WO2016159329A1 - Composition de formation de motif et procédé de formation de motif - Google Patents

Composition de formation de motif et procédé de formation de motif Download PDF

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WO2016159329A1
WO2016159329A1 PCT/JP2016/060853 JP2016060853W WO2016159329A1 WO 2016159329 A1 WO2016159329 A1 WO 2016159329A1 JP 2016060853 W JP2016060853 W JP 2016060853W WO 2016159329 A1 WO2016159329 A1 WO 2016159329A1
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group
pattern
self
block
pattern forming
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PCT/JP2016/060853
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English (en)
Japanese (ja)
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裕之 小松
智博 小田
雅史 堀
岳彦 成岡
永井　智樹
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Jsr株式会社
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Priority to KR1020177027155A priority Critical patent/KR102604419B1/ko
Priority to JP2017510241A priority patent/JP6652721B2/ja
Publication of WO2016159329A1 publication Critical patent/WO2016159329A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • the present invention relates to a pattern forming composition and a pattern forming method.
  • pattern miniaturization is required in the pattern formation process.
  • a method of forming a self-organized pattern using a so-called self-organized phase separation (microdomain) structure that spontaneously forms an ordered pattern has been proposed.
  • a method for forming such a self-assembled pattern a block copolymer obtained by copolymerizing a monomer compound having specific properties and a monomer compound having different properties is used, and an ultrafine pattern is formed by self-assembly.
  • There are known methods for forming see JP 2008-149447 A, JP 2002-519728 A and JP 2003-218383 A). According to this method, by annealing the film containing the block copolymer, it is possible to form a pattern in a self-aligning manner by utilizing the property that polymer structures having the same properties are gathered together.
  • the present invention has been made based on the circumstances as described above, and the purpose thereof is a pattern capable of forming a self-assembled film with few defects in a regular arrangement structure and thus forming a pattern with a good shape.
  • the object is to provide a forming composition and a pattern forming method.
  • the invention made in order to solve the above problems includes a block copolymer (hereinafter also referred to as “[A] block copolymer”) that forms a phase separation structure by self-assembly, and a solvent (hereinafter referred to as “[B A first block comprising a substituted or unsubstituted styrene unit (hereinafter also referred to as “repeating unit (I)”). (Hereinafter also referred to as “block (a)”) and a second block (hereinafter also referred to as “block (b)”) comprising a (meth) acrylate unit (hereinafter also referred to as “repeating unit (II)”).
  • group (1) a first group (hereinafter also referred to as “group (1)”) bonded to at least one end of the main chain, and the group (1) binds a methyl group to the main chain side bond.
  • ClogP is -1 or more and 3 or less when Characterized in that it is a monovalent group which forms a compound.
  • Another invention made to solve the above-described problems includes a step of forming a phase-separated self-assembled film on one surface side of the substrate (hereinafter also referred to as a “self-assembled film forming step”), and the self
  • This is a pattern forming method including a step of removing a part of the organized film (hereinafter also referred to as “removing step”), and forming the self-assembled film with the pattern forming composition.
  • Directed Self Assembly refers to a phenomenon in which an organization or structure is spontaneously built without being caused only by control from an external factor.
  • Main chain refers to a chain composed of carbon atoms derived from carbon atoms constituting a polymerizable carbon-carbon double bond of a monomer in a block copolymer. However, the said chain
  • Terminal in “at least one terminal of the main chain” means that no bond is formed with the adjacent repeating unit among the carbon atoms of the main chain of the repeating unit located at the end of the block copolymer. Refers to a carbon atom.
  • ClogP is also referred to as “ClogPow”, and is a value of the octanol / water partition coefficient (logP) calculated by the ClogP method. The larger the value, the higher the hydrophobicity (lipid solubility).
  • the pattern forming composition and the pattern forming method of the present invention it is possible to form a self-assembled film with few defects in a regular array structure, and thus to form a pattern with a good shape. Therefore, they can be suitably used in pattern formation processes in the manufacture of various electronic devices such as semiconductor devices and liquid crystal devices that are required to be further miniaturized.
  • FIG. 2 is a schematic cross-sectional view illustrating an example of a state after forming a pre-pattern on the lower layer film in FIG. 1. It is typical sectional drawing which shows an example after forming a coating film with the composition for pattern formation between the pre-patterns in FIG. It is typical sectional drawing which shows an example of the state after making the coating film in FIG. 3 into a self-organization film
  • FIG. 5 is a schematic cross-sectional view showing an example of a state after removing a part of phases and a pre-pattern of the self-assembled film in FIG. 4.
  • the composition for pattern formation of this invention contains a [A] block copolymer and a [B] solvent.
  • the pattern forming composition may contain other optional components as long as the effects of the present invention are not impaired.
  • the block copolymer has a block (a), a block (b), and a group (1), and forms a phase separation structure by self-assembly.
  • Each of the blocks is composed of a chain structure of repeating units derived from one type of monomer.
  • the same type of blocks are aggregated by heating or the like to form a phase composed of the same type of blocks.
  • phases formed from different types of blocks do not mix with each other, it is presumed that a phase separation structure having an ordered pattern in which different types of phases are periodically and alternately repeated can be formed.
  • the composition can form a self-assembled film with few defects in the ordered arrangement structure.
  • the group (1) is a relatively highly hydrophilic group that forms a compound having a ClogP of ⁇ 1 or more and 3 or less, assuming that a methyl group is bonded to the main chain side bond. Therefore, by bonding the group (1) to at least one terminal of the main chain, the hydrophilicity of the terminal of the block to which the group (1) is connected can be increased. As a result, the physical property difference such as polarity between the block (a) composed of the relatively hydrophobic repeating unit (I) and the block (b) composed of the relatively hydrophilic repeating unit (II) is moderate. Therefore, it is considered that a self-assembled film with few defects in the regular arrangement structure can be formed.
  • the block copolymer may further have a block composed of a repeating unit other than the repeating unit (I) and the repeating unit (II). Moreover, the [A] block copolymer may have 1 type or multiple types of block (a), and may have 1 type or multiple types of block (b).
  • Examples of the block copolymer include a diblock copolymer having 2 blocks, a triblock copolymer having 3 blocks, and a tetrablock copolymer having 4 blocks. .
  • the block copolymer may be either a linear polymer or a branched polymer.
  • the number of arms of the star copolymer can be, for example, 2 or more and 7 or less.
  • the star copolymer examples include an asymmetric star copolymer (Miktoarm copolymer).
  • asymmetric star copolymer refers to a star copolymer in which each arm is formed of a different monomer, and is different from a symmetric star polymer in which each arm is formed of the same monomer. Refers to things.
  • [A] block copolymers are preferably linear polymers.
  • the [A] block copolymer is a diblock copolymer and a triblock copolymer from the viewpoint of easily forming a desired fine pattern. More preferred are polymers, and even more preferred are diblock copolymers.
  • the block copolymer may have a linking group between the blocks. Hereinafter, each block, group (1) and linking group will be described.
  • Block (a) Block (a) consists of repeating unit (I).
  • the repeating unit (I) is a substituted or unsubstituted styrene unit.
  • repeating unit (I) is a substituted styrene unit
  • substituent replacing the styrene unit include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and an isobutyl group.
  • Alkyl groups having 1 to 20 carbon atoms such as tert-butyl group; An alkenyl group such as an ethenyl group; Alkoxy groups such as methoxy group and tert-butoxy group; Groups containing heteroatoms such as an acetoxy group, a nitro group, a cyano group; Examples thereof include groups containing halogen atoms such as chlorine atom, bromine atom and iodine atom.
  • an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 4 carbon atoms is more preferable, and a tert-butyl group is particularly preferable.
  • the bonding site of the substituent may be a main chain portion of the styrene unit (carbon derived from two carbon atoms constituting the polymerizable carbon-carbon double bond of styrene), or the ortho position of the aromatic ring of the styrene unit, It may be in meta or para position.
  • the binding site for the substituent is preferably the para position of the aromatic ring of the styrene unit.
  • the number of the substituents in the substituted styrene unit is not particularly limited, but is preferably 1 to 3, more preferably 1 and 2, and further preferably 1.
  • styrene unit a substituted styrene unit is preferred, a styrene unit substituted with an alkyl group is more preferred, a styrene unit substituted with a tert-butyl group is more preferred, and the para position of the aromatic ring is substituted with a tert-butyl group
  • the styrene units made are particularly preferred.
  • Block (b) consists of repeating unit (II).
  • the repeating unit (II) is a (meth) acrylic acid ester unit.
  • Examples of the monomer giving the (meth) acrylate unit include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
  • (Meth) acrylic acid alkyl ester (meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 1-methylcyclopentyl, (meth) acrylic acid 2-ethyladamantyl, (meth) acrylic acid 2- ( (Meth) acrylic acid alicyclic saturated hydrocarbon esters such as adamantane-1-yl) propyl; (Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and naphthyl (meth) acrylate; Examples include (meth) acrylic acid-substituted alkyl esters such as 2-hydroxyethyl (meth) acrylate, 3-hydroxyadamantyl (meth) acrylate, and 3-glycidylpropyl (meth) acrylate.
  • (meth) acrylic acid alkyl ester is preferable from the viewpoint of improving pattern formability and
  • the mass ratio ((I) / (II)) of the content ratio of the repeating unit (I) to the repeating unit (II) in the [A] block copolymer can be appropriately selected according to the line / space width ratio of the desired line and space pattern, the dimensions of the contact hole pattern or the cylinder pattern, and the like.
  • the mass ratio is preferably in the range of 40/60 to 60/40, more preferably 50/50, from the viewpoint of forming a better phase separation structure.
  • the mass ratio is preferably in the range of 30/70 to 40/60, or 70/30 to 60/40.
  • the group (1) is bonded to at least one terminal of the main chain of the [A] block copolymer.
  • the group (1) is preferably linked to the block (b).
  • the group (1) may be bonded to a plurality of terminals of the main chain of the [A] block copolymer. In this case, the plurality of groups (1) may be the same or different.
  • the group (1) is preferably formed by a terminal terminator described later and a group formed by a polymerization initiator, and more preferably formed by a terminal terminator.
  • the group (1) is a monovalent group that forms a compound having a ClogP of ⁇ 1 or more and 3 or less when a methyl group is bonded to the main chain side bond.
  • the lower limit of ClogP is preferably ⁇ 0.7, more preferably ⁇ 0.5, and further preferably ⁇ 0.4.
  • the upper limit of ClogP is preferably 2.5, more preferably 1.8, still more preferably 1.0, and particularly preferably 0.
  • ClogP a value obtained by using molecular model creation software (for example, “Chem Bio Draw Ultra 13.0, Chemical properties window” built in “Chemdraw Ver. 12” of CambridgeSoft) is used.
  • ClogP of the compound formed when a methyl group is bonded to the main chain side bond described above is a parameter that indirectly represents the hydrophilicity of the group (1).
  • the methyl group is a relatively small, simple and non-polar group. Therefore, no matter what structure the group (1) has, the influence of the methyl group on the ClogP is relatively small and substantially constant. Therefore, the ClogP is a parameter that increases or decreases mainly with the hydrophilicity of the group (1), and reflects the tendency of the hydrophilicity of the group (1) with high accuracy.
  • the lower limit of the carbon number of the group (1) is usually 1, preferably 2 and more preferably 3.
  • 20 is preferable, 10 is more preferable, 7 is further more preferable, and 6 is especially preferable.
  • Group (1) usually contains a heteroatom.
  • the number of heteroatoms of group (1) 1 is preferred and 2 is more preferred.
  • the upper limit of the number of heteroatoms in the group (1) is preferably 5, more preferably 4, and even more preferably 3.
  • the “hetero atom” refers to an atom other than a carbon atom and a hydrogen atom.
  • the number of heteroatoms in the group (1) is 2 or more, the 2 or more heteroatoms may be the same or different.
  • the group (1) preferably has 6 or less carbon atoms and 2 or more heteroatoms.
  • the ClogP can be easily adjusted in the above range.
  • hetero atom examples include halogen atoms such as fluorine atom, chlorine atom and bromine atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom and silicon atom, and among these, oxygen atom, nitrogen atom and sulfur atom. Atoms are preferred.
  • group (1) for example, a part or all of hydrogen atoms of a group containing a hetero atom-containing group between carbon-carbon of a hydrocarbon group, a hydrocarbon group, or a group containing a hetero atom-containing group described above And a group substituted with.
  • the “hydrocarbon group” includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • the “hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • the “chain hydrocarbon group” refers to a hydrocarbon group that does not include a cyclic structure but includes only a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group.
  • alicyclic hydrocarbon group refers to a hydrocarbon group that includes only an alicyclic structure as a ring structure and does not include an aromatic ring structure, and includes a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic group. Includes both hydrocarbon groups.
  • alicyclic hydrocarbon group does not need to be composed only of the alicyclic structure, and a part thereof may include a chain structure.
  • “Aromatic hydrocarbon group” refers to a hydrocarbon group containing an aromatic ring structure as a ring structure.
  • the aromatic hydrocarbon group does not need to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic structure.
  • Examples of the monovalent hydrocarbon group include 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 hydrocarbon having 6 to 20 carbon atoms. And aromatic hydrocarbon groups.
  • Examples of the monovalent chain hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group; An alkenyl group such as an ethenyl group, a propenyl group, a butenyl group; Examples thereof include alkynyl groups such as ethynyl group and propynyl group.
  • Examples of the monovalent alicyclic hydrocarbon group include monovalent monocyclic alicyclic saturated hydrocarbon groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group; A monovalent monocyclic alicyclic unsaturated hydrocarbon group such as a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group; Monovalent polycyclic alicyclic saturated hydrocarbon group such as norbornyl group, adamantyl group, tricyclodecyl group, tetracyclododecyl group; And monovalent polycyclic alicyclic unsaturated hydrocarbon groups such as a norbornenyl group, a tricyclodecenyl group, and a tetracyclododecenyl group.
  • Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, anthryl group, and trityl group; Examples include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and the like.
  • hetero atom-containing group examples include —CO— (carbonyl group), —CS— (thiocarbonyl group), —O— (ether group), —S— (thioether group), —COO— (ester group), And —SO 2 — (sulfonyl group), —SO 2 O— (thioester group), or a combination of these.
  • substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Alkoxy groups such as methoxy group, ethoxy group, 2-ethylpentoxy group, carboxy group, hydroxy group, cycloalkoxy group, aryloxy group, alkoxycarbonyl group, cycloalkyloxyoxycarbonyl group, aryloxycarbonyl group, acyl group, Examples thereof include polar groups such as amino group, amide group, cyano group, isocyanate group and sulfo group.
  • the amino group includes an amino group in which part or all of the hydrogen atoms are substituted with an alkyl group such as a methyl group or an ethyl group.
  • Examples of the group (1) include groups represented by the following formulas (1-1) to (1-7) (hereinafter also referred to as “group (1-1) to group (1-7)”). It is done.
  • R 1 is a monovalent organic group containing a hetero atom having 1 to 20 carbon atoms.
  • the group represented by the above formula (1-1) does not include the groups represented by the above formulas (1-2) to (1-7).
  • R 2 , R 3 , R 5 and R 6 are each independently an alkyl group having 1 to 10 carbon atoms.
  • R 4 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • R 7 is a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • t is an integer of 1 to 2.
  • u and v are each independently an integer of 0 to 2.
  • Me is a methyl group. * Indicates a main chain side bond which is a site bonded to the end of the main chain of the [A] block copolymer.
  • Examples of the monovalent organic group containing a hetero atom having 1 to 20 carbon atoms represented by R 1 include a group containing a hetero atom-containing group between carbon-carbon of a hydrocarbon group, a hydrocarbon group, or the above hetero atom. Examples include a group in which part or all of the hydrogen atoms of the group including the containing group are substituted with a substituent. Examples of the hydrocarbon group, heteroatom-containing group, and substituent include the same groups as described above.
  • the monovalent organic group containing a hetero atom having 1 to 20 carbon atoms represented by R 1 is preferably a group containing an ester group, a group containing a carboxy group, or a group containing —SO 2 —.
  • the ester group contained in R 1 may form a lactone structure. Further, the group represented by the above formula (1-1) is preferably introduced into the [A] block copolymer using a halogen compound described later. R 1 preferably does not contain a hydroxy group from the viewpoint of ease of introduction when the group represented by the formula (1-1) is introduced into the [A] block copolymer using a halogen compound. .
  • Examples of the alkyl group represented by R 2 , R 3, and R 6 include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Among these, a methyl group is preferable.
  • Examples of the alkyl group represented by R 5 include a methyl group, an ethyl group, a propyl group, and a 2-ethylhexyl group. Among these, a methyl group and a 2-ethylhexyl group are preferable, and a methyl group is more preferable. .
  • Examples of the monovalent organic group represented by R 4 include the same groups as the monovalent organic group represented by R 1 .
  • R 4 is preferably a methyl group.
  • Examples of the monovalent hydrocarbon group represented by R 7 include a monovalent chain hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, and a carbon number. Examples thereof include monovalent aromatic hydrocarbon groups of 6 to 10, among which an aromatic hydrocarbon group is preferable, and a phenyl group is more preferable.
  • the t is preferably 1. Moreover, as said u and v, 0 and 1 are preferable and 1 is more preferable.
  • group (1) examples include groups represented by the following formulas.
  • the value of ClogP of a compound formed when a methyl group is bonded to the main chain side bond of each group is also shown.
  • * indicates a main chain side bond that is a site bonded to the end of the main chain of the [A] block copolymer.
  • Me is a methyl group.
  • Et is an ethyl group.
  • those containing a hydroxy group, an amino group, a carbonyl group, a carboxyl group, a sulfonyl group, an ester group, a thiol group, an alkoxy group and a combination thereof are preferable.
  • a hydroxy group, an amino group, a methoxy group and an ethoxy group are preferable. More preferred are those containing at least two of the groups.
  • the other end of the main chain may be unmodified, and a terminal group other than the group (1) is bonded. You may do it.
  • the terminal group other than the group (1) include an alkyl group having 1 to 10 carbon atoms.
  • the block copolymer may have a linking group between the adjacent block (a) and block (b).
  • the pattern forming composition can form a self-assembled film with fewer defects in the regularly arranged structure because the [A] block copolymer has a linking group.
  • the linking group include divalent organic groups having 1 to 50 carbon atoms.
  • the divalent organic group is preferably a divalent organic group having 1 to 20 carbon atoms having one or more aromatic rings, and two of the hydrogen atoms of the alkanediyl group having 1 to 5 carbon atoms are aromatic.
  • a group substituted with a group hydrocarbon group is more preferred.
  • alkanediyl group examples include a methyl group, an ethyl group, and a propyl group, and an ethyl group is preferable.
  • aromatic hydrocarbon group examples include a phenyl group and a naphthyl group, and a phenyl group is preferable.
  • Examples of the monomer that gives the linking group include diphenylethylene.
  • Diphenylethylene improves the stability of the anion terminal produced in the middle when the [A] block copolymer is synthesized by anionic polymerization. Thereby, the dispersion degree of the obtained [A] block copolymer becomes smaller, and as a result, the variation in the dimension of the pattern formed by the pattern forming composition can be further reduced.
  • the block copolymer may have one or more linking groups.
  • the lower limit of the weight average molecular weight (Mw) of the block copolymer is preferably 5,000, more preferably 10,000, even more preferably 15,000, and particularly preferably 21,000.
  • the upper limit of Mw of the [A] block copolymer is preferably 100,000, more preferably 75,000, still more preferably 40,000, and particularly preferably 24,000.
  • the lower limit of the number average molecular weight (Mn) of the block copolymer is preferably 4,500, more preferably 9,500, still more preferably 14,500, and particularly preferably 20,000.
  • the upper limit of Mn of the [A] block copolymer is preferably 95,000, more preferably 72,000, further preferably 38,000, and particularly preferably 23,500.
  • the lower limit of the degree of dispersion (Mw / Mn) of the block copolymer is usually 1.
  • the upper limit of Mw / Mn of the [A] block copolymer is usually 4, preferably 2, more preferably 1.5, still more preferably 1.2, and particularly preferably 1.1.
  • Mw and Mn of the [A] block copolymer are values measured by GPC under the following conditions.
  • Sample injection volume 100 ⁇ L
  • Detector Differential refractometer Standard material: Monodisperse polystyrene
  • the lower limit of the content of the block copolymer is preferably 80% by mass, more preferably 90% by mass, still more preferably 95% by mass, based on the total solid content in the pattern forming composition. 99 mass% is especially preferable.
  • the lower limit of the concentration of the [A] block copolymer in the pattern forming composition is preferably 0.3% by mass, more preferably 0.7% by mass, still more preferably 1.0% by mass, and 1.3% Mass% is particularly preferred.
  • the upper limit of the concentration of the [A] block copolymer in the pattern forming composition is preferably 5% by mass, more preferably 3% by mass, further preferably 2% by mass, and particularly preferably 1.7% by mass. preferable.
  • [A] Synthesis method of block copolymer for example, a first method in which each block is formed in a desired order and then the group (1) is introduced by treating the polymerization terminal with a terminal stopper, Polymerization is started using the polymerization initiator that forms (1), and the block is formed by treating the polymerization terminal with a terminal terminator after the second method that forms each block in the desired order.
  • the 3rd method etc. which introduce
  • Each block of the block copolymer can be synthesized by, for example, living cation polymerization, living anion polymerization, living radical polymerization, coordination polymerization (Ziegler-Natta catalyst, metallocene catalyst), and the like. Living anionic polymerization is preferable from the viewpoint that (1) can be easily introduced.
  • the block copolymer is an asymmetric star copolymer (Mictoarm type copolymer)
  • the [A] block copolymer is 1,3-bis (1-phenylethenyl) benzene.
  • It can be synthesized from a method using anionic polymerization via a method, a method using a group capable of binding an arm from a method such as click chemistry, a method using a reagent having a different starting point in the polymerization system, and the like.
  • an anionic polymerization initiator is first used as a method of synthesizing each block by living anionic polymerization.
  • the block (a) is formed by polymerization of the monomer that gives the block (a) in an appropriate solvent
  • the monomer that gives the block (b) is added in the same manner, and the block (a) is connected to the block.
  • a linking group may be formed between the block (a) and the block (b) by a reaction such as diphenylethylene.
  • Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; Ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, 2-heptanone, cyclohexanone; Ethers such as tetrahydrofuran, dimethoxyethanes, diethoxyethan
  • the reaction temperature in the polymerization may be appropriately determined according to the type of polymerization initiator described later, but the lower limit of the reaction temperature is usually ⁇ 150 ° C., and preferably ⁇ 80 ° C.
  • the upper limit of the reaction temperature is usually 50 ° C, preferably 40 ° C.
  • the lower limit of the reaction time in the polymerization is usually 5 minutes, and preferably 20 minutes.
  • the upper limit of the reaction time in the polymerization is usually 24 hours and preferably 12 hours.
  • polymerization initiator used in the polymerization examples include alkyl lithium, alkyl magnesium halide, sodium naphthalene, alkylated lanthanoid compounds; potassium alkoxides such as t-butoxy potassium and 18-crown-6-ether potassium; dimethyl zinc, Alkyl zinc such as diethyl zinc; alkyl aluminum such as trimethylaluminum; aromatic metal compounds such as benzyl potassium, cumyl potassium, cumyl cesium, and the like.
  • the lower limit of the ClogP of the polymerization initiator is preferably -1, more preferably -0.3, and even more preferably 0.3.
  • the upper limit of ClogP of the polymerization initiator is preferably 2, more preferably 1, and still more preferably 0.4.
  • the initiator (i-1) is 3.17
  • the polymerization initiator (i-2) is 3.57
  • the polymerization initiator (i-3) is 0.368
  • the polymerization initiator (i-4) is 3.3. 21.
  • the polymerization initiator (i-5) is 3.37.
  • ClogP of a polymerization initiator is ClogP calculated
  • the polymerization initiator used for the polymerization is preferably an alkyl lithium compound, more preferably sec-butyl lithium.
  • the polymerization initiator (i-3) is preferred as the polymerization initiator used for the polymerization.
  • examples of the terminal terminator include halogen compounds in which the group (1) and a halogen atom are bonded, dialkylformamide, glycidyl ether, epoxycycloalkane, epoxy compounds (provided that , Except for the above-mentioned glycidyl ether and epoxycycloalkane), substituted or unsubstituted thiirane or substituted or unsubstituted thietane, alkylpyrrolidone, carbon dioxide and the like.
  • the halogen atom include a chlorine atom, a fluorine atom, and a bromine atom. Among these, a chlorine atom and a bromine atom are preferable, and a bromine atom is more preferable.
  • the lower limit of ClogP of the above end terminator is preferably -1.5, more preferably -1.0, still more preferably -0.5, and particularly preferably -0.3.
  • the upper limit of ClogP of the terminal stopper is preferably 4.0, more preferably 3.2, further preferably 2.2, particularly preferably 1.4, and particularly preferably 0.
  • the above halogen compound or carbon dioxide can be used as a terminal terminator.
  • the group (1-2) is introduced, for example, dialkylformamide can be used as the terminal terminator.
  • the group (1-3) is introduced, for example, substituted or unsubstituted thiirane or substituted or unsubstituted thietane can be used as the terminal terminator.
  • glycidyl ether can be used as the terminal terminator.
  • alkylpyrrolidone can be used as the terminal terminator.
  • the group (1-6) is introduced, for example, an epoxy compound described later can be used as the terminal terminator.
  • an epoxycycloalkane can be used as a terminal terminator.
  • a method as shown in the following scheme and the like can be mentioned. That is, the block copolymer obtained by the above-described living anion polymerization or the like is modified by adding a terminal terminator to modify the terminal [A] block copolymer in which the group (1) is introduced at the terminal of the main chain.
  • a polymer can be obtained.
  • block (a) is a polystyrene block
  • block (b) is a methyl (meth) acrylate block
  • a terminal terminator is an epoxy compound described later.
  • the group (1) to be introduced is a group (1-4).
  • n is an integer of 2 or more.
  • m is an integer of 1 or more.
  • R 5 has the same meaning as in the above formula (1-4).
  • the terminal terminator is a halogen compound, dialkylformamide, alkylpyrrolidone, substituted or unsubstituted thiirane, substituted or unsubstituted thietane, glycidyl ether, epoxycycloalkane, carbon dioxide, etc.
  • the main chain is obtained by the same method.
  • the group (1) can be introduced at the end of
  • the above [A] block copolymer is preferably recovered by a reprecipitation method. That is, after completion of the reaction, the target copolymer is recovered as a powder by introducing the reaction solution into a reprecipitation solvent.
  • a reprecipitation solvent alcohols, ultrapure water, alkanes and the like can be used singly or in combination of two or more.
  • the polymer can be recovered by removing low molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation, or the like.
  • the pattern forming composition contains a [B] solvent.
  • the solvent is not particularly limited as long as it can dissolve or disperse at least the [A] block copolymer.
  • Examples of the solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like.
  • alcohol solvent examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol.
  • ether solvent examples include dialkyl ether solvents such as diethyl ether, dipropyl ether, and dibutyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; And aromatic ring-containing ether solvents such as diphenyl ether and anisole.
  • ketone solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone, ethyl-n-butyl ketone, and methyl-n-hexyl ketone.
  • Chain ketone solvents such as di-iso-butyl ketone and trimethylnonanone: Cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and methylcyclohexanone: Examples include 2,4-pentanedione, acetonylacetone, acetophenone, and the like.
  • amide solvents examples include cyclic amide solvents such as N, N′-dimethylimidazolidinone and N-methylpyrrolidone; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, Examples thereof include chain amide solvents such as N-methylacetamide, N, N-dimethylacetamide, and N-methylpropionamide.
  • ester solvent examples include methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, i-pentyl acetate, and acetic acid.
  • acetate solvents such as sec-pentyl, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether
  • Polyhydric alcohol partial ether acetate solvents such as acetate, propylene glycol monobutyl ether acetate, dipropylene
  • hydrocarbon solvent examples include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, Aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane; Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents and the like.
  • ester solvents and ketone solvents are preferable, ester solvents are more preferable, polyhydric alcohol partial ether acetate solvents are more preferable, and propylene glycol monomethyl ether acetate is particularly preferable.
  • the pattern forming composition may contain one or more [B] solvents.
  • composition for pattern formation may contain, surfactant etc. are mentioned, for example.
  • surfactant As an arbitrary component which the said composition for pattern formation may contain, surfactant etc. are mentioned, for example.
  • the said pattern formation composition can improve the applicability
  • the pattern forming method of the present invention includes a step of forming a self-assembled film with the pattern forming composition and a step of removing a part of the self-assembled film.
  • the pattern forming method includes a step of forming a lower layer film on one surface side of the substrate (hereinafter also referred to as “lower layer film forming step”) and / or one of the substrates before the self-assembled film forming step. You may further provide the process (henceforth a "pre-pattern formation process”) which forms a pre pattern in the surface side.
  • the pattern forming method since the above-described pattern forming composition is used for forming the self-assembled film, it is possible to form a self-assembled film with few defects in the ordered arrangement structure, and thus a good shape. A pattern can be formed.
  • each process will be described with reference to the drawings.
  • This step is a step of forming a lower layer film on one surface side of the substrate.
  • a substrate with a lower layer film in which the lower layer film 102 is formed on one surface (upper surface) side of the substrate 101 can be obtained.
  • the self-assembled film in the self-assembled film forming step described later is formed on the surface of the lower layer film 102 opposite to the substrate 101.
  • the phase-separated structure (microdomain structure) of the self-assembled film has an interaction with the lower layer film 102 in addition to the interaction between each block of the [A] block copolymer contained in the pattern forming composition. Therefore, the structure control may be facilitated by forming the lower layer film 102.
  • the transfer process can be improved by forming it on the lower layer film 102.
  • the substrate 101 a conventionally known substrate such as a silicon wafer or a wafer coated with aluminum can be used.
  • underlayer film forming composition used for forming the underlayer film 102 conventionally known organic underlayer film forming materials and the like can be used, and examples thereof include an underlayer film forming composition containing a crosslinking agent.
  • a method for forming the lower layer film 102 is not particularly limited.
  • the lower layer film forming composition is applied on the substrate 101 by a known method such as a spin coating method, and then cured by exposure and / or heating.
  • the method of forming etc. are mentioned.
  • Examples of radiation used for this exposure include visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, ⁇ -rays, molecular beams, and ion beams.
  • the upper limit of the heating temperature is not particularly limited, but is preferably 550 ° C, more preferably 450 ° C, and further preferably 300 ° C.
  • the upper limit of the heating time is preferably 1,200 seconds, more preferably 600 seconds, and even more preferably 300 seconds.
  • the lower limit of the average thickness of the lower layer film 102 is not particularly limited, but is preferably 1 nm, more preferably 2 nm, and further preferably 3 nm.
  • the upper limit of the average thickness of the lower layer film 102 is not particularly limited, but is preferably 20,000 nm, more preferably 1,000 nm, still more preferably 100 nm, and particularly preferably 10 nm.
  • This step is a step of forming the pre-pattern 103.
  • This pre-pattern may be formed on the substrate, or may be formed on the surface of the lower layer film 102 opposite to the substrate 101 as shown in FIG.
  • the shape of the phase separation structure by self-organization of a coating film 104 (see FIG. 3) described later is controlled, and a finer pattern can be formed.
  • the phase separation structure of the self-assembled film obtained by the pattern forming composition can be finely controlled by the material, size, shape and the like of the prepattern 103.
  • the pre-pattern 103 can be appropriately selected according to the shape of a desired pattern.
  • a line and space pattern, a hole pattern, a cylinder pattern, or the like can be used.
  • the pattern forming method includes a pre-pattern forming step, a self-assembled film 105 to be described later is formed in a non-stacked region of the normal pre-pattern 103.
  • a method for forming the pre-pattern 103 a method similar to a known resist pattern forming method may be used.
  • a composition used for forming the pre-pattern 103 a conventional resist composition such as a composition containing a polymer having an acid dissociable group, a radiation sensitive acid generator and an organic solvent may be used. it can.
  • a commercially available chemically amplified resist composition is applied onto the substrate 101 or the lower layer film 102 to form a resist film. Next, exposure is performed by irradiating a desired region of the resist film with radiation through a mask having a specific pattern.
  • Examples of the radiation include electromagnetic waves such as ultraviolet rays, far ultraviolet rays, and X-rays; and charged particle beams such as electron beams and ⁇ rays.
  • far ultraviolet rays are preferable
  • ArF excimer laser light and KrF excimer laser are more preferable
  • ArF excimer laser light is more preferable.
  • immersion exposure can also be performed as an exposure method.
  • a desired pre-pattern 103 can be formed by performing post-exposure baking (PEB) and performing development using an alkali developer, a developer containing an organic solvent as a main component, or the like.
  • PEB post-exposure baking
  • the obtained pre-pattern 103 further accelerates curing by, for example, heat treatment after irradiating ultraviolet rays having a wavelength of 254 nm.
  • the lower limit of the heat treatment temperature is 100 ° C., for example.
  • the upper limit of the heat treatment temperature is, for example, 200 ° C.
  • the lower limit of the heat treatment time is, for example, 1 minute.
  • the upper limit of the heat treatment time is, for example, 30 minutes.
  • the surface of the pre-pattern 103 may be subjected to a hydrophobic treatment or a hydrophilic treatment.
  • a hydrogenation treatment by exposing to hydrogen plasma for a certain period of time can be cited.
  • the self-organization of the coating film 104 can be further promoted.
  • This step is a step for forming a phase-separated self-assembled film (self-assembled film having a phase-separated structure) on the substrate using the pattern forming composition.
  • the pattern forming composition is directly applied onto the substrate to form a coating film, thereby forming a self-assembled film having a phase separation structure.
  • the pattern forming composition is applied to a region on the lower layer film 102 sandwiched between the prepatterns 103.
  • a self-assembled film 105 having a phase separation structure is formed on the lower layer film 102 formed on the substrate 101.
  • the self-assembled film to be formed include a film having a phase separation structure having an interface substantially perpendicular to the substrate 101, such as the self-assembled film 105 in FIG.
  • the pattern forming composition it is possible to obtain the self-assembled film 105 with few defects in the regularly arranged structure while suppressing coating defects due to excellent coating properties.
  • the phase separation structure is preferably formed along the pre-pattern, and the interface formed by the phase separation is substantially parallel to the side surface of the pre-pattern. More preferred.
  • a block having high affinity with the side surface of the pre-pattern 103 (referred to as “block ( ⁇ )”) Forms a block ( ⁇ ) phase 105 b along the pre-pattern 103, and a block having a low affinity (referred to as “block ( ⁇ )”) forms a block ( ⁇ ) phase 105 a at a position away from the pre-pattern 103.
  • block ( ⁇ ) a block having high affinity with the side surface of the pre-pattern 103
  • block having a low affinity referred to as “block ( ⁇ )”
  • the method for applying the pattern forming composition to one surface side of the substrate 101 to form the coating film 104 is not particularly limited.
  • the pattern forming composition to be used is applied by a spin coating method or the like. And the like. Thereby, the composition for pattern formation can be applied onto the substrate 101. Further, when the prepattern 103 is formed on the substrate 101, the pattern forming composition can be filled between the prepatterns 103 on the lower layer film 102.
  • the lower limit of the average thickness of the coating film 104 to be formed is, for example, 10 nm.
  • the upper limit of the average thickness of the formed coating film 104 is, for example, 60 nm.
  • Examples of a method for forming the self-assembled film 105 by phase-separating the coating film 104 include an annealing method.
  • Examples of the annealing method include a method of heating with an oven, a hot plate or the like.
  • a minimum of annealing temperature it is usually 80 ° C, 120 ° C is preferred, 160 ° C is more preferred, and 200 ° C is still more preferred.
  • the upper limit of the annealing temperature is usually 400 ° C., preferably 350 ° C., more preferably 300 ° C., and particularly preferably 260 ° C.
  • 10 seconds are preferred, 20 seconds are more preferred, 40 seconds are still more preferred, and 90 seconds are especially preferred.
  • the upper limit of the annealing time is preferably 120 minutes, more preferably 30 minutes, further preferably 10 minutes, and particularly preferably 3 minutes.
  • the lower limit of the average thickness of the self-assembled film 105 thus obtained is preferably 0.1 nm, more preferably 1 nm, and more preferably 5 nm.
  • the upper limit of the average thickness of the self-assembled film 105 is preferably 500 nm, more preferably 100 nm, and even more preferably 50 nm.
  • this step is a step of removing a part of the block ( ⁇ ) phase 105 a in the phase separation structure of the self-assembled film 105.
  • the block ( ⁇ ) phase 105a can be removed by an etching process using the difference in etching rate of each phase separated by self-assembly.
  • the radiation for example, when the phase to be removed by etching is a poly (meth) acrylate block phase, radiation having a wavelength of 254 nm can be used. Since the poly (meth) acrylic acid ester block phase is decomposed by the radiation irradiation, it is more easily etched.
  • Examples of the method for removing the block ( ⁇ ) phase include known methods such as reactive ion etching (RIE) such as chemical dry etching and chemical wet etching; and physical etching such as sputter etching and ion beam etching. Of these, reactive ion etching (RIE) is preferable. Among them, chemical dry etching using CF 4 , O 2 gas, etc., and chemical wet etching (wet development) using a liquid etching solution such as an organic solvent or hydrofluoric acid. Is more preferable.
  • RIE reactive ion etching
  • RIE reactive ion etching
  • wet development using a liquid etching solution such as an organic solvent or hydrofluoric acid. Is more preferable.
  • organic solvent examples include alkanes such as n-pentane, n-hexane and n-heptane; cycloalkanes such as cyclohexane, cycloheptane and cyclooctane; ethyl acetate, n-butyl acetate, i-butyl acetate and propion Saturated carboxylic acid esters such as methyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone; methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol, etc. Examples include alcohols. These solvents can be used alone or in combination of two or more. In this step, instead of removing the block phase ( ⁇ ), the block phase ( ⁇ ) may be removed.
  • alkanes such as n-pentane, n-he
  • Pre-pattern removal process When the pre-pattern 103 is formed on the substrate, it is preferable to remove the pre-pattern 103 by this step as shown in FIGS. By removing the pre-pattern 103, it is possible to form a finer and more complicated pattern (pattern consisting of 105b in FIG. 5). Note that the description of the removal method of the block ( ⁇ ) phase 105a described above can be applied to the removal method of the pre-pattern 103. Moreover, this process may be performed simultaneously with the said removal process, and may be performed before or after a removal process.
  • the pattern forming method further includes a normal substrate pattern forming step after the removing step.
  • This step is a step of patterning by etching the lower layer film 102 and the substrate 101 using a part of the remaining self-assembled film (pattern consisting of 105b in FIG. 5) as a mask.
  • the block ( ⁇ ) phase 105b used as a mask is removed from the substrate by a dissolution treatment or the like, and finally a patterned substrate (pattern) can be obtained.
  • Examples of the obtained pattern include a line and space pattern and a hole pattern.
  • the same method as in the removing step can be used, and the etching gas and the etching liquid can be appropriately selected according to the material of the substrate and the like.
  • the substrate is made of a silicon material
  • a mixed gas of chlorofluorocarbon gas and SF 4 can be used.
  • the substrate is a metal film
  • a mixed gas of BCl 3 and Cl 2 or the like can be used.
  • a pattern obtained by the pattern forming method is suitably used for a semiconductor element or the like, and the semiconductor element is widely used for an LED, a solar cell or the like.
  • a self-assembled film having a phase separation structure such as a sea-island structure, a cylinder structure, or a bicontinuous structure. A fine pattern can be obtained.
  • the mixture was aged for 120 minutes, and then 10 g of tetrahydrofuran and 12.7 mL (119.8 mmol) of methyl methacrylate were added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was aged for 120 minutes, and then 0.045 g (1.13 mmol) of methanol as an end terminator (C-1) was added to terminate the polymerization end.
  • the obtained polymer solution was purified by precipitation in methanol, and then filtered to obtain a white solid.
  • the obtained white solid was dissolved in methyl isobutyl ketone to give a 10% by mass solution.
  • 500 g of a 1% by mass oxalic acid aqueous solution was poured and stirred, and after standing, the lower aqueous layer was removed. This operation was repeated three times to remove the Li salt.
  • 500 g of ultrapure water was poured into this solution and stirred, and the lower aqueous layer was removed. This operation was repeated three times to remove oxalic acid.
  • the solution was concentrated and dropped into 2,000 g of methanol to precipitate a polymer. This polymer was filtered under reduced pressure, further washed twice with methanol, and then dried under reduced pressure at 60 ° C.
  • the block copolymer (A-1) was found to contain each of the repeating units (I) derived from 4-tert-butylstyrene and the repeating units (II) derived from methyl methacrylate. Were 50.0 mass% (39 mol%) and 50.0 mass% (61 mol%), respectively.
  • the block copolymer (A-1) is a diblock copolymer.
  • Styrene 22.1 mL (0.192 mol) was added dropwise over 30 minutes to confirm that the polymerization system was orange. At the time of this dropwise injection, care was taken so that the internal temperature of the reaction solution did not exceed -60 ° C. After completion of the dropwise addition, the mixture was aged for 30 minutes, and then 0.21 mL (0.0015 mol) of 1,1-diphenylethylene and 1.96 mL (0.0010 mol) of 0.5N tetrahydrofuran solution of lithium chloride were added, and the polymerization system was dark red It was confirmed that it became.
  • This block copolymer (A-22) had Mw of 42,000, Mn of 40,000, and Mw / Mn of 1.05. Further, as a result of 1 H-NMR analysis, the block copolymer (A-22) had a content ratio of the repeating unit (I) derived from styrene and the repeating unit (II) derived from methyl methacrylate of 50. They were 0 mass% (50.3 mol%) and 50.0 mass% (49.7 mol%).
  • the block copolymer (A-22) is a diblock copolymer.
  • Styrene 22.1 mL (0.192 mol) was added dropwise over 30 minutes to confirm that the polymerization system was orange. At the time of this dropwise injection, care was taken so that the internal temperature of the reaction solution did not exceed -60 ° C. After completion of the dropwise addition, the mixture was aged for 30 minutes, and then 0.11 mL (0.00078 mol) of 1,1-diphenylethylene and 1.04 mL (0.0005 mol) of 0.5N tetrahydrofuran solution of lithium chloride were added, and the polymerization system was dark red It was confirmed that it became.
  • This block copolymer (A-23) had Mw of 81,000, Mn of 77,000, and Mw / Mn of 1.05. Further, as a result of 1 H-NMR analysis, the block copolymer (A-23) has a content ratio of the repeating unit (I) derived from styrene and the repeating unit (II) derived from methyl methacrylate of 50. They were 0 mass% (50.3 mol%) and 50.0 mass% (49.7 mol%).
  • the block copolymer (A-23) is a diblock copolymer.
  • the end terminator used for the synthesis of the block copolymers (A-1) to (A-23) is as follows: the end terminator (C-1) is methanol, and the end terminator (C-2) is ⁇ -bromo- ⁇ . -Butyrolactone, terminal stopper (C-3) is N, N-dimethylformamide, terminal stopper (C-4) is propylene sulfide, terminal stopper (C-5) is glycidyl methyl ether, terminal stopper (C- 6) N-methylpyrrolidone, terminal stopper (C-7) ethyl bromohexanoate, terminal stopper (C-8) carbon dioxide, terminal stopper (C-9) methanesulfonyl chloride, terminal stopper (C-10) is 1,2-epoxycyclohexane, terminal stopper (C-11) is styrene oxide, terminal stopper (C-12) is 2-ethylhexyl glycidyl ether, terminal stop
  • n and m are each independently an integer of 2 or more.
  • Me is a methyl group.
  • Et is an ethyl group.
  • Ph is a phenyl group.
  • ClogP ⁇ Calculation of ClogP>
  • the terminator ClogP used in the synthesis and the compound ClogP formed when the main chain side bond of the end group of the block copolymer is bonded to a methyl group are described in “Chemdraw Ver. 12” of CambridgeSoft. ".
  • the ClogP of the compound formed when the main chain side bond of the terminal group of this block copolymer is bonded to the methyl group is described below as “ClogP of the terminal group linked to block (a) or block (b)”. May be written. When the terminal is unmodified (hydrogen atom), the above calculation was not performed.
  • Table 1 below shows the content of each repeating unit of the block copolymers (A-1) to (A-23), the end terminator used in the synthesis, ClogP of this end terminator, block (a) or block ( The terminal groups ClogP, Mw, Mn, and Mw / Mn linked to b) are shown.
  • ClogP since the terminal terminator (C-1) is a terminal terminator that does not form a terminal group, ClogP is omitted and “ ⁇ ” is displayed.
  • “4TBS” refers to 4-tert-butylstyrene.
  • ST indicates styrene.
  • MMA refers to methyl methacrylate.
  • the 1st arm was put into 1,000 mL of methanol, precipitated and purified, and sufficiently dried in a vacuum dryer at 60 ° C.
  • the Miktoarm type block copolymers (A-24) and (A-25) synthesized in Synthesis Examples 24 and 25 have a structure represented by the following formula (A), and X, Y described in the formulas And Z each represent the following structure.
  • the styrene unit contained in Y in the following formula is the block (a).
  • the methacrylic acid ester unit contained in X and Z in the following formula is the block (b).
  • block (b) included in X of the following formula is block X
  • block (a) included in Y of the following formula is block Y
  • block (b) included in Z of the following formula is block Z, respectively.
  • each n is independently an integer of 2 or more. * Indicates a bond that binds to a site other than X, Y and Z in the formula (A).
  • Table 2 below shows the end terminators used for the synthesis of the block copolymers (A-24) and (A-25), the end groups linked to ClogP, block X, block Y or block Z of this end terminator.
  • ClogP, Mw, Mn, and Mw / Mn are shown.
  • ClogP since the terminal terminator (C-1) is a terminal terminator that does not form a terminal group, ClogP is omitted and “ ⁇ ” is displayed.
  • polymer Polymerized for 3 hours.
  • the obtained polymer solution was purified by precipitation with 3 L of methanol to remove residual monomers, initiators and the like.
  • This polymer had Mw of 8,285, Mn of 5,355, and Mw / Mn of 1.54.
  • the polymer was diluted with propylene glycol monomethyl ether acetate to obtain a 10% by mass polymer solution (N-1).
  • a mixed solution was obtained by mixing and dissolving 150 g of this polymer solution (N-1) and 9,850 g of propylene glycol monomethyl ether acetate as a solvent.
  • the obtained mixed solution was filtered through a membrane filter having a pore size of 0.1 ⁇ m to prepare a composition for forming a lower layer film.
  • the film After applying the pattern-forming compositions (S-1) to (S-25) to the substrate on which the lower layer film is formed so that the average thickness of the coating film to be formed is 35 nm, the film is formed at 230 ° C. for 120 seconds. Baked. By this firing, a self-assembled film having a fingerprint pattern was formed on the substrate on which the lower layer film was formed. About the fingerprint pattern which spreads on this board
  • Pattern Forming Composition For the pattern forming compositions (S-1) to (S-12) and (S-16) to (S22), an ordered arrangement structure (fingerprint pattern) is formed on the substrate by the following method. The self-assembled film was prepared, and the pitch of the fingerprint pattern was measured and the edge roughness was evaluated.
  • Fingerprint pattern pitch measurement was performed by periodic analysis using the IMEC calculation tool built in the SEM from the image with the magnification of 300,000 times.
  • the pitch (nm) of the fingerprint putter indicates that the smaller the value, the finer the pitch in the formed phase separation structure.
  • FER Fingerprint Pattern Edge Roughness Evaluation Fingerprint pattern edge roughness (FER) evaluation was analyzed from the image with a magnification of 300,000 times using a FER calculation tool built in the SEM. The FER (nm) indicates that the smaller the value is, the smaller the edge roughness of the formed fingerprint pattern is, that is, the smaller the occurrence of defects in the ordered structure in the self-assembled film, the better. FER (nm) is evaluated as “good” when it is 3.5 nm or less, and “bad” when it exceeds 3.5 nm.
  • Table 3 below shows the evaluation results of the pattern forming compositions (S-1) to (S-12) and (S-16) to (S22). Table 3 below also shows ClogP of the terminal group linked to the block (a) or the block (b) of the [A] block copolymer contained in the pattern forming composition.
  • Table 4 below shows the evaluation results of the pattern forming compositions (S-13) to (S-15) and (S-23) to (S-25). Table 4 below also shows ClogP of terminal groups linked to the block (a) or the block (b) of the [A] block copolymer contained in the pattern forming composition.
  • the block copolymers (A-24) and (A-25) each have two blocks (b). Therefore, in Table 4, ClogP of each terminal group connected to two blocks (b) is written together.
  • the pattern forming compositions of Examples 1 to 14 can form a self-assembled film with fewer defects in the ordered arrangement structure than the pattern forming compositions of Comparative Examples 1 to 5. I understood. Further, as shown in Table 4, the pattern forming compositions of Examples 15 to 18 formed self-assembled films with fewer defects in the regular arrangement structure than the pattern forming compositions of Comparative Examples 6 and 7. I understood that I could do it. That is, it is judged that the pattern forming compositions of Examples 1 to 18 can be used for forming a pattern having a good shape.
  • the pattern forming composition, the pattern forming method, and the block copolymer of the present invention a self-assembled film with few defects in a regular arrangement structure can be formed, and as a result, a pattern with a good shape can be formed. Therefore, they can be suitably used in pattern formation processes in the manufacture of various electronic devices such as semiconductor devices and liquid crystal devices that are required to be further miniaturized.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de formation d'un motif, qui contient un solvant et un copolymère séquencé qui forme une structure de séparation de phase par assemblage propre et qui est caractérisée en ce que : le copolymère séquencé présente un premier bloc composé d'une unité styrène substituée ou non substituée, un deuxième bloc composé d'une unité ester de (méth)acrylate et un premier groupe qui est lié à au moins une extrémité de la chaîne principale; et le premier groupe est un groupe monovalent qui forme un composé ayant un ClogP allant de -1 à 3 (inclus) lorsqu'un groupe méthyle est lié à l'extrémité de liaison côté chaîne principale. Il est préférable que le premier groupe soit formé au moyen d'un terminateur de chaîne; et, si tel est le cas, il est préférable que le ClogP du terminateur de chaîne soit compris entre -1,5 et 4,0 (inclus). Le ClogP d'un composé qui est formé lorsqu'un groupe méthyle est lié à l'extrémité de liaison côté chaîne principale du premier groupe est de préférence inférieur ou égal à 2,5. Le nombre d'atomes de carbone dans le premier groupe est de préférence de 1 à 20 (inclus). Le nombre d'hétéroatomes dans le premier groupe est de préférence de 1 à 5 (inclus).
PCT/JP2016/060853 2015-04-01 2016-03-31 Composition de formation de motif et procédé de formation de motif WO2016159329A1 (fr)

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JP6652721B2 (ja) 2020-02-26
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KR102604419B1 (ko) 2023-11-22

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