Classifications

• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/22—Esters containing halogen
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present invention relates to compounds, (co) polymers, compositions, and pattern forming methods.
• the general resist material so far is a polymer-based resist material capable of forming an amorphous film.
• examples thereof include polymer-based resist materials such as polymethylmethacrylate and polyhydroxystyrene or polyalkylmethacrylate having an acid dissociation group (see, for example, Non-Patent Document 1).
• a line pattern of about 10 to 100 nm is formed by irradiating a resist thin film prepared by applying a solution of these resist materials on a substrate with ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays, or the like. ing.
• the reaction mechanism of lithography using an electron beam or extreme ultraviolet rays is different from that of ordinary optical lithography.
• the goal is to form fine patterns of several nm to ten and several nm.
• a resist material having higher sensitivity to the exposure light source is required.
• it is required to further increase the sensitivity in terms of throughput.
• an inorganic resist material having a metal element such as titanium, tin, hafnium or zirconium has been proposed (see, for example, Patent Document 1).
• the conventionally developed resist composition having high sensitivity characteristics has problems such as insufficient pattern quality such as large pattern defects and large roughness, insufficient sensitivity improvement, and insufficient etching resistance. Further, the stability of the resist liquid is not sufficient, and there is a difficulty in developing it for actual semiconductor manufacturing. Based on these circumstances, a resist that achieves both high resolution and high sensitivity is required.
• a positive pattern using an alkaline developer is used for a pattern formed of a hydrophilic resin and a hydrophobic resin after exposure and baking.
• Materials and processes have been studied for each of the formation (PTI) and the negative pattern formation (PTI) using an organic solvent developer.
• the solubility of the hydrophobic resin pattern in PTI in the alkaline developer is compared with that in the organic solvent developer of the hydrophilic resin pattern in NTI. Since the solubility is high, it is more difficult for NTI to make fine lines, and it is difficult to sufficiently secure the resolution on the fine line side due to pattern collapse caused by swelling of the resin.
• the present invention provides a resin material capable of forming a film having high resolution and high sensitivity, a resist composition containing these, a method for forming a resist pattern using the same, and a method for forming an insulating film.
• the purpose is.
• the present inventors have found that a (co) polymer containing a compound having a specific structure has high solubility in a safe solvent, and forms a film for photography of these compounds and the like.
• a film having high resolution and high sensitivity can be formed when used in a composition for use or for forming a film for resist, and have completed the present invention. That is, the present invention is as follows.
• [1] A compound having one or more halogens and two or more substituents having unsaturated double bonds.
• R 1 , R 2 and R 3 are independently hydrogen atoms, halogens, linear organic groups having 1 to 20 carbon atoms, branched organic groups having 3 to 20 carbon atoms, or 3 carbon atoms.
• L represents a divalent linking group A represents an organic group having 1 to 30 carbon atoms.
• X represents Cl, Br or I, or contains a halogen atom selected from the group consisting of Cl, Br and I, and has a single bond, an ester group, an ether group, an amide group, an imide group, a urethane group, Represents a hydrocarbon group having 1 to 30 carbon atoms bonded to A via a urea group, a thioether group, a phosphine group or a phosphate ester group.
• n 0 represents an integer from 2 to 5
• n 2 represents an integer from 1 to 5.
• [6] A (co) polymer having a structural unit derived from the compound according to any one of [1] to [5]. [7] The copolymer according to [6], which further has a structural unit having a functional group whose solubility in an alkaline developer is improved by the action of an acid or a base. [8] The (co) polymer according to [6] or [7], wherein the content of Fe, Al, Sb, Ru and W is less than 1 ppm. [9] A resist composition containing the compound according to any one of [1] to [5] and / or the (co) polymer according to any one of [6] to [8].
• a pattern forming method including.
• the present invention it is possible to provide a compound and a composition capable of forming a film having high resolution and sensitivity, and a method for forming a resist pattern and a method for forming an insulating film using the same.
• the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
• Halogen-containing polymerizable compound One of the present embodiments relates to a compound having one or more halogens and two or more substituents having an unsaturated double bond, and more specifically, a halogen represented by the general formula (A). Concerning the contained polymerizable compound.
• R 1 , R 2 and R 3 are independently hydrogen atoms, halogens, linear organic groups having 1 to 20 carbon atoms, branched organic groups having 3 to 20 carbon atoms, or 3 carbon atoms.
• L represents a divalent linking group A represents an organic group having 1 to 30 carbon atoms.
• X represents Cl, Br or I, or contains a halogen atom selected from the group consisting of Cl, Br and I, and has a single bond, an ester group, an ether group, an amide group, an imide group, a urethane group, Represents a hydrocarbon group having 1 to 30 carbon atoms bonded to A via a urea group, a thioether group, a phosphine group or a phosphate ester group.
• n 0 represents an integer from 2 to 5
• n 2 represents an integer from 1 to 5.
• the compound of the present embodiment preferably contains two or more ester moieties containing a polymerizable functional group in the compound.
• a copolymer containing at least a constituent unit having the above as a resin for lithography a resin pattern formed after the processes of exposure, baking (PEB, Post Exposure Bake), and development is applied to a developing solution.
• Solubility can be suppressed, pattern collapse due to a mechanism such as resin swelling can be suppressed, especially in fine pattern formation, and the resolution of a fine line pattern can be improved.
• the introduction of the ester structure into the phenolic hydroxyl group can reduce the time-dependent change of the resist resin derived from the pKa of the phenolic hydroxyl group, and as a result, the time-lapse. It can also have a secondary effect of maintaining the later pattern quality.
• the compound in the present embodiment is characterized by having a halogen element in the compound.
• halogen element improves activity in the lithography process, improves efficiency in lithography, or secures a margin for efficiency in lithography, resulting in a more favorable allocation of material design performance. In addition, it can contribute to the improvement of lithography performance and the improvement of manufacturing stability. This effect is particularly noticeable in short wavelength or electron beam exposure processes such as EUV and EB.
• the compound represented by the general formula (A) is preferably a compound represented by the general formula (1).
• R 1 represents a hydrogen atom, halogen or methyl group.
• R 4 independently represents a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms.
• A represents an organic group having 1 to 30 carbon atoms.
• n 0 represents an integer from 2 to 5
• n 1 represents 0 or 1 and represents n 2 represents an integer from 1 to 5.
• R 4 represents a linear organic group having 1 to 20 carbon atoms, branched organic group having 3 to 20 carbon atoms, and two or more selected from the group consisting of cyclic organic group having 3-20 carbon atoms It may be a combination.
• R 4 may have a substituent.
• the R 4, for example, may have a substituent group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms or 1 to 6 carbon atoms; which may have a substituent, the carbon number An alkenyl group having 2 to 20 carbon atoms or 2 to 6 carbon atoms; an alkynyl group having 2 to 20 carbon atoms, 2 to 10 carbon atoms or 2 to 6 carbon atoms which may have a substituent: Cycloalkyl group having 3 to 20 carbon atoms and 3 to 10 carbon atoms or 3 to 6 carbon atoms which may have a substituent; may have a substituent and has 3 to 20 carbon atoms and carbon atoms.
• Examples thereof include an aryl group having 5 to 20 carbon atoms, 5 to 10 carbon atoms or 5 to 6 carbon atoms; a combination thereof and the like.
• R 4 include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, which may have a substituent.
• Icosyl group cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloicosyl group, adamantyl group, ethylene group, propylene group, butylene group, phenyl group, naphthyl group , Anthracene group, phenanthrene group, tetracene group, chrysen group, triphenylene group, pyrene group, benzopyrene group, azulene group, fluorene group and the like. These may include ether bonds, ketone bonds, and ester bonds.
• the illustrated group includes an isomer.
• the propyl group contains an n-propyl group and an isopropyl group
• the butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group and a tert-butyl group.
• the substituent of R 4 is not particularly limited, but for example, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, or a branched aliphatic hydrocarbon.
• Hydrogen group, cyclic aliphatic hydrocarbon group, aryl group, aralkyl group, alkoxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloxy group, allyloyloxy group, alkylsilyl group and various crosslinkable groups Examples include acid dissociable groups.
• crosslinkable group is a group that is crosslinked by acid, alkali, light or heat, and is a group that is crosslinked in the presence of a catalyst or in the absence of a catalyst.
• the crosslinkable group is not particularly limited, and is, for example, a group having an allyl group, a group having a (meth) acryloyl group, a group having an epoxy (meth) acryloyl group, a group having a urethane (meth) acryloyl group, and a hydroxyl group.
• the “acid dissociative group” is a group that cleaves in the presence of an acid to generate an alkali-soluble group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group) or the like.
• the acid dissociative group is not particularly limited, but is appropriately selected from those proposed in, for example, hydroxystyrene resins used in chemically amplified resist compositions for KrF and ArF, (meth) acrylic acid resins, and the like. Can be used. Specific examples of the acid dissociative group include those described in International Publication No. 2016/158168.
• A may have a substituent.
• Examples of the compound serving as the skeleton of A include alkenes having 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms or 1 to 6 carbon atoms, which may have a substituent; May have an alkene having 2 to 30 carbon atoms, 2 to 20 carbon atoms, 2 to 10 carbon atoms or 2 to 6 carbon atoms; may have a substituent, 2 to 30 carbon atoms, carbon Alkenes with 2 to 20 carbon atoms or 2 to 6 carbon atoms; may have substituents, 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms or 3 carbon atoms.
• Cycloalkane to 6 may have a substituent; a cycloalkene having 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms or 3 to 6 carbon atoms; having a substituent. It may have 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms or 3 to 6 carbon atoms; it may have a substituent, 5 to 30 carbon atoms, 5 to 5 carbon atoms. 20. Alkenes having 5 to 10 carbon atoms or 5 to 6 carbon atoms; combinations thereof and the like can be mentioned.
• Specific examples of the compound forming the skeleton of A include, for example, methane, ethane, propane, butene, pentane, hexane, heptane, octane, nonane, decane, icosane, triacontane, and cyclo, which may have a substituent.
• Preferred skeletons of A include benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene, and combinations thereof, which may have substituents. Can be used as appropriate. More preferred skeletons of A include benzene and adamantane.
• the substituent of the compound that forms the skeleton of A is not particularly limited, but is, for example, a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, or a linear group.
• Aliphatic hydrocarbon group branched aliphatic hydrocarbon group, cyclic aliphatic hydrocarbon group, aryl group, aralkyl group, alkoxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloxy group, allyloyloxy group, Examples thereof include an alkylsilyl group, various crosslinkable groups, and an acid dissociable group.
• Crosslinkable group the “acid-dissociable group” is not particularly limited, can be used for example as described in the description of the R 4.
• At least one n 1 is 0 and at least one n 1 is 1.
• n 2 is an integer of 1 to 5, preferably an integer of 2 to 5, and more preferably an integer of 2 to 3.
• the compound represented by the formula (1) is preferably a compound represented by the following formula (2) from the viewpoint of easy reactivity.
• R 1 , A, n 0 , n 1 , and n 2 are as defined in the above formula (1).
• the compound represented by the formula (1) is more preferably a compound represented by the following formula (3) from the viewpoint of etching resistance.
• B represents an organic group having 5 to 30 carbon atoms including an aromatic ring
• R 1 , n 0 , n 1 , and n 2 are as defined in the above formula (1).
• B may have a substituent.
• Examples of the compound serving as the skeleton of B include arenes having 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, and 5 to 6 carbon atoms, which may have a substituent. ..
• the compound forming the skeleton of B include, for example, benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, and azulene, which may have a substituent.
• Examples include fluorene and combinations thereof. These may include ether bonds, ketone bonds, and ester bonds.
• a more preferred skeleton of B is benzene.
• the substituent of the compound that forms the skeleton of B is not particularly limited, but is, for example, a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, or a linear group.
• Aliphatic hydrocarbon group branched aliphatic hydrocarbon group, cyclic aliphatic hydrocarbon group, aryl group, aralkyl group, alkoxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloxy group, allyloyloxy group, Examples thereof include an alkylsilyl group, various crosslinkable groups and an acid dissociable group, and a hydroxyl group or an acid dissociable group is preferable.
• Crosslinkable group the “acid-dissociable group” is not particularly limited, can be used for example as described in the description of the R 4.
• the acid dissociative group bonded to the aromatic ring of B is preferably a group that cleaves in the presence of an acid to generate a hydroxyl group.
• the compound represented by the formula (1) is more preferably a compound represented by the following formula (3') from the viewpoint of etching resistance.
• B' represents an organic group having 5 to 30 carbon atoms including an alicyclic
• R 1 , n 0 , n 1 , and n 2 are as defined in the above formula (1).
• B' may have a substituent.
• the compound forming the skeleton of B'in include, for example, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosane, cyclotriacontane, adamantane, which may have a substituent. Combinations and the like can be mentioned. These may include ether bonds, ketone bonds, and ester bonds. A more preferred skeleton of B'is adamantane.
• the substituent of the compound that forms the skeleton of B' is not particularly limited, but is, for example, a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, or a straight chain.
• Alkyl special group branched aliphatic hydrocarbon group, cyclic aliphatic hydrocarbon group, aryl group, aralkyl group, alkoxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloxy group, allyloyloxy group.
• Alkylsilyl group various crosslinkable groups and acid dissociable groups.
• Crosslinkable group the “acid-dissociable group” is not particularly limited, can be used for example as described in the description of the R 4.
• R 1 represents a hydrogen atom or a methyl group.
• a halogen group for example, an iodine group
• an alcohol derivative containing a hydroxy group-containing aromatic is used as a halogen group.
• An esterification reaction may be carried out.
• a method of reacting iodine chloride in an organic solvent by carrying out an iodination reaction on a hydroxybenzyl alcohol derivative for example, Japanese Patent No. 5754842.
• a method of dropping iodine into an alkaline aqueous solution of phenol in the presence of an alkaline atmosphere and ⁇ -cyclodextrin Japanese Patent Laid-Open No. 63-101342, JP-A-2003-64012 is known.
• Japanese Patent Laid-Open No. 63-101342, JP-A-2003-64012 Japanese Patent Laid-Open No. 63-101342, JP-A-2003-64012
• the halogen-containing polymerizable compound of the present embodiment can be synthesized by esterifying the alcohol moiety of the produced iodine-introduced hydroxybenzyl alcohol derivative by the method described later.
• the iodine-containing hydroxy compound represented by the general formula (a) is reacted with the (meth) acrylic acid compound represented by the general formula (b). Methods can be mentioned, but are not limited to this.
• R 4 , A, n 0 , n 1 , n 2 are as defined in equation (1)
• R 1 is as defined in formula (1)
• R B is .R B is selected from the group consisting of hydroxyl group, a halogen atom and (meth) acryloyloxy group , Preferably a halogen atom such as a chlorine atom.
• the compound represented by the general formula (a) is preferably a compound represented by the general formula (a1).
• A, n 0 , n 1 , n 2 are as defined in the above formula (1)).
• the compound represented by the general formula (a) is preferably a compound represented by the general formula (a2).
• B represents an organic group having 5 to 30 carbon atoms including an aromatic ring.
• n 0 , n 1 , and n 2 are as defined in the above equation (1))
• the compound represented by the general formula (a) is preferably a compound represented by the general formula (a3).
• B' represents an organic group having 5 to 30 carbon atoms including an alicyclic ring.
• n 0 , n 1 , and n 2 are as defined in the above equation (1))
• the (meth) acrylic acid compound represented by the general formula (b) of the present invention is exemplified below.
• (meth) acrylic acid compounds (meth) acrylic acid chloride is preferable from the viewpoint of reactivity.
• Formula iodine-containing hydroxy compound represented by (a), and represented by the general formula (b) (meth) the amount of the acrylic acid compound may be suitably adjusted according to the number of n 0.
• reaction temperature and reaction time depend on the substrate concentration and the catalyst used, but generally, the reaction temperature is -20 ° C to 100 ° C, the reaction time is 1 hour to 10 hours, and the pressure is normal pressure, reduced pressure or pressurized. it can. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
• a polymerization inhibitor may be added to the series of reactions, and a generally available commercially available product can be used.
• a polymerization inhibitor may be added to the series of reactions, and a generally available commercially available product can be used.
• a generally available commercially available product can be used.
• 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, N-nitroso-N- (1-naphthyl)
• Nitroso compounds such as hydroxylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaftor, p-nitrosophenol, N, N'-dimethyl-p-nitrosoaniline, phenothiazine, methylene blue, 2-mercapto Sulfur-containing compounds such as benzoimidazole, N, N'-dipheny
• the halogen-containing polymerizable compound of the present embodiment obtained by the reaction can be obtained from known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification methods using activated charcoal, and the like. It can be isolated and purified as a desired high-purity monomer by a combined method.
• the (co) polymer of the present embodiment preferably has a structural unit derived from the halogen-containing polymerizable compound. It has a repeating unit represented by the following formula (A). (In the formula (A-1), R 1 , R 2 , R 3 , L, A, X, n 0 , and n 2 are as defined in the above formula (A)).
• the compound represented by the general formula (A-1) is preferably a compound represented by the general formula (1-1).
• R 1 , R 4 , A, n 0 , n 1 , and n 2 are as defined in the above equation (1)).
• the (co) polymer according to the present embodiment having a structural unit derived from the halogen-containing polymerizable compound may polymerize the halogen-containing polymerizable compound according to the present embodiment, or the halogen-containing polymerizable compound according to the present embodiment. Can be obtained by polymerizing with other monomers. Examples of other monomers include those having a functional group whose solubility in an alkaline developer is improved by the action of an acid or a base.
• the (co) polymer according to the present embodiment can be used as a material for forming a film for lithography.
• RC13 together with the carbon atom to which RC13 is attached, represents a cycloalkyl group or a heterocycloalkyl group having 4 to 20 carbon atoms.
• the point * represents the connection point with the adjacent repeating unit.
• R C12 is hydrogen or an alkyl group having a carbon number of 1 ⁇ 3, R C13 together with the carbon atom to which R C13 are attached, a cycloalkyl group or a heterocycle having 4 to 10 carbon atoms It is an alkyl group.
• R 13 may have a substituent (eg, an oxo group).
• RC21 represents a hydrogen or methyl group RC22 and RC23 each independently represent an alkyl group having 1 to 4 carbon atoms.
• RC24 represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. Two or three of RC22 to RC24 may be combined with the carbon atoms to which they are bonded to form an alicyclic structure having 3 to 20 carbon atoms.
• the point * represents the connection point with the adjacent repeating unit.
• RC22 represents an alkyl group having 1 to 3 carbon atoms and RC24 is a cycloalkyl group having 5 to 10 carbon atoms.
• the alicyclic structure R C22 ⁇ R C24 is formed, for example, may include a plurality of rings, such as adamantyl groups. Further, the alicyclic structure may have a substituent (for example, a hydroxyl group or an alkyl group).
• the repeating unit monomer raw material represented by the general formula (C2) is not limited, for example, 2-methyl-2- (meth) acrylic loyloxyadamantane, 2-ethyl-2- (meth) acrylic loyloxyadamantane, and the like.
• a (co) polymer having a structural unit derived from the halogen-containing polymerizable compound according to the present embodiment is preferable in order to improve the performance of the film-forming material for lithography.
• the polymerization reaction is carried out by dissolving a monomer as a repeating unit in a solvent, adding a catalyst, and heating or cooling.
• the reaction conditions can be arbitrarily set depending on the type of initiator, the starting method such as heat and light, temperature, pressure, concentration, solvent, additive and the like.
• the (co) polymer according to the present embodiment may be produced by radical polymerization using a radical generator such as azoisobutyronitrile or peroxide, or ion polymerization using a catalyst such as alkyllithium or Grinard reagent. It can be carried out by a known method.
• the solvent used in the polymerization reaction a commercially available commercially available product can be used.
• various solvents such as alcohol, ether, hydrocarbon, and halogen-based solvent can be appropriately used as long as the reaction is not inhibited.
• a plurality of solvents may be mixed and used as long as the above reaction is not inhibited.
• the (co) polymer obtained by the polymerization reaction can be purified by a known method. Specifically, ultrafiltration, crystallization, microfiltration, acid cleaning, water cleaning with an electrical conductivity of 10 mS / m or less, and extraction can be performed in combination.
• the compound in the present embodiment is obtained as a crude product by the above reaction and then further purified to remove residual metal impurities. That is, in the compound manufacturing process, from the viewpoint of prevention of deterioration of the resin over time and storage stability, and further, from the viewpoint of process suitability when resinified and applied to the semiconductor manufacturing process, manufacturing profitability due to defects, etc. It is preferable to avoid residual gold-damaged impurities resulting from the mixing of metal components used as reaction aids or mixed from reaction kettles for manufacturing or other manufacturing equipment.
• the compound in the present embodiment is characterized by having a halogen element as a substituent to improve the exposure efficiency in the lithography process and thereby improving the lithography performance, but the metal-containing impurities remain in the system.
• the halogen element characteristic of the compound of the present embodiment becomes unstable and the desired characteristics cannot be obtained, or unexpected secondary factors such as decomposition of the resin and formation of bonds between the resins due to desorption of the halogen element or the like occur.
• the following reaction will be induced, resulting in performance deterioration in terms of sensitivity, resolution, roughness, exposure stability, defects, etc. in lithography. From these factors, it is preferable to reduce metal-containing impurities.
• the halogen element is destabilized by Fe, Al, Sb, Ru, W and the like.
• the residual amount of the metal impurities is preferably less than 1 ppm, more preferably less than 100 ppb, and even more preferably less than 50 ppb with respect to each resin.
• metal species such as Fe, Al, Sb, Ru, and W, which are classified as transition metals
• the metal residual amount is 1 ppm or more, the material is modified or deteriorated over time due to the interaction with the compound in the present embodiment. There are concerns that may be a factor in this. Further, if it is 1 ppm or more, the remaining amount of metal cannot be sufficiently reduced when a resin for a semiconductor process is prepared using the prepared compound, and defects and performance derived from residual metal in the semiconductor manufacturing process cannot be sufficiently reduced. There is concern that it may cause a decrease in profitability due to deterioration.
• the purification method is not particularly limited, but the step of dissolving the compound in the present embodiment in a solvent to obtain a solution (S) and the obtained solution (S) and an acidic aqueous solution are brought into contact with each other to obtain the above-mentioned.
• the solvent used in the step of obtaining the solution (S) includes an organic solvent which is optionally immiscible with water, including a step of extracting impurities in the compound in the present embodiment (first extraction step). According to the purification method, the content of various metals that can be contained as impurities in the resin can be reduced.
• the compound in the present embodiment is dissolved in an organic solvent that is arbitrarily immiscible with water to obtain a solution (S), and the solution (S) is further brought into contact with an acidic aqueous solution for extraction treatment. be able to.
• the organic phase and the aqueous phase can be separated to obtain a resin having a reduced metal content.
• the solvent that is not arbitrarily miscible with the water used in the above purification method is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable, and specifically, the solubility in water at room temperature is 30%.
• the organic solvent is less than, more preferably less than 20%, and particularly preferably less than 10%.
• the amount of the organic solvent used is preferably 1 to 100 times by mass with respect to the total amount of the resins used.
• solvents such as diethyl ether and diisopropyl ether
• esters such as ethyl acetate, n-butyl acetate and isoamyl acetate, methyl ethyl ketone and methyl isobutyl.
• Ketones such as ketones, ethyl isobutyl ketones, cyclohexanones, cyclopentanones, 2-heptanones, 2-pentanones; ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl Glycol ether acetates such as ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and chloroform. ..
• toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, and methyl isobutyl ketone, ethyl acetate, cyclohexanone and propylene glycol monomethyl ether acetate are more preferable.
• Methyl isobutyl ketone and ethyl acetate are even more preferable.
• the acidic aqueous solution used in the above purification method is appropriately selected from generally known organic compounds or aqueous solutions in which an inorganic compound is dissolved in water.
• an aqueous solution of mineral acid in which mineral acids such as hydrochloric acid, sulfuric acid, nitrate and phosphoric acid are dissolved in water, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid and maleic acid.
• Each of these acidic aqueous solutions can be used alone, or two or more of them can be used in combination.
• one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitrate and phosphoric acid, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid
• An aqueous solution of a carboxylic acid such as tartrate acid or citric acid is more preferable, an aqueous solution of sulfuric acid, oxalic acid, tartrate acid or citrate is more preferable, and an aqueous solution of oxalic acid is even more preferable.
• polyvalent carboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate to metal ions and produce a chelating effect, so that the metal can be removed more effectively.
• water used here it is preferable to use water having a low metal content, for example, ion-exchanged water, etc., in line with the purpose of the purification method in the present embodiment.
• the pH of the acidic aqueous solution used in the above purification method is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the resin.
• the pH range is about 0 to 5, preferably about pH 0 to 3.
• the amount of the acidic aqueous solution used in the above purification method is not particularly limited, but the amount used may be used from the viewpoint of reducing the number of extractions for removing the metal and ensuring operability in consideration of the total amount of the liquid. It is preferable to adjust. From the above viewpoint, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, more preferably 20 to 100% by mass, based on 100% by mass of the solution (S).
• the metal component can be extracted from the resin in the solution (S) by bringing the acidic aqueous solution into contact with the solution (S).
• the above solution (S) may further contain an organic solvent that is optionally miscible with water.
• an organic solvent that is arbitrarily miscible with water is contained, the amount of the resin charged can be increased, the liquid separation property is improved, and purification can be performed with high pot efficiency.
• the method of adding an organic solvent that is arbitrarily miscible with water is not particularly limited.
• any of a method of adding to a solution containing an organic solvent in advance, a method of adding to water or an acidic aqueous solution in advance, and a method of adding after contacting a solution containing an organic solvent with water or an acidic aqueous solution may be used.
• the method of adding to a solution containing an organic solvent in advance is preferable in terms of workability of operation and ease of control of the amount to be charged.
• the organic solvent that is arbitrarily miscible with the water used in the above purification method is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable.
• the amount of the organic solvent that is arbitrarily miscible with water is not particularly limited as long as the solution phase and the aqueous phase are separated, but is 0.1 to 100 times by mass with respect to the total amount of the resins used. It is preferable, it is more preferably 0.1 to 50 times by mass, and further preferably 0.1 to 20 times by mass.
• ethers such as tetrahydrofuran and 1,3-dioxolane
• alcohols such as methanol, ethanol and isopropanol
• acetone. N-Methylpyrrolidone and the like
• aliphatic hydrocarbons such as ethylene glycol monoethyl ether, ethylene glycol monobuty
• N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable.
• Each of these solvents can be used alone, or two or more of them can be mixed and used.
• the temperature at which the extraction process is performed is usually 20 to 90 ° C, preferably 30 to 80 ° C.
• the extraction operation is performed by, for example, stirring well and then allowing the mixture to stand. As a result, the metal content contained in the solution (S) shifts to the aqueous phase. Further, by this operation, the acidity of the solution is lowered, and the deterioration of the resin can be suppressed.
• the above mixed solution is separated into a solution phase containing a resin and a solvent and an aqueous phase by standing, so the solution phase is recovered by decantation or the like.
• the standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation between the solution phase containing the solvent and the aqueous phase.
• the standing time is 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more.
• the extraction process may be performed only once, it is also effective to repeat the operations of mixing, standing, and separating a plurality of times.
• the purification method it is preferable to include a step (second extraction step) of extracting impurities in the resin by further contacting the solution phase containing the resin with water after the first extraction step.
• the above extraction treatment is performed using an acidic aqueous solution, and then the solution phase containing the resin and the solvent extracted and recovered from the aqueous solution is further subjected to the extraction treatment with water.
• the above-mentioned extraction treatment with water is not particularly limited, but can be carried out, for example, by mixing the above solution phase and water well by stirring or the like, and then allowing the obtained mixed solution to stand.
• the solution phase can be recovered by decantation or the like.
• the water used here is preferably water having a low metal content, for example, ion-exchanged water, etc., in line with the object of the present embodiment.
• the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times.
• the conditions such as the ratio of use of both in the extraction treatment, the temperature, and the time are not particularly limited, but the same as in the case of the contact treatment with the acidic aqueous solution may be used.
• Moisture that can be mixed in the solution containing the resin and the solvent thus obtained can be easily removed by performing an operation such as vacuum distillation. Further, if necessary, a solvent can be added to the above solution to adjust the resin concentration to an arbitrary concentration.
• the compound purification method according to the present embodiment can also be purified by passing a solution of the resin dissolved in a solvent through a filter.
• the content of various metals in the resin can be effectively and remarkably reduced.
• the amounts of these metal components can be measured by the method described in Examples described later.
• the term "passing liquid" in the present embodiment means that the solution passes from the outside of the filter to the inside of the filter and moves to the outside of the filter again. For example, the solution is simply transferred to the surface of the filter.
• the mode of contacting with the ion exchange resin and the mode of moving the solution outside the ion exchange resin while contacting the solution on the surface are excluded.
• the filter used for removing the metal component in the solution containing the resin and the solvent can usually be a commercially available filter for liquid filtration.
• the filtration accuracy of the filter is not particularly limited, but the nominal pore size of the filter is preferably 0.2 ⁇ m or less, more preferably less than 0.2 ⁇ m, still more preferably 0.1 ⁇ m or less, still more preferably 0. It is less than .1 ⁇ m, more preferably 0.05 ⁇ m or less.
• the lower limit of the nominal pore size of the filter is not particularly limited, but is usually 0.005 ⁇ m.
• the nominal pore size referred to here is a nominal pore size indicating the separation performance of the filter, and is determined by a test method determined by the filter manufacturer, such as a bubble point test, a mercury intrusion method test, and a standard particle supplementation test. Hole diameter. When a commercially available product is used, it is a value described in the manufacturer's catalog data.
• the filter passing step may be performed twice or more.
• a hollow fiber membrane filter As the form of the filter, a hollow fiber membrane filter, a membrane filter, a pleated membrane filter, and a filter filled with a filter medium such as non-woven fabric, cellulose, and Keisou soil can be used.
• the filter is one or more selected from the group consisting of a hollow fiber membrane filter, a membrane filter and a pleated membrane filter.
• the material of the filter includes polyolefins such as polyethylene and polypropylene, polyethylene-based resins having a functional group capable of ion-exchange by graft polymerization, polyamides, polyesters, polar group-containing resins such as polyacrylonitrile, polyethylene fluoride (PTFE) and the like. Fluorine-containing resin can be mentioned.
• the filter medium of the filter is at least one selected from the group consisting of polyamide, poreolefin resin and fluororesin.
• polyamide is particularly preferable from the viewpoint of reducing heavy metals such as chromium. From the viewpoint of avoiding metal elution from the filter medium, it is preferable to use a filter other than the sintered metal material.
• Polyamide-based filters are not limited to the following, but are, for example, Polyfix Nylon Series manufactured by KITZ Micro Filter Co., Ltd., Uruchi Pleated P-Nylon 66 manufactured by Nippon Pole Co., Ltd., Ulchipore N66, and 3M Ltd. Life Asure PSN series and Life Asure EF series manufactured by KITZ Corporation can be mentioned.
• the polyolefin-based filter is not limited to the following, but includes, for example, Uruchi Pleated PE Clean and Ion Clean manufactured by Nippon Pole Co., Ltd., Protego Series manufactured by Nippon Integris Co., Ltd., Microguard Plus HC10, Optimizer D, and the like. Can be mentioned.
• polyester filter examples include, but are not limited to, Jeraflow DFE manufactured by Central Filter Industry Co., Ltd., Breeze type PMC manufactured by Nippon Filter Co., Ltd., and the like.
• the polyacrylonitrile-based filter is not limited to the following, and examples thereof include ultrafilters AIP-0013D, ACP-0013D, and ACP-0053D manufactured by Advantech Toyo Co., Ltd.
• Examples of the fluororesin-based filter examples include, but are not limited to, Enflon HTPFR manufactured by Nippon Pole Co., Ltd., Lifesure FA series manufactured by 3M Ltd., and the like. Each of these filters may be used alone or in combination of two or more.
• the filter may contain an ion exchanger such as a cation exchange resin, a cation charge modifier that causes a zeta potential in the organic solvent solution to be filtered, and the like.
• an ion exchanger such as a cation exchange resin, a cation charge modifier that causes a zeta potential in the organic solvent solution to be filtered, and the like.
• the filter containing the ion exchanger include, but are not limited to, the Protego series manufactured by Entegris Japan KK and the clan graft manufactured by Kurashiki Textile Manufacturing Co., Ltd.
• the filter containing a substance having a positive zeta potential such as polyamide polyamine epichlorohydrin cationic resin is not limited to the following, but for example, Zeta Plus 40QSH and Zeta Plus 020GN manufactured by 3M Ltd. , Or Life Asure EF series and the like.
• composition containing halogen-containing polymerizable compound or (co) polymer thereof contains a halogen-containing polymerizable compound or a (co) polymer thereof, and is particularly suitable for lithography technology.
• the composition can be used for lithographic film forming applications, for example, resist film forming applications (that is, "resist composition”).
• the composition is used for upper layer film forming use (that is, “upper layer film forming composition”), intermediate layer forming use (that is, “intermediate layer forming composition”), and lower layer film forming use (that is, "” It can be used as a composition for forming an underlayer film ”) or the like.
• it is possible to form a film having high sensitivity and to impart a good resist pattern shape.
• composition of this embodiment can also be used as an optical component forming composition to which a lithography technique is applied.
• Optical components are used in film and sheet forms, as well as plastic lenses (prism lenses, lenticular lenses, microlenses, frennel lenses, viewing angle control lenses, contrast improving lenses, etc.), retardation films, electromagnetic wave shielding films, and prisms.
• TFT organic thin film transistor
• the composition is an embedded film and a flattening film on a photodiode, a flattening film before and after a color filter, a microlens, and a flattening on a microlens, which are members of a solid-state image sensor for which a particularly high refractive index is required. It can be suitably used as a film and a conformal film.
• the composition of the present embodiment contains a halogen-containing polymerizable compound or a (co) polymer (B) thereof, and if necessary, a base material (A), a solvent (S), an acid generator (C), and an acid. It may contain other components such as the diffusion control agent (E). Hereinafter, each component will be described.
• the "base material (A)” is a compound (including a resin) other than the halogen-containing polymerizable compound or its (co) polymer, and is g-ray, i-ray, KrF excimer laser (248 nm). , ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), and a substrate applied as a resist for electron beam (EB) (for example, a substrate for lithography or a substrate for resist).
• These base materials are not particularly limited and can be used as the base material (A) in the present embodiment.
• Examples of the base material (A) include phenol novolac resin, cresol novolac resin, hydroxystyrene resin, (meth) acrylic resin, hydroxystyrene- (meth) acrylic copolymer, cycloolefin-maleic anhydride copolymer, and the like.
• Examples thereof include cycloolefins, vinyl ether-maleic anhydride copolymers, inorganic resist materials having metal elements such as titanium, tin, hafnium and zirconium, and derivatives thereof.
• phenol novolac resin cresol novolac resin, hydroxystyrene resin, (meth) acrylic resin, hydroxystyrene- (meth) acrylic copolymer, and titanium, tin, hafnium and zirconium.
• Inorganic resist materials having metal elements such as, and derivatives thereof are preferable.
• the derivative is not particularly limited, and examples thereof include those having a dissociative group introduced therein and those having a crosslinkable group introduced therein.
• the derivative into which the dissociative group or the crosslinkable group is introduced can exhibit a dissociative reaction or a crosslinkable reaction by the action of light, acid or the like.
• Dissociative group refers to a characteristic group that produces a functional group such as an alkali-soluble group that cleaves and changes its solubility.
• the alkali-soluble group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group.
• a phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is particularly preferable.
• Crosslinkable group means a group that crosslinks in the presence of a catalyst or in the absence of a catalyst.
• the crosslinkable group is not particularly limited, and has, for example, an alkoxy group having 1 to 20 carbon atoms, a group having an allyl group, a group having a (meth) acryloyl group, a group having an epoxy (meth) acryloyl group, and a hydroxyl group. Examples thereof include a group having a urethane (meth) acryloyl group, a group having a glycidyl group, and a group having a vinylphenylmethyl group.
• solvent (S) As the solvent in this embodiment, a known solvent can be appropriately used as long as the halogen-containing polymerizable compound or its (co) polymer (B) is at least soluble.
• Specific examples of the solvent are not particularly limited, but for example, ethylene glycol mono such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate.
• Alkyl ether acetates ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, Propropylene glycol monoalkyl ether acetates such as propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate , Lactic acid esters such as n-butyl lactic acid and n-amyl lactic acid; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl a
• Aliphatic carboxylic acid esters methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxy Other esters such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate, etc.
• aromatic hydrocarbons such as toluene and xylene
• ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN);
• N, N -Amids such as dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone
• lactones such as ⁇ -lactone and the like can be mentioned, but are not particularly limited.
• the solvent used in the present embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate and ethyl lactate. Yes, more preferably at least one selected from PGMEA, PGME, CHN, CPN and ethyl lactate.
• the amount of the solid component and the amount of the solvent are not particularly limited, but are 1 to 80% by mass of the solid component and 20 to 99% by mass of the solvent with respect to the total mass of the amount of the solid component and the solvent. It is preferable, more preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, further preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably 2 to 10% by mass of the solid component. It is mass% and solvent 90-98 mass%.
• acid generator (C) In the composition of the present embodiment, acid is directly or indirectly generated by irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray and ion beam. It is preferable to contain one or more acid generators (C).
• the acid generator (C) is not particularly limited, but for example, the acid generator (C) described in International Publication WO2013 / 024778 can be used.
• the acid generator (C) may be used alone or in combination of two or more.
• the amount of the acid generator (C) used is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, further preferably 3 to 30% by mass, and 10 to 25% by mass of the total mass of the solid component. Especially preferable.
• the acid generator (C) within the above range, a pattern profile with high sensitivity and low edge roughness tends to be obtained.
• the method of generating the acid is not particularly limited. Finer processing is possible by using an excimer laser instead of ultraviolet rays such as g-rays and i-rays, and further fine processing is possible by using electron beams, extreme ultraviolet rays, X-rays, and ion beams as high-energy rays. Is possible.
• the acid diffusion control agent (E) having an action of controlling the diffusion of the acid generated from the acid generator in the resist film by irradiation to prevent an unfavorable chemical reaction in the unexposed region and the like. May be blended into the composition.
• the storage stability of the composition of the present embodiment tends to be improved.
• the resolution of the film formed by using the composition of the present embodiment can be improved, and the retention time before irradiation and the pulling after irradiation can be improved. It is possible to suppress the change in the line width of the resist pattern due to the fluctuation with the standing time, and the process stability tends to be excellent.
• the acid diffusion control agent (E) is not particularly limited, and examples thereof include radiodegradable basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds.
• the acid diffusion control agent (E) is not particularly limited, but for example, the one described in International Publication WO2013 / 024778 can be used.
• the acid diffusion control agent (E) may be used alone or in combination of two or more.
• the blending amount of the acid diffusion control agent (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.01 to 5% by mass, and 0. 0.01 to 3% by mass is particularly preferable.
• the blending amount of the acid diffusion control agent (E) is within the above range, it tends to be possible to prevent deterioration of resolution, pattern shape, dimensional fidelity, and the like. Further, even if the leaving time from the electron beam irradiation to the heating after the irradiation is long, it is possible to suppress the deterioration of the shape of the upper layer portion of the pattern.
• the blending amount is 10% by mass or less, it tends to be possible to prevent deterioration of sensitivity, developability of the unexposed portion, and the like. Further, by using such an acid diffusion control agent, the storage stability of the resist composition is improved, the resolution is improved, and the retention time before irradiation and the retention time after irradiation vary. The change in the line width of the resist pattern can be suppressed, and the process stability tends to be excellent.
• composition of the present embodiment if necessary, a cross-linking agent, a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant and an organic carboxylic acid or an oxo acid of phosphorus or One or two or more kinds of various additives such as the derivative can be added.
• the cross-linking agent means a compound capable of cross-linking at least one of the base material (A) or the halogen-containing polymerizable compound or its (co) polymer (B).
• the cross-linking agent is preferably an acid cross-linking agent capable of intramolecularly or intermolecularly cross-linking the base material (A) in the presence of an acid generated from the acid generator (C).
• Examples of such an acid cross-linking agent include compounds having one or more groups (hereinafter, referred to as “crosslinkable groups”) capable of cross-linking the base material (A).
• crosslinkable group examples include (i) hydroxy (alkyl group having 1 to 6 carbon atoms), alkoxy having 1 to 6 carbon atoms (alkyl group having 1 to 6 carbon atoms), and acetoxy (alkyl group having 1 to 6 carbon atoms).
• a group derived from the aromatic group of (vi), a polymerizable multiple bond-containing group such as a vinyl group or an isopropenyl group, and the like can be mentioned.
• a crosslinkable group of the cross-linking agent in the present embodiment a hydroxyalkyl group, an alkoxyalkyl group and the like are preferable, and an alkoxymethyl group is particularly preferable.
• the cross-linking agent having a cross-linking group is not particularly limited, but for example, the acid cross-linking agent described in International Publication WO2013 / 024778 can be used.
• the cross-linking agent may be used alone or in combination of two or more.
• the blending amount of the cross-linking agent is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on the total mass of the solid components.
• the dissolution accelerator is a component having an action of increasing the solubility of a solid component in a developing solution and appropriately increasing the dissolution rate of the compound during development.
• the dissolution accelerator is preferably one having a low molecular weight, and examples thereof include a low molecular weight phenolic compound. Examples of the low molecular weight phenolic compound include bisphenols and tris (hydroxyphenyl) methane. These dissolution accelerators can be used alone or in combination of two or more.
• the blending amount of the dissolution accelerator is appropriately adjusted according to the type of the solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total mass of the solid component. % Is more preferable, and 0% by mass is particularly preferable.
• the dissolution control agent is a component having an action of controlling the solubility of a solid component in a developing solution and appropriately reducing the dissolution rate during development.
• a dissolution control agent one that does not chemically change in steps such as firing of the resist film, irradiation, and development is preferable.
• the dissolution control agent is not particularly limited, but for example, aromatic hydrocarbons such as phenanthrene, anthracene and acenaphthene; ketones such as acetophenone, benzophenone and phenylnaphthylketone; and methylphenylsulfone, diphenylsulfone, dinaphthylsulfone and the like. Sulfones and the like can be mentioned. These dissolution control agents may be used alone or in combination of two or more.
• the blending amount of the dissolution control agent is appropriately adjusted according to the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0-1% by mass of the total mass of the solid component. Is more preferable, and 0% by mass is particularly preferable.
• the sensitizer has the effect of absorbing the energy of the irradiated radiation and transferring that energy to the acid generator (C), thereby increasing the amount of acid produced, improving the apparent sensitivity of the resist. It is an ingredient to make.
• a sensitizer include benzophenones, biacetyls, pyrenes, phenothiazines, fluorenes, and the like, but are not particularly limited. These sensitizers can be used alone or in combination of two or more.
• the blending amount of the sensitizer is appropriately adjusted according to the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total mass of the solid component. More preferably, 0% by mass is particularly preferable.
• the surfactant is a component having an action of improving the coatability, striation, developability of the resist, etc. of the composition of the present embodiment.
• the surfactant may be any of an anionic surfactant, a cationic surfactant, a nonionic surfactant or an amphoteric surfactant.
• Preferred surfactants include nonionic surfactants.
• the nonionic surfactant has a good affinity with the solvent used for producing the composition of the present embodiment, and can further enhance the effect of the composition of the present embodiment.
• nonionic surfactant examples include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the like, but are not particularly limited.
• Commercially available products of these surfactants include Ftop (manufactured by Gemco), Megafuck (manufactured by Dainippon Ink and Chemicals, Inc.), Florard (manufactured by Sumitomo Three-M), and Asahigard under the following trade names.
• the blending amount of the surfactant is appropriately adjusted according to the type of the solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total mass of the solid component. % Is more preferable, and 0% by mass is particularly preferable.
• an organic carboxylic acid or phosphorus oxo acid or its derivative For the purpose of preventing sensitivity deterioration or improving the resist pattern shape, retention stability, etc., an organic carboxylic acid or phosphorus oxo acid or a derivative thereof can be further contained as an arbitrary component.
• the organic carboxylic acid or the oxo acid of phosphorus or a derivative thereof can be used in combination with an acid diffusion control agent, or may be used alone.
• the organic carboxylic acid for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
• Examples of phosphorus oxo acids or derivatives thereof include phosphoric acids such as phosphoric acid, di-n-butyl ester of phosphoric acid, and diphenyl ester of phosphoric acid, or derivatives of their esters, phosphonic acid, dimethyl phosphonic acid ester, and di-phosphonic acid.
• Examples include phosphonic acids such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester and phosphonic acid dibenzyl ester or derivatives such as their esters, phosphinic acid such as phosphinic acid and phenylphosphinic acid and derivatives such as their esters. Of these, phosphonic acid is particularly preferable.
• the organic carboxylic acid or phosphorus oxo acid or its derivative can be used alone or in combination of two or more.
• the blending amount of the organic carboxylic acid or the oxo acid of phosphorus or a derivative thereof is appropriately adjusted according to the type of the compound used, but is preferably 0 to 49% by mass, preferably 0 to 5% by mass, based on the total mass of the solid component. More preferably, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.
• the composition of the present embodiment may contain one or more additives other than the above-mentioned components, if necessary.
• additives include dyes, pigments, adhesive aids and the like.
• a dye or a pigment because the latent image of the exposed portion can be visualized and the influence of halation during exposure can be alleviated.
• an adhesive aid because the adhesiveness to the substrate can be improved.
• examples of other additives include anti-halation agents, storage stabilizers, antifoaming agents, shape improvers and the like, specifically 4-hydroxy-4'-methylchalcone and the like.
• the total amount of the optional component (F) can be 0 to 99% by mass, preferably 0 to 49% by mass, more preferably 0 to 10% by mass, based on the total mass of the solid components. , 0 to 5% by mass is further preferable, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.
• the composition solution is applied to a substrate such as a silicon wafer, metal, plastic, glass, ceramic, etc. by an appropriate coating means such as a spin coater, a dip coater, a roller coater, or the like.
• a resist film is formed, and in some cases, heat treatment is performed in advance at a temperature of about 50 ° C. to 200 ° C., and then exposure is performed through a predetermined mask pattern.
• the thickness of the coating film is, for example, about 0.1 to 20 ⁇ m, preferably about 0.3 to 2 ⁇ m.
• Light rays of various wavelengths, such as ultraviolet rays and X-rays, can be used for the exposure.
• the light sources include an F2 excimer laser (wavelength 157 nm), an ArF excimer laser (wavelength 193 nm), and a KrF excimer laser (wavelength 248 nm).
• Far ultraviolet rays, extreme ultraviolet rays (wavelength 13n), X-rays, electron beams, etc. are appropriately selected and used.
• the exposure conditions such as the exposure amount are appropriately selected according to the compounding composition of the above resin and / or the compound, the type of each additive, and the like.
• a predetermined resist pattern is formed by developing with an alkaline developer at 10 to 50 ° C. for 10 to 200 seconds, preferably at 20 to 25 ° C. for 15 to 90 seconds.
• alkali developing solution examples include alkali metal hydroxides, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, and 1,8-diazabicyclo- [5.
• Alkaline compounds such as 4.0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonen are usually concentrated in an amount of 1 to 10% by weight, preferably 1 to 3% by weight.
• An alkaline aqueous solution dissolved so as to be used is used. Further, a water-soluble organic solvent or a surfactant can be appropriately added to the developer composed of the alkaline aqueous solution.
• the composition of the present embodiment can be used as a patterning material for lithography applications.
• the lithography process can be used in various applications such as semiconductors, liquid display panels, display panels using OLEDs, power devices, CCDs, and other sensors.
• the composition of the present embodiment is used on the upper surface side of an insulating layer such as a silicon oxide film or other oxide film in the step of forming a device element on a silicon wafer.
• a pattern is formed on the insulating film on the substrate side by etching based on the formed pattern, and a metal film or semiconductor material is laminated based on the formed insulating film pattern to form a circuit pattern to form a semiconductor element or other device.
• the composition of the present embodiment can be preferably used for the purpose of constructing.
• the following compounds M3 to M5, MRA1, MRA3, and MRA5 were synthesized according to the method of Synthesis Example 1-1 using the corresponding raw materials.
• the following compounds MRB1, MRB3, MRB5, MRC1, MRC3, and MRC5 were synthesized according to the method of Synthesis Example 1-1 by appropriately reducing the amount of methacrylic acid used using the corresponding raw materials.
• the molecular weight (Mw) of this resin was 12000, and the dispersity (Mw / Mn) was 1.90.
• the following chemical formula (P-MAC-0I) is simply described to indicate the ratio of each structural unit, but in P-MAC-0I, each structural unit forms an independent block. It is not a block copolymer.
• a maskless shot exposure was performed by increasing the exposure amount from 1 mJ / cm2 to 80 mJ / cm2 by 1 mJ / cm2 with an EUV exposure device (manufactured by EUVES-7000), and then 90 at 110 ° C.
• the wafer was baked for seconds (PEB), developed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and exposed to 80 shots of shots on the wafer to obtain a wafer.
• PEB baked for seconds
• TMAH tetramethylammonium hydroxide
• the film thickness is measured with an interference film thickness meter, profile data of the film thickness with respect to the exposure amount is acquired, and the exposure amount with the largest inclination of the film thickness fluctuation amount with respect to the exposure amount is sensitive. It was calculated as a value (mJ / cm2) and used as an index of the EUV sensitivity of the resist.
• EB pattern evaluation A resin solution containing the resin prepared in the synthesis example or the synthesis comparative example was applied onto a silicon wafer and baked at 110 to 130 ° C. for 60 seconds to form a photoresist layer having a film thickness of 100 nm.
• the resin solution contains 5 parts by mass of the resin prepared in the synthesis example or the synthetic comparative example, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 0.1 part by mass of tributylamine, and 92 parts by mass of PGMEA. Formulated and prepared. Then, it was exposed with an electron beam drawing apparatus (ELS-7500, 50 keV), baked (PEB) at 115 ° C.
• ELS-7500 electron beam drawing apparatus
• PEB baked
• TMAH tetramethylammonium hydroxide
• the prepared resin solution was subjected to forced aging treatment under light-shielding conditions of 40 ° C./240 hours, EB pattern evaluation was similarly performed on the liquid after aging treatment, and a pattern image by SEM was similarly acquired to obtain roughness and roughness. Residue (scum) count between patterns was performed.
• a PTI (positive) pattern was formed using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution as an alkaline developer, and PTI roughness evaluation was performed. Further, organic solvent development was carried out using butyl acetate as a developing solution to form an NTI (negative) pattern, and NTI scum evaluation was carried out.
• TMAH tetramethylammonium hydroxide
• the quality of the resin prepared using the compound of the present invention obtained in the synthetic example was evaluated before and after the purification treatment. That is, the resin film formed on the wafer using the resin prepared by using the compound of the present invention was transferred to the substrate side by etching, and then the defect was evaluated.
• a 12-inch silicon wafer was subjected to thermal oxidation treatment to obtain a substrate having a silicon oxide film having a thickness of 100 nm.
• a resin solution of a resin prepared by using the compound of the present invention is formed on the substrate by adjusting spin coating conditions so as to have a thickness of 100 nm, and then a film is formed at 150 ° C. for 1 minute, followed by 350 ° C. for 1 minute.
• a laminated substrate was prepared by laminating a resin prepared using the compound of the present invention on silicon with a thermal oxide film.
• TELIUS manufactured by Tokyo Electron Limited
• the resin film was etched under the conditions of CF4 / O2 / Ar to expose the substrate on the surface of the oxide film.
• an etching treatment was performed under the condition that the oxide film was etched at 100 nm with a gas composition ratio of CF4 / Ar to prepare an etched wafer.
• the prepared etched wafer was measured for the number of defects of 19 nm or more with a defect inspection device SP5 (manufactured by KLA-tencor), and was carried out as a defect evaluation by etching treatment with a laminated film.
• Example E01 Purification of M1 resin with acid
• a solution (10% by mass) of the M1 resin obtained in Synthesis Example 1 dissolved in PGMEA was charged.
• 37.5 g of an aqueous oxalic acid solution (pH 1.3) was added, and the mixture was stirred for 5 minutes and allowed to stand for 30 minutes.
• the oil phase and the aqueous phase were separated, and the aqueous phase was removed.
• a solution containing a resin prepared by using the obtained compound of the present invention was filtered through a UPE filter having a nominal pore size of 3 nm manufactured by Entegris Japan, Inc. under the condition of 0.5 MPa, and then etched with a laminated film. Defect assessment was performed.
• Example E02 Purification of M2 resin with acid
• a solution (10% by mass) of the M2 resin obtained in Synthesis Example 2 dissolved in PGMEA was charged.
• 37.5 g of an aqueous oxalic acid solution (pH 1.3) was added, and the mixture was stirred for 5 minutes and allowed to stand for 30 minutes.
• the oil phase and the aqueous phase were separated, and the aqueous phase was removed.
• a solution containing a resin prepared by using the obtained compound of the present invention was filtered through a UPE filter having a nominal pore size of 3 nm manufactured by Entegris Japan, Inc. under the condition of 0.5 MPa, and then etched with a laminated film. Defect assessment was performed.
• Example E03 Purification by passing through a filter In a class 1000 clean booth, the M1 resin obtained in Synthesis Example 1 was placed in a 1000 mL volume four-necked flask (bottom punching type) with propylene glycol monomethyl ether (PGME). 500 g of a solution with a concentration of 10% by mass dissolved in the flask was charged, and then the air inside the flask was removed under reduced pressure, then nitrogen gas was introduced and returned to atmospheric pressure, and the nitrogen gas was ventilated at 100 mL / min to provide internal oxygen. After adjusting the concentration to less than 1%, the mixture was heated to 30 ° C. with stirring.
• PGME propylene glycol monomethyl ether
• the above solution is withdrawn from the bottom punching valve, and a nylon hollow fiber membrane filter (manufactured by KITZ Microfilter Co., Ltd.) with a nominal pore diameter of 0.01 ⁇ m at a flow rate of 100 mL / min via a pressure resistant tube made of fluororesin is used.
• a product name: Polyfix Nylon series was passed through pressure filtration so that the filtration pressure was 0.5 MPa.
• the filtered resin solution was diluted with EL grade PGMEA (reagent manufactured by Kanto Chemical Co., Inc.) and the concentration was adjusted to 10% by mass to obtain a PGMEA solution of M1 resin having a reduced metal content.
• a solution containing a resin prepared by using the obtained compound of the present invention was filtered through a UPE filter having a nominal pore size of 3 nm manufactured by Entegris Japan, Inc. under the condition of 0.5 MPa, and then etched with a laminated film. Defect assessment was performed. The oxygen concentration was measured with an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the same applies hereinafter).
• Example E04 As a purification process using a filter, IONKLEEN manufactured by Nippon Pole, a nylon filter manufactured by Nippon Pole, and an UPE filter manufactured by Entegris Japan with a nominal pore diameter of 3 nm were connected in series in this order to construct a filter line. The liquid was passed by pressure filtration so that the filtration pressure was 0.5 MPa in the same manner as in Example E03, except that the prepared filter line was used instead of the 0.1 ⁇ m nylon hollow fiber membrane filter. .. By diluting with EL grade PGMEA (reagent manufactured by Kanto Chemical Co., Inc.) and adjusting the concentration to 10% by mass, a PGMEA solution of M1 resin having a reduced metal content was obtained.
• EL grade PGMEA reagent manufactured by Kanto Chemical Co., Inc.
• a solution sample was prepared by pressure-filtering a solution containing a resin prepared using the prepared compound of the present invention with a UPE filter having a nominal pore size of 3 nm manufactured by Entegris Japan, Inc. so that the filtration pressure was 0.5 MPa. After that, an etching defect evaluation was performed on the laminated film.
• Example E05 The solution sample prepared in Example E01 was further pressure-filtered using the filter line prepared in Example E04 so that the filtration pressure was 0.5 MPa, and then the solution sample was prepared with a laminated film. Etching defect evaluation was performed.
• Example E06 For the M3 resin prepared in (Synthesis Example 3), a solution sample purified by the same method as in Example E05 was prepared, and then an etching defect evaluation was carried out on the laminated film.
• Example E07 For the M4 resin prepared in (Synthesis Example 4), a solution sample purified by the same method as in Example E05 was prepared, and then an etching defect evaluation was carried out on the laminated film.
• Example E08 For the M5 resin prepared in (Synthesis Example 5), a solution sample purified by the same method as in Example E05 was prepared, and then an etching defect evaluation was carried out on the laminated film.
• Example E09 For the MAD1 resin prepared in (Synthesis Example 6), a solution sample purified by the same method as in Example E01 was prepared, and then an etching defect evaluation was carried out on the laminated film.
• Example E10 For the MAD1 resin prepared in (Synthesis Example 6), a solution sample purified by the same method as in Example E01 was prepared, and then an etching defect evaluation was carried out on the laminated film.
• the washed ion exchange resin is added to the ethyl acetate solution of the above compound M1 so as to have the same mass as the resin solid content, stirred at room temperature for one day, and then ion exchange treatment is performed by filtering the ion exchange resin. The washing was repeated 3 times to prepare an ethyl acetate solution of the ion-exchanged compound M1. Further, the same treatment was carried out for the other monomers to prepare an ion-exchanged monomer-containing ethyl acetate solution. Use the obtained ion-exchanged monomer-containing ethyl acetate solution, use electronic grade Purimepure manufactured by Kanto Chemical Co., Inc.
• a compound represented by the chemical formula (P-MAC-0I) was obtained by the same scheme as in Synthesis Example 1 using an instrument washed with ultrapure water after immersion for 1 day. Further, in the post-treatment after synthesis, a 5 nm nylon filter (manufactured by Poll) and a 15 nm PTFE filter (manufactured by Entegris) are used in this order for purification treatment, and then dried under reduced pressure to form a white powder.
• a polymer (M1-CL resin) (the chemical structure is a polymer represented by the formula (P-MAC-0I)) was obtained. Table 3 shows the results of measuring the inorganic element content of the polymer by the above method.
• the prepared polymer was evaluated for metal content and PE-CVD defects in the same manner as in Example E01.

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• 2020
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