroethylene filter having a pore size of 0.2 ⁇ m.
  • Silicon-containing compositions (J-2) to (J-17) of Examples 2-2 to 2-21, and silicon-containing compositions (j-1) and (j-2) of Comparative Examples 2-1 and 2-2 were prepared by a similar operation to that of Example 2-1 except that for each component, the type and the blended amount shown in Table 2 below were used.
  • compositions prepared as described above were evaluated with regard to resist pattern configuration and film removability with an alkali-liquid by the following methods.
  • the results of the evaluations are shown in Table 2 below.
  • a material for organic underlayer film formation (“HM8006,” available from JSR Corporation) was applied on a 12-inch silicon wafer by spin-coating using a spin-coater (“CLEAN TRACK ACT 12,” available from Tokyo Electron Limited), and thereafter heating was conducted at 250° C. for 60 sec to form an organic underlayer film having an average thickness of 100 nm.
  • Each silicon-containing composition prepared as described above was applied on the organic underlayer film, and subjected to heating at 220° C. for 60 sec, followed by cooling at 23° C. for 30 sec to form a silicon-containing film having an average thickness of 20 nm.
  • a radiation-sensitive resin composition (“ARF AR2772JN” available from JSR Corporation) was applied on each silicon-containing film formed as described above, and heating was conducted at 90° C. for 60 sec, followed by cooling at 23° C. for 30 sec to form a resist film having an average thickness of 100 nm.
  • an ArF immersion scanner (“S610C” available from Nikon Corporation) was used to conduct an exposure through a mask with a mask size for forming 40 nm line/80 nm pitch under optical conditions involving NA of 1.30 and Dipole.
  • the substrate was heated at 100° C. for 60 sec, followed by cooling at 23° C. for 60 sec. Thereafter, a development was carried out using n-butyl acetate (20° C.
  • a substrate for evaluation having a resist pattern formed thereon.
  • a scanning electron microscope (“CG-4000,” available from Hitachi High-Technologies Corporation) was used.
  • CG-4000 scanning electron microscope
  • an exposure dose at which a 1:1 line and space pattern with a line width of 40 nm was formed was defined as an optimum exposure dose.
  • the resist pattern configuration was evaluated to be: “A” (favorable) in a case of the cross-sectional shape of the pattern being rectangular; “B” (somewhat favorable) in a case of the cross section of the pattern being accompanied by tailing; or “C” (unfavorable) in a case of a residue (defect) existing on the pattern.
  • Each silicon-containing composition prepared as described above was applied on a 12-inch silicon wafer, and subjected to heating at 220° C. for 60 sec, followed by cooling at 23° C. for 30 sec to form a silicon-containing film having an average thickness of 20 nm.
  • a cross section of each substrate for evaluation thus obtained was observed using a field emission scanning electron microscope (“SU8220,” available from Hitachi High-Technologies Corporation), and was evaluated to be: “A” (favorable) in a case of the silicon-containing film not remaining after being immersed in the removing liquid for 5 min; “B” (somewhat favorable) in a case of the silicon-containing film remaining after being immersed in the removing liquid for 5 min, and the silicon-containing film not remaining after being immersed in the removing liquid for 10 min; or “C” (unfavorable) in a case of the silicon-containing film remaining after being immersed in the removing liquid for 5 min and for 10 min.
  • SU8220 field emission scanning electron microscope
  • the silicon-containing films formed from the silicon-containing compositions of the Examples enabled forming thereon a resist pattern that is superior in terms of rectangularity of a cross-sectional shape, as compared with the silicon-containing films formed from the silicon-containing compositions of the Comparative Examples. Furthermore, the silicon-containing films formed from the silicon-containing compositions of the Examples exhibited favorable film removability, as compared with the silicon-containing films formed from the silicon-containing compositions of the Comparative Examples.
  • the silicon-containing composition and the method of producing a semiconductor substrate of the embodiments of the present invention enable forming a resist pattern that is superior in terms of rectangularity of the cross-sectional shape, and forming an easily removable silicon-containing film. Therefore, these can be suitably used in production of a semiconductor substrate, and the like.

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