WO2007108253A1 - Composition de réserve positive de formation de film de réserve épais, stratifié de réserve épais, et procédé de formation de motif de réserve - Google Patents

Composition de réserve positive de formation de film de réserve épais, stratifié de réserve épais, et procédé de formation de motif de réserve Download PDF

Info

Publication number
WO2007108253A1
WO2007108253A1 PCT/JP2007/052555 JP2007052555W WO2007108253A1 WO 2007108253 A1 WO2007108253 A1 WO 2007108253A1 JP 2007052555 W JP2007052555 W JP 2007052555W WO 2007108253 A1 WO2007108253 A1 WO 2007108253A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
resist
alkyl group
acid
film
Prior art date
Application number
PCT/JP2007/052555
Other languages
English (en)
Japanese (ja)
Inventor
Hiroshi Shimbori
Masahiro Masujima
Toshihiro Yamaguchi
Sachiko Yoshizawa
Original Assignee
Tokyo Ohka Kogyo Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokyo Ohka Kogyo Co., Ltd. filed Critical Tokyo Ohka Kogyo Co., Ltd.
Publication of WO2007108253A1 publication Critical patent/WO2007108253A1/fr

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Definitions

  • the present invention relates to a positive resist composition for forming a thick film resist film used for forming a thick film resist film on a support, a thick film resist laminate, and a resist pattern forming method.
  • a resist film having a resist composition force is formed on a substrate, and the resist film is selectively exposed with radiation such as light or an electron beam to perform development processing.
  • radiation such as light or an electron beam to perform development processing.
  • a step of forming a resist pattern having a predetermined shape on the resist film is performed.
  • a resist composition in which the exposed portion changes to a property that dissolves in the developer is referred to as a positive type
  • a resist composition in which the exposed portion changes to a property that does not dissolve in the developer is referred to as a negative type.
  • a resist material having high resolution is required.
  • a chemically amplified resist composition containing a base resin and an acid generator that generates an acid upon exposure is used.
  • a positive chemically amplified resist has a resin component that increases alkali solubility by the action of an acid and an It contains an acid generator component that generates acid by light, and when an acid is generated from the acid generator by exposure at the time of resist pattern formation, the exposed portion becomes alkali-soluble.
  • the resin component of the chemically amplified positive resist composition is derived from a resin prepared by protecting the hydroxyl group of polyhydroxystyrene (PHS) resin with an acid dissociable, dissolution inhibiting group, or (meth) acrylic acid.
  • PHS polyhydroxystyrene
  • a resin having a carboxy group of a resin (acrylic resin) having a structural unit as a main chain is protected with an acid dissociable, dissolution inhibiting group.
  • acid dissociable, dissolution inhibiting groups examples include 1-chain ether groups typified by ethoxyethyl groups, so-called acetal groups such as cyclic ether groups typified by tetrahydrovinyl groups, and tertiary groups typified by tert butyl groups.
  • Alkyl groups; tertiary alkoxy carbo yl groups typified by tert butoxy carbo ls are used (see, for example, Patent Document 1).
  • a resist film formed using a resist composition in the manufacture of a semiconductor element or the like is usually a thin film having a thickness of about 100 to 800 nm, but the resist composition has a larger film thickness, for example, It is also used to form thick resist films with a thickness of 1 ⁇ m or more.
  • connection terminals that have protruding electrode force are provided on the upper surface of a support such as a substrate
  • the bump force that protrudes from the support is also required.
  • a thick resist film is used to form connection terminals composed of connection terminals, support posts called metal posts protruding from the support, and solder balls formed thereon.
  • a thick resist film is formed on a support, exposed through a predetermined mask pattern, visualized, and portions where bumps and metal posts are formed are selectively removed ( A stripped resist pattern is formed, and the removed part (non-resist part) is filled with a conductor such as copper, gold, nickel, or solder, and then the resist pattern around it is removed. be able to.
  • a photosensitive resin composition having a quinonediazide group-containing compound used for forming a pump or wiring is disclosed! Speak (see, for example, Patent Document 2).
  • the resist pattern formed as described above includes a etching process using the resist pattern as a frame, an etching process using the resist pattern as a mask, and a high energy input. It can be used for a ransion process. Therefore, it can be used for manufacturing MEMS (Micro Electro Mechanical Systems) in which these steps are performed.
  • MEMS Micro Electro Mechanical Systems
  • MEMS is an advanced small system that integrates various fine structures (functional elements such as sensors, conductor structures such as wiring and connection terminals) on a support by micromachining technology.
  • Patent Document 3 describes a method of manufacturing a microphone device such as a magnetic head using a resist pattern having a specific shape formed using a positive resist composition containing novolac resin. .
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-341538
  • Patent Document 2 JP 2002-258479 A
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-110536
  • the conventionally used non-chemically amplified type resist resist composition as described in Patent Documents 2 and 3 cannot be sufficiently finely processed, and a fine resist pattern, for example, 400 nm or less. It is difficult to form a resist pattern having dimensions.
  • a resist composition used for thick resist film formation is also required to have a low viscosity.
  • the resist composition solution used to form a thick film needs to have a certain degree of viscosity in order to form a thick coating film.
  • high-viscosity resist composition solutions cannot be used in mass production equipment (such as coaters used to form resist films) due to piping, pumps, nozzles, etc. that supply the resist composition solution. There are some restrictions.
  • the present invention has been made in view of the above circumstances, and can form a thick resist film having a thickness of 1 to 15 m that can be reduced in viscosity and has good in-plane uniformity. It is an object of the present invention to provide a positive resist composition for forming a thick film resist film, a thick film resist laminate using the positive resist composition, and a resist pattern forming method.
  • the first aspect of the present invention is a positive resist composition for forming a thick resist film having a thickness of 1 to 15 m,
  • a resin component (A) whose alkali solubility is increased by the action of an acid and an acid generator component (B) which generates an acid upon exposure are dissolved in an organic solvent (S).
  • a positive resist composition is a mixed solvent with other solvent (S2) 5 to 90 weight 0/0.
  • the second aspect of the present invention is a thick film resist laminate in which a 1 to 15 m thick resist film made of the positive resist composition of the first aspect is laminated on a support.
  • the third aspect of the present invention is a process of forming a thick resist film having a thickness of 1 to 15 m on a support using the positive resist composition of the first aspect, and the thick film resist.
  • a resist pattern forming method including a step of selectively exposing a film and a step of forming a resist pattern by alkali development of the thick film resist film.
  • exposure is a concept including general irradiation of radiation, and includes irradiation of an electron beam.
  • a positive resist for forming a thick resist film capable of forming a thick resist film having a thickness of 1 to 15 ⁇ m and capable of reducing the viscosity and having a good in-plane uniformity of film thickness.
  • Type resist composition, a thick film resist laminate using the positive resist composition, and a method for forming a resist pattern can be provided.
  • FIG. 1A is a schematic diagram for explaining a step of forming a resist pattern in a method of forming a magnetic film pattern by a plating method using a resist pattern as a frame.
  • FIG. 1B is a schematic diagram for explaining a process of forming a magnetic film in a method of forming a magnetic film pattern by a plating method using a resist pattern as a frame.
  • FIG. 1C is a schematic diagram for explaining a step of obtaining a magnetic film pattern in a method of forming a magnetic film pattern by a plating method using a resist pattern as a frame.
  • FIG. 2 is a schematic diagram for explaining a method for evaluating in-plane uniformity of a thick resist film thickness. Explanation of symbols
  • the positive resist composition of the present invention is used for forming a thick film resist film having a film thickness of 1 to 15 m.
  • the resin component (A) hereinafter referred to as ( A) component
  • an acid generator component (B) hereinafter referred to as (B) component
  • S organic solvent
  • the component (A) is alkali-insoluble before exposure, and when acid is generated from the component (B) upon exposure, the acid increases the alkali solubility of the component (A). . Therefore, a positive resist composition is used in resist pattern formation. When the resist film thus obtained is selectively exposed, the exposed portion turns alkali-soluble, while the unexposed portion remains alkali-insoluble and can be alkali-developed.
  • the component (S) is a mixed solvent of 10 to 95% by mass of propylene glycol monomethyl ether (hereinafter referred to as PG ME) and 5 to 90% by mass of the other solvent (S2).
  • PG ME propylene glycol monomethyl ether
  • PGME is a solvent having a viscosity of 1.9 centipoise (cp) at boiling points of 121 ° C and 20 ° C.
  • any conventional chemical amplification type may be used as long as the (S) component containing the solvent (S2) can dissolve each component used to form a uniform solution.
  • the resist solvent one or more kinds of known solvents can be appropriately selected and used.
  • Examples of the solvent (S2) include ratatones such as ⁇ -petit-mouth rataton; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl- ⁇ -amyl ketone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, diethylene glycol, Polyhydric alcohols such as propylene glycol and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycolol monoacetate, propylene glycolanol monoacetate, or dipropylene glycol monoacetate; Or monoalkyl ethers such as monomethyl ether, monoethinoreethenole, monopropinoreethenore, monobutinoreethenore, etc.
  • ratatones such as ⁇ -petit-mouth rataton
  • ketones such as acetone, methyl ethyl ketone, cyclohe
  • Is a derivative of a polyhydric alcohol such as a compound having an ether bond such as monofluoroether (except PGME); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, acetic acid Esters such as ethyl, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; azole, ether benzyl ether, cresyl methyl ether, diphenylenoate, dipenti Noreite Nore, Feneto Monore, Butinorefueninorete Nore, Ethylbenzene, Jetylbenzene, Amylbenzene, Isopropylbenzene, Toluene, Aromatic organic solvents such as xylene, cymene and mesitylene can be mentioned.
  • These solvents (S 2) may be used alone or in combination of two or more.
  • the solvent (S2) a solvent having a boiling point higher than that of PGM E having a boiling point of about 121 ° C is preferred because the effect of the present invention is excellent.
  • the boiling point is in the range of 125 to 200 ° C. Those having a boiling point in the range of 125 to 150 ° C are more preferable.
  • the solvent (S2) is selected from the group power consisting of propylene glycol monomethyl ether acetate (PGMEA; boiling point approx. 146 ° C), butyl acetate (boiling point approx. 126 ° C) and amyl acetate (boiling point approx. 142 ° C).
  • PGMEA propylene glycol monomethyl ether acetate
  • butyl acetate butyl acetate
  • amyl acetate butyl acetate
  • the proportion of PGME in the component (S) is 10 to 95% by mass, more preferably 30 to 95% by mass, and particularly preferably 50 to 95% by mass.
  • the ratio of the solvent (S2) in the component (S) is 5 to 90% by mass, and 5 to 70% by mass is more preferable, and 5 to 50% by mass is particularly preferable.
  • the positive resist composition (solution) can be reduced in viscosity.
  • a thick resist film having a thickness of 1 to 15111 can be formed.
  • the shape of the resist pattern formed on the thick resist film is also highly rectangular and good.
  • the proportion of PGME in the component (S) is 95% by mass or less (that is, the proportion of the solvent (S2) is 5% by mass or more), excellent in-plane film thickness uniformity is provided on the support. A thick film resist film can be formed. Therefore, the height of the resist pattern to be formed is uniform and the shape is good.
  • the ratio of PGME to the solvent (S2) depends on the desired viscosity, coatability, in-plane uniformity of the positive resist composition, striation (the central force of the resist film is also radial). For example, the higher the ratio of PGME, the lower the viscosity of the positive resist composition.
  • the amount of component (S) used is not particularly limited, and the resist film thickness to be formed as long as it is a concentration that can be applied to a support such as a substrate, ease of application to the mass production equipment to be used, etc. This is set as appropriate.
  • the (S) component since it is suitable for forming a thick resist film having a film thickness of 1 to 15 / zm, the (S) component usually has a solid concentration in the positive resist composition of 15 to 60% by mass, The amount is preferably 20 to 60% by mass, particularly preferably 25 to 55% by mass.
  • the component (A) is not particularly limited, and a base resin generally used for a chemically amplified positive resist composition can be used.
  • a resin having an acid dissociable, dissolution inhibiting group is usually used as the base resin for a positive resist composition.
  • the acid dissociable, dissolution inhibiting group is a group that can be separated from the (A) component by the acid generated from the (B) component during exposure, and has an alkali dissolution inhibiting property that makes the entire (A) component insoluble in alkali before dissociation. In addition, after dissociation, the entire component (A) is changed to alkali-soluble.
  • the acid dissociable, dissolution inhibiting group will be described in more detail in the structural unit (a2) described later.
  • U As a resin having an acid dissociable, dissolution inhibiting group, U is preferable. Fats are mentioned. A high-resolution pattern can be formed by using strong rosin. In addition, since fine processing can be performed even in the case of a thick film, a pattern with a high aspect ratio can be formed, and as a result, resistance to dry etching and the like is improved.
  • the PHS-based resin is a resin having a structural unit (al) (a structural unit derived from hydroxystyrene force) to be described later, specifically, polyhydroxystyrene, hydroxystyrene-styrene copolymer. And hydroxystyrene acrylate copolymer.
  • examples of the PHS-based resin include a resin having a structural unit (al) and a structural unit having an acid dissociable, dissolution inhibiting group.
  • structural unit (a2) described later a structural unit derived from an acrylate ester having an acid dissociable, dissolution inhibiting group
  • structural unit (a4) structural unit (a structural unit in which the hydrogen atom of the hydroxyl group in al) is substituted with an acid dissociable, dissolution inhibiting group-containing group).
  • strong PHS-based resin has structural units other than the above structural units, such as structural unit (a3) (structural unit that also induces styrene power), structural unit (a5) (having an alcoholic hydroxyl group).
  • structural unit (a3) structural unit that also induces styrene power
  • structural unit (a5) structural unit having an alcoholic hydroxyl group.
  • a structural unit derived from an acrylic ester ester), etc. has been proposed as a structural unit of a resin for resists, and may contain any structural unit.
  • the “structural unit” means a monomer unit (monomer unit) constituting the resin component (polymer).
  • Hydrostyrene is a narrowly-defined hydroxystyrene, and a hydrogen atom at the ⁇ -position of the narrowly-defined hydroxystyrene is a halogen atom, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), or a halogenated alkyl group (preferably Is a concept including those substituted with other substituents such as a halogenated alkyl group having 1 to 5 carbon atoms, and derivatives thereof.
  • “Hydroxystyrene force-derived structural unit” means a structural unit formed by cleavage of an ethylenic double bond of hydroxystyrene.
  • the “ ⁇ -position of the structural unit derived from hydroxystyrene (the carbon atom at the position)” is a carbon atom to which a benzene ring is bonded, unless otherwise specified.
  • “Acrylic acid esters” include those in which a hydrogen atom is bonded to the carbon atom at position a and a substituent (an atom or group other than a hydrogen atom) is bonded to the position a in addition to the acrylic acid ester. Include concepts. Examples of the substituent include a halogen atom such as a fluorine atom, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), a halogenated alkyl group (preferably a halogenated alkyl group having 1 to 5 carbon atoms), and the like. Can be mentioned.
  • a structural unit derived from an acrylate ester means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
  • the ⁇ -position ( ⁇ -position carbon atom) of a structural unit derived from an acrylate ester is a carbon atom to which a carbo group is bonded unless otherwise specified.
  • Alkyl group means linear, branched and cyclic monovalent saturation unless otherwise specified. It includes hydrocarbon groups.
  • the structural unit (al) is a structural unit from which hydroxystyrene power is also derived.
  • structural unit (al) for example, a structural unit represented by the following general formula (al-1) can be exemplified.
  • R represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, a halogen atom or a halogenated lower alkyl group
  • R 6 represents a lower alkyl group having 1 to 5 carbon atoms
  • q represents an integer of 0-2.
  • R represents a hydrogen atom, a lower alkyl group, a halogen atom or a halogenated lower alkyl group.
  • the lower alkyl group of R is an alkyl group having 1 to 5 carbon atoms, and a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, which are preferably linear or branched alkyl groups, are preferred.
  • a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, which are preferably linear or branched alkyl groups, are preferred.
  • the methyl group is preferred industrially.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
  • the no- or rogenated lower alkyl group is one in which a part or all of the above-mentioned lower alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. In the present invention, it is preferable that all hydrogen atoms are halogenated.
  • the halogenated lower alkyl group is preferably a linear or branched halogenated lower alkyl group, particularly trifluoro.
  • the trifluoromethyl group (one CF) is most preferred, with fluorinated lower alkyl groups such as methyl, pentafluoroethyl, heptafluoropropyl, and nonafluorobutyl being more preferred.
  • R is more preferably a hydrogen atom or a hydrogen atom that is preferably a methyl group.
  • Examples of the lower alkyl group having 1 to 5 carbon atoms of R 6 include the same lower alkyl groups as those described above for R.
  • q is an integer of 0-2. Of these, q is preferably 0 or 1, and particularly preferably 0 from an industrial viewpoint.
  • substitution position of R 6 is when q is 1. Any of 1-position, m-position and p-position is acceptable. Furthermore, when q is 2, any substitution position can be combined.
  • p is an integer of 1 to 3, preferably 1.
  • the substitution position of the hydroxyl group may be any of the o-position, m-position and p-position when p is 1.
  • the p-position is preferred because it is readily available and inexpensive.
  • any substitution position can be combined.
  • one type or a mixture of two or more types can be used as the structural unit (al).
  • Component (A) the amount of the structural unit (al) is, (A) to the total structural units constituting the component 10 to 95 mol 0/0 it is preferably a tool 20 and 85 mole 0/0 force more preferably S, particularly preferably preferred Shi ingredients 60-70 mol% 30 to 80 mole 0/0 force of et. Within this range, moderate alkali solubility can be obtained, and the balance with other structural units is good.
  • the structural unit (a2) is a structural unit derived from an acrylate ester having an acid dissociable, dissolution inhibiting group.
  • structural unit (a2) for example, a structural unit represented by the following general formula (a2-1) can be exemplified.
  • R is the same as R in the general formula (al-1), and R 1 represents an organic group having an acid dissociable, dissolution inhibiting group or an acid dissociable, dissolution inhibiting group.
  • the “acid dissociable, dissolution inhibiting group” means that when an acid is generated from the component (B) by exposure, it is dissociated by the acid and removed from the component (A) after exposure. It means the group to release.
  • the “organic group having an acid dissociable, dissolution inhibiting group” means an acid dissociable, dissolution inhibiting group, an acid group or an atom that is not dissociated by an acid (that is, an acid dissociable, dissolution inhibiting group that is not dissociated by an acid, A group composed of (A) a group or atom that remains bonded to the component even after dissociation).
  • the acid dissociable, dissolution inhibiting group and the organic group having an acid dissociable, dissolution inhibiting group may be collectively referred to as “an acid dissociable, dissolution inhibiting group-containing group”.
  • the acid dissociable, dissolution inhibiting group is not particularly limited.
  • resins for resist compositions such as for KrF excimer laser and ArF excimer laser. It can be appropriately selected and used.
  • chain-tertiary alkoxycarbonyl groups and chain-like tertiary groups exemplified in the following acid dissociable, dissolution inhibiting groups (I) and (II), and the acid dissociable, dissolution inhibiting group-containing group (IV).
  • Examples include tertiary alkoxy carboalkyl groups.
  • the organic group having an acid dissociable, dissolution inhibiting group is not particularly limited.
  • many of the proposed resins for resist yarn and composition such as for KrF excimer laser and ArF excimer laser are used.
  • Specific examples include the organic groups having the acid dissociable, dissolution inhibiting groups listed above.
  • the organic group having an acid dissociable, dissolution inhibiting group ( ⁇ ) has the following acid dissociable, dissolution inhibiting groups.
  • Organic group (II) and the like can be mentioned.
  • Acid dissociable, dissolution inhibiting group (I) is a chain or cyclic tertiary alkyl group.
  • the chain tertiary alkyl group preferably has 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms. More specifically, examples of the chain-like tertiary alkyl group include a tert-butyl group and a tert-amyl group.
  • a cyclic tertiary alkyl group is a monocyclic or polycyclic monovalent saturated hydrocarbon group containing a tertiary carbon atom on the ring.
  • the cyclic tertiary alkyl group preferably has 4 to 12 carbon atoms, and more preferably 5 to LO. More specific examples of the cyclic tertiary alkyl group include 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, 1-methylcyclohexyl group, 2-methyl-2-adamantyl group, 2 —Ethyl-2-adamantyl group and the like can be mentioned.
  • a chain-like tertiary alkyl group is preferred, and a tert-butyl group is particularly preferred from the viewpoint of excellent effects of the present invention.
  • the acid dissociable, dissolution inhibiting group ( ⁇ ) is a group represented by the following general formula ( ⁇ ).
  • X represents an aliphatic cyclic group, an aromatic cyclic hydrocarbon group or a lower alkyl group
  • R 2 represents a hydrogen atom or a lower alkyl group
  • X and R 2 each independently represent 1 carbon atom.
  • R 3 represents a lower alkyl group or a hydrogen atom;
  • X represents an aliphatic cyclic group, an aromatic cyclic hydrocarbon group, or a lower alkyl group.
  • aliphatic in the present specification and claims is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
  • the “aliphatic cyclic group” means a monocyclic group or polycyclic group having no aromaticity, which may be either saturated or unsaturated, but is usually preferably saturated.
  • the aliphatic cyclic group in X is a monovalent aliphatic cyclic group.
  • many aliphatic cyclic groups have been proposed for conventional ArF resists, and the intermediate forces of those can be selected and used as appropriate.
  • the aliphatic cyclic group examples include an aliphatic monocyclic group having 5 to 7 carbon atoms and an aliphatic polycyclic group having 10 to 16 carbon atoms.
  • Examples of the aliphatic monocyclic group having 5 to 7 carbon atoms include groups in which one hydrogen atom has been removed from a monocycloalkane, specifically, one hydrogen atom from cyclopentane, cyclohexane or the like. Examples include groups excluding.
  • Examples of the aliphatic polycyclic group having 10 to 16 carbon atoms include groups in which one hydrogen atom has been removed from bicycloalkane, tricycloalkane, tetracycloalkane and the like.
  • adamantane groups in which one hydrogen atom has been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclodecane.
  • adamantyl group, a norbornyl group, and a tetracyclodode- yl group are industrially preferable, and an adamantyl group is particularly preferable.
  • aromatic cyclic hydrocarbon group represented by X examples include aromatic polycyclic groups having 10 to 16 carbon atoms. Specific examples include groups in which one hydrogen atom has been removed from naphthalene, anthracene, phenanthrene, pyrene, and the like. Specific examples include 1 naphthyl group, 2-naphthyl group, 1-anthracyl group, 2-anthracyl group, 1-phenanthryl group, 2-phenanthryl group, 3 phenanthryl group, 1-pyrenyl group, and the like. 2 A naphthyl group is particularly preferred industrially.
  • the lower alkyl group for X the same as the lower alkyl group for R in the above formula (al-1) can be mentioned, and a methyl group or an ethyl group is more preferable, and an ethyl group is most preferable.
  • examples of the lower alkyl group for R 2 include the same as the lower alkyl group for R in the above formula (al-1). Industrially, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.
  • R 3 represents a lower alkyl group or a hydrogen atom.
  • Examples of the lower alkyl group for R 3 include the same as the lower alkyl group for R 3 .
  • R 3 is preferably a hydrogen atom industrially.
  • X and R 2 are each independently an alkylene group having 1 to 5 carbon atoms, and the end of X and the end of R 2 may be bonded to each other! /.
  • a cyclic group is formed by R 2 , X, the oxygen atom to which X is bonded, and the carbon atom to which the oxygen atom and R 2 are bonded.
  • the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydrofuranyl group and a tetrahydrofuranyl group.
  • R 3 is preferably a hydrogen atom, and R 2 is preferably a hydrogen atom or a lower alkyl group, since the effects of the present invention are excellent.
  • Specific examples include, for example, a group in which X is a lower alkyl group, that is, 1 alkoxyalkyl group includes 1-methoxyethyl group, 1 ethoxyethyl group, 1 isopropoxycetyl group, 1 n butoxychetyl group, 1 tert butoxychetyl group, methoxymethyl group Ethoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, tert-butoxymethyl group and the like.
  • 1 alkoxyalkyl group includes 1-methoxyethyl group, 1 ethoxyethyl group, 1 isopropoxycetyl group, 1 n butoxychetyl group, 1 tert butoxychetyl group, methoxymethyl group Ethoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, tert-butoxymethyl group and the like.
  • examples of the group in which X is an aliphatic cyclic group include 1-cyclohexyloxychetyl group, 1 1- (2-adamantyl) oxymethyl group, and 1 1 (1 -Adamantyl) oxetyl group and the like.
  • Examples of the group in which X is an aromatic cyclic hydrocarbon group include a 11- (2-naphthyl) oxetyl group represented by the following formula ( ⁇ -b).
  • 1 ethoxyethyl group is particularly preferred.
  • the organic group (III) having an acid dissociable, dissolution inhibiting group is a group represented by the following general formula (III).
  • the organic group ( ⁇ ) having such a structure when an acid is generated from the component (B) by exposure, the acid causes an oxygen atom bonded to Y to a carbon atom bonded to R 4 and R 5 . The bond is broken and — C (R 4 ) (R 5 ) — OX is dissociated.
  • X ′ represents an aliphatic cyclic group, an aromatic cyclic hydrocarbon group or a lower alkyl group
  • R 4 represents a hydrogen atom or a lower alkyl group
  • X and R 4 are each independently carbon.
  • An alkylene group of 1 to 5 which may be bonded to the end of X and the end of R 4 R 5 represents a lower alkyl group or a hydrogen atom
  • Y represents an aliphatic cyclic group.
  • the aliphatic cyclic group, aromatic cyclic hydrocarbon group and lower alkyl group as X ′ are the aliphatic cyclic group as X in the above formula (II), aromatic Examples thereof are the same as the cyclic hydrocarbon group and the lower alkyl group.
  • Examples of the lower alkyl group as R 4 include the same lower alkyl groups as R 2 in the above formula ( ⁇ ).
  • Examples of the lower alkyl group as R 5 include the same lower alkyl groups as R 3 in the above formula ( ⁇ ).
  • Examples of the aliphatic cyclic group for Y include an aliphatic cyclic group in X above and a group obtained by removing one hydrogen atom.
  • the acid dissociable, dissolution inhibiting group-containing group (IV) includes the acid dissociable, dissolution inhibiting groups (I) to (II) and the organic group (III) having an acid dissociable, dissolution inhibiting group (hereinafter referred to as “acid”). Dissociable, dissolution-inhibiting groups, etc. (I) to ( ⁇ ) ”are sometimes classified as)! These are oxalic acid-dissociable, dissolution-inhibiting group-containing groups.
  • the acid dissociable, dissolution inhibiting group-containing group (IV) is not classified into the above-mentioned acid dissociable, dissolution inhibiting group-containing groups (I) to (III) among the conventionally known acid dissociable, dissolution inhibiting group-containing groups! Acid-dissociable, dissolution inhibiting group-containing groups can be used.
  • acid dissociable, dissolution inhibiting groups that are not classified in (i) to (m) include chain tertiary alkoxycarbo groups, chain tertiary alkoxy forces. Examples thereof include a l-alkyl group.
  • the chain tertiary alkoxy carbo group preferably has 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms.
  • Specific examples of the chain-like tertiary alkoxycarbonyl group include a tert-butoxycarbonyl group and a tert-amyloxycarbonyl group.
  • the chain tertiary alkoxy carboalkyl group preferably has 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms.
  • Specific examples of the chain-like tertiary alkoxycarbonylalkyl group include a tert butoxycarboromethyl group and a tert amyloxycarboromethyl group.
  • an acid dissociable, dissolution inhibiting group-containing group in the structural unit (a2) since it is excellent in the effects of the present invention, an acid dissociable, dissolution inhibiting group, etc.
  • it preferably contains an acid dissociable, dissolution inhibiting group (I).
  • one type or a mixture of two or more types can be used as the structural unit (a2).
  • Component (A), the proportion of the structural unit (a2), the (A) to the total structural units constituting the component 1-80 mole 0 / is preferred instrument 1 to 60 mole 0/0 be 0 Shi favored more preferred instrument 50 mole 0/0
  • Gasara ingredients 1-40 mol% is particularly preferred instrument 2 to 35 mole% being most preferred.
  • a pattern can be obtained when the resist composition is made to be above the lower limit value, and the balance with other structural units is good when it is made the upper limit value or less.
  • the structural unit (a3) is a structural unit that also induces styrene power.
  • the component (A) preferably has the structural unit (a3).
  • styrene refers to styrene in the narrow sense, and those in which the ⁇ -position hydrogen atom of styrene in the narrow sense is substituted with other substituents such as a halogen atom, an alkyl group, a halogenated alkyl group, and derivatives thereof.
  • a concept that includes “Structural unit derived from styrene” means a structural unit formed by cleavage of an ethylenic double bond of styrene. In styrene, the hydrogen atom of the phenyl group is substituted with a substituent such as a lower alkyl group! It ’s okay.
  • structural unit (a3) structural units represented by general formula (a3-l) shown below can be exemplified.
  • R 7 represents a lower alkyl group having 1 to 5 carbon atoms, and r represents an integer of 0 to 3.
  • examples of R include the same as R in the formula (al-1).
  • Examples of the lower alkyl group having 1 to 5 carbon atoms of R 7 include the same as the lower alkyl group having 1 to 5 carbon atoms of R 6 in the above formula (al-1).
  • r is an integer of 0-3. Of these, r is preferably 0 or 1, particularly preferably 0.
  • the substitution position of R 7 may be any of o-position, m-position and p-position when r is 1 to 3, and any substitution position may be combined when r is 2 or 3. it can.
  • one type may be used alone, or two or more types may be used in combination.
  • the proportion of the structural unit (a3) is preferably 1 to 20 mol% with respect to all the structural units constituting the component (A). 5 to 15 mol% is particularly preferred. Within this range, the balance with other structural units that are highly effective by having the structural unit (a3) is also good.
  • the structural unit (a4) is a structural unit in which the hydrogen atom of the hydroxyl group in the structural unit (al) is substituted with an acid dissociable, dissolution inhibiting group-containing group.
  • Examples of the acid dissociable, dissolution inhibiting group-containing group in the structural unit (a4) include the structural unit (a2). The thing similar to what was mentioned in said is mentioned. Among them, the acid dissociable, dissolution inhibiting group, etc. (I) to (ii) a group force consisting of forces is preferable because it contains at least one selected from the viewpoint of the effect of the present invention, and particularly the acid dissociable, dissolution inhibiting group (I). Or (II) preferred to contain U ⁇ .
  • one type or a mixture of two or more types can be used as the structural unit (a4).
  • component (A) has structural unit (a4)
  • the proportion of structural unit (a4) in component (A) is 5 to 50 mol% with respect to all structural units constituting component (A). 5 to 45 mol% is more preferable 10 to 40 mol% is more preferable 15 to 40 mol% is particularly preferable.
  • the structural unit (a5) is a structural unit derived from an acrylate ester having an alcoholic hydroxyl group. By having a strong structural unit (a5), the effect of the present invention is further improved.
  • the structural unit (a5) include structural units having a chain or cyclic alkyl group having an alcoholic hydroxyl group. That is, the structural unit (a5) is preferably a structural unit derived from an acrylate ester having a linear or cyclic alkyl group containing an alcoholic hydroxyl group.
  • Structural Unit (a5) Strength When it has a structural unit derived from an acrylate ester having an alcoholic hydroxyl group-containing cyclic alkyl group (hereinafter sometimes simply referred to as “a structural unit having a hydroxyl group-containing cyclic alkyl group”). In addition, the resolution is improved and the etching resistance is improved.
  • the structural unit (a5) may be a structural unit derived from an acrylate ester having an alcoholic hydroxyl group-containing chain alkyl group (hereinafter, simply referred to as “structural unit having a hydroxyl group-containing chain alkyl group”). ), The hydrophilicity of the entire component (A) is increased, the affinity with the image liquid is increased, and the resolution is improved.
  • the structural unit having a hydroxyl group-containing cyclic alkyl group for example, a structure in which a hydroxyl group-containing cyclic alkyl group is bonded to an ester group [—c (o) o—] of an acrylic ester.
  • Examples include units.
  • the “hydroxyl group-containing cyclic alkyl group” is a group in which a hydroxyl group is bonded to a cyclic alkyl group.
  • hydroxyl groups are preferably bonded, and more preferably one.
  • the cyclic alkyl group may be monocyclic or polycyclic, but is preferably a polycyclic group.
  • the cyclic alkyl group preferably has 5 to 15 carbon atoms! / ,.
  • cyclic alkyl group examples include the following.
  • Examples of the monocyclic cyclic alkyl group include groups in which 1 to 4 hydrogen atoms have been removed from cycloalkane. More specifically, examples of the monocyclic cyclic alkyl group include groups in which 1 to 4 hydrogen atoms have been removed from cyclopentane or cyclohexane, and among these, a cyclohexyl group is preferred. ! /.
  • Examples of the polycyclic cyclic alkyl group include groups in which 1 to 4 hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane and the like. More specifically, groups obtained by removing 1 to 4 hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are exemplified. Many such cyclic alkyl groups have been proposed as constituting acid dissociable, dissolution inhibiting groups in, for example, a resin composition for a photoresist composition for ArF excimer laser processes! Can be used. Of these, a cyclohexyl group, adamantyl group, norbornyl group, and tetracyclododecanyl group are preferred because they are commercially available.
  • a cyclohexyl group and an adamantyl group are preferred, and an adamantyl group is particularly preferred.
  • a structural unit having a hydroxyl group-containing cyclic alkyl group for example, a structural unit (a5-1) represented by the following general formula (a5-1) is preferable.
  • R is the same as R in the above formula (al-1), and s is an integer of 1 to 3.] ]
  • examples of R include the same as R in the above formula (al-1).
  • s is an integer of 1 to 3, and 1 is most preferable.
  • the bonding position of the hydroxyl group is not particularly limited, but it is preferable that the hydroxyl group is bonded to the 3rd position of the adamantyl group!
  • Examples of the structural unit having a hydroxyl group-containing chain alkyl group include a structural unit in which a chain hydroxyalkyl group is bonded to an ester group [c (o) o] of an acrylate ester.
  • the “chain hydroxyalkyl group” means a group in which part or all of the hydrogen atoms in a chain (straight chain or branched chain) alkyl group are substituted with a hydroxyl group.
  • a structural unit (a5-2) represented by the following general formula (a5-2) is particularly preferable.
  • R is the same as R in the general formula (a4-1), and R. Is a chain-like hydroxyalkyl group It is. ]
  • R in the formula (a5-2) is the same as R in the general formula (a4-1).
  • the linear hydroxyalkyl group of R 8 is preferably a lower hydroxyalkyl group having 10 or less carbon atoms, more preferably a lower hydroxyalkyl group having 2 to 8 carbon atoms, and further preferably 2 carbon atoms. -4 linear lower hydroxyalkyl groups.
  • the number of hydroxyl groups and the bonding position in the hydroxyalkyl group are not particularly limited. Usually, the number of hydroxyl groups is one, and the bonding position is preferably the terminal of the alkyl group.
  • one type or a mixture of two or more types can be used as the structural unit (a5).
  • the proportion of structural unit (a5) is the total of all the structural units of the component (A), 5 to 50 mole 0/0 is preferred instrument 5 to 45 mole 0/0 Gayo Ri preferred instrument 10 to 40 mol% and more preferably fixture 15 to 40 mol% is particularly preferred.
  • the component (A) includes other structural units (a6) other than the structural units (al) to (a5) as long as the effects of the present invention are not impaired! .
  • the structural unit (a6) is not classified into the structural units (al) to (a5) described above, and is not particularly limited as long as it is other structural units.
  • ArF excimer lasers for ArF excimer lasers, for KrF positive excimer lasers (preferably Can be used for resists such as ArF excimer laser), which have been known for their strength.
  • the component (A) is preferably a copolymer containing at least the structural units (al) and (a2).
  • the effect of the present invention is further improved.
  • the resist pattern formed on the thick resist film formed using the above-mentioned resist resist composition has a good shape.
  • the powerful copolymer may be a structural unit (al) and (a2) a powerful copolymer (binary copolymer), and also has structural units (al) and (a2), Further, it is a copolymer having at least one of the structural units (a3), (a4) and (a5) (3- to 5-component copolymer).
  • the component (A) is composed of the structural unit (al) and the (a2) binary copolymer (A1-2) which also has a force; the structural unit (al), (a2) and (a3) Powerful terpolymer (A1 — 3); Structural unit (al), (a2), (a3) and (a4) Powerful quaternary copolymer (Al— 4— 1); Structural unit (al) (A2), (a3) and (a5)
  • the quaternary copolymer (Al-4-2) having a force is particularly preferred, and the terpolymer (A1-3) is particularly preferred.
  • the proportion of the structural unit (al) is 10 to 95 mol 0 with respect to all the structural units constituting the ternary copolymer (A1-3). It is preferable / 0 device 20 to 85 mole 0/0, more preferably tool 30-80 mol% and more preferably tool 60-70 mol% is especially preferred.
  • the proportion of the structural unit (a2), and most preferably particularly preferably fixture 2-35 mol% and more preferably fixture 1-50 mole% 1 to 80 mole 0/0 is preferred instrument 1 to 60 mole 0/0 .
  • the proportion of the structural unit (a3) from 1 to 20 mol 0/0 is it is preferred instrument 3-15 mole 0/0, more preferably tool 5 to 15 mole 0/0 and particularly good preferable.
  • the component (A) is particularly preferably a copolymer containing three structural units represented by the following general formula (A-11).
  • R is the same as R in the above formula (al-1), and R 9 is a tertiary alkyl group having 4 to 12 carbon atoms.
  • a monomer for deriving each structural unit is polymerized by a conventional method, for example, a known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN).
  • a radical polymerization initiator such as azobisisobutyronitrile (AIBN).
  • AIBN azobisisobutyronitrile
  • a monomer in which the hydroxyl group of hydroxystyrene is protected with a protecting group such as a acetyl group and a monomer corresponding to the structural unit (a2) were prepared, and these monomers were copolymerized by a conventional method. Thereafter, it can be prepared by substituting the protecting group with a hydrogen atom to form the structural unit (al) by hydrolysis.
  • the component (A) preferably has a mass average molecular weight (Mw; converted to polystyrene by gel permeation chromatography (GPC), the same shall apply hereinafter) in the range of 20,000 to 50,000, , 000 to 40,000 force is preferred, 20,000 to 30,000 force is better than ⁇ !
  • Mw mass average molecular weight
  • GPC gel permeation chromatography
  • Diffeta is a general defect detected when a resist pattern after development is observed from directly above, for example, using a surface defect observation device (trade name “KLA”) manufactured by KLA Tencor. Examples of defects include scum after development, bubbles, dust, bridges between resist patterns, uneven color, and precipitates. Improvement of the differential is important as a resist pattern with high resolution is required.
  • the dispersity is preferably 1.0 to 5.0 force S, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.
  • one type may be used alone, or two or more types may be used in combination.
  • the content of the component (A) should be adjusted according to the thickness of the resist film to be formed.
  • the component (B) is not particularly limited, and those that have been proposed as acid generators for chemical amplification resists can be used.
  • acid generators include onium salt-based acid generators such as ododonium salts and sulfo-um salts, oxime sulfonate-based acid generators, bisalkyl or bisarylsulfonyldiazomethanes.
  • Various kinds of acid generators such as diazomethane acid generators such as poly (bissulfol) diazomethane, nitrobenzilsulfonate acid generators, iminosulfonate acid generators, and disulfone acid generators are known.
  • Examples of the form salt-based acid generator include an acid generator represented by the following general formula (b-0).
  • 1 represents a linear, branched, or cyclic alkyl group, or a linear, branched, or cyclic fluorinated alkyl group
  • R 52 represents a hydrogen atom, a hydroxyl group, a halogen atom, or a linear chain. Or a branched alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group
  • R 53 is an aryl group that may have a substituent.
  • U and are integers 1 to 3;
  • R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group.
  • the linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
  • the cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to carbon atoms: LO.
  • the fluorinated alkyl group is most preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the fluorination rate of the alkyl group (the ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. All hydrogen atoms are replaced with fluorine atoms. This is preferable because the strength of the acid increases.
  • R 51 is most preferably a linear alkyl group or a fluorinated alkyl group.
  • R 52 is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group, a linear or branched halogenoalkyl group, or a linear or branched alkoxy group.
  • examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
  • the halogenated alkyl group is a group in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms.
  • the alkyl group here are the same as the “alkyl group” in R 52 .
  • the halogen atom to be substituted include the same as those described for the “norogen atom” in R 52 above.
  • the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
  • R 52 is preferably a hydrogen atom.
  • R 53 is an aryl group which may have a substituent, preferably an aryl group having 6 to 20 carbon atoms.
  • the structure of the basic ring (matrix ring) excluding the substituent includes a naphthyl group, Examples thereof include a phenyl group and an anthracenyl group, and a phenyl group is desirable from the viewpoint of the effects of the present invention and the absorption of exposure light such as an ArF excimer laser.
  • substituents examples include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group).
  • aryl group for R 53 those having no substituent are more preferable.
  • u ′ ′ is an integer of 1 to 3, 2 or 3 is preferred, and 3 is particularly desirable.
  • Preferable examples of the acid generator represented by the general formula (b-0) include the following.
  • onion salt-based acid generator represented by the general formula (b—O) include compounds represented by the following general formula (b—1) or (b—2). Is mentioned.
  • R 1 " ⁇ 3 ", R 5 "to R 6 " each independently represents an aryl group or an alkyl group;
  • R 4 " represents a linear, branched or cyclic alkyl group or a fluorinated alkyl. Represents at least one of,, ⁇ "represents an aryl group, and at least one of R 5 " to R 6 "represents an aryl group.
  • the aryl group of R lw to R 3 is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl groups, alkoxy groups. It may not be substituted with a group, a halogen atom, etc.
  • the aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at low cost. For example, a phenol group and a naphthyl group can be mentioned.
  • alkyl group that may be substituted with a hydrogen atom of the aryl group examples include 1 carbon atom.
  • the alkyl group of ⁇ 5 is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
  • alkoxy group that may be substituted with a hydrogen atom of the aryl group, a methoxy group and an ethoxy group are preferred, with an alkoxy group having 1 to 5 carbon atoms being preferred.
  • the halogen atom that may be substituted for the hydrogen atom of the aryl group is preferably a fluorine atom.
  • the “ ⁇ ” alkyl group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, A decanyl group and the like can be mentioned, and a methyl group can be mentioned as a preferable one because it is excellent in resolution and can be synthesized at low cost.
  • R lw to R 3 ′′ are most preferably a phenyl group or a naphthyl group, respectively.
  • R 4 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group.
  • the linear or branched alkyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the cyclic alkyl group is a cyclic group as shown by the above R 1 ′′, preferably a carbon number of 4 to 15 carbon atoms, more preferably a carbon number of 4 to 10 carbon atoms. Most preferably, the number is from 6 to 10.
  • the fluorinated alkyl group is most preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Further, the fluorination rate of the fluorine alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to: LO 0%, more preferably 50 to 100%. Those substituted with atoms are preferred because the strength of the acid is increased.
  • R 4 ′′ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
  • R 5 ′′ and R 6 ′′ each independently represent an aryl group or an alkyl group. At least one of R 5 “and R 6 " represents an aryl group. It is preferred that both R 5 ′′ and R 6 ′′ are aryl groups.
  • Examples of the aryl group of R 5 "and R 6 " include those similar to the aryl groups of,, ⁇ .
  • R 5 ′′ and R 6 ′′ are most preferably a phenol group.
  • acid salt-based acid generators represented by the formulas (b-1) and (b-2) include difluoro-rhodonium trifluoromethanesulfonate, nonafluorobutanesulfonate, bis (4 —Tert-butylphenol) Jodonium trifluoromethanesulfonate or nonafluorobutane sulfonate, trifluoromethane trifluoromethanesulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate, Tri (4 methylphenol) sulfo-trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfotrifluoromethanesulfonate, Its heptafluoropropane sulfonate Or
  • ohmic salts in which the ionic part of these ohmic salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.
  • the anion part is replaced with a caron part represented by the following general formula (b-3) or (b-4).
  • a -um salt-based acid generator can also be used (the cation moiety is the same as (b-1) or (b-2)).
  • X represents a C 2-6 alkylene group in which at least one hydrogen atom is replaced by a fluorine atom; ⁇ ", ⁇ "each independently represents at least one hydrogen atom is fluorine. Represents an alkyl group having 1 to 10 carbon atoms substituted with an atom.
  • X is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 3 carbon atoms. 5 and most preferably 3 carbon atoms.
  • ⁇ "and ⁇ " are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably It is C1-C7, More preferably, it is C1-C3.
  • the carbon number of the alkylene group of X "or the carbon number of the alkyl group of ⁇ " and ⁇ " is preferably as small as possible because it has good solubility in the resist solvent within the above carbon number range. ⁇ .
  • U is preferred because of its improved transparency to electron beams and the alkylene group or
  • the proportion of fluorine atoms in the alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to: LOO%, and most preferably a perful in which all hydrogen atoms are substituted with fluorine atoms. It is a fluoroalkylene group or a perfluoroalkyl group.
  • the oxime sulfonate-based acid generator is a compound having at least one group represented by the following general formula (B-1), and generates acid upon irradiation with radiation. It is what has.
  • Such oxime sulfonate acid generators are widely used for chemically amplified resist compositions, and can be arbitrarily selected and used.
  • R 31 and R 32 each independently represents an organic group.
  • the organic group of R 31 and R 32 is a group containing a carbon atom, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc. ) Etc.).
  • a linear, branched or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a fluorine atom and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.
  • “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
  • 1 to 20 carbon atoms are preferable. 1 to 10 carbon atoms are more preferable. 1 to 8 carbon atoms are more preferable. 1 to 6 carbon atoms are particularly preferable.
  • halogenated alkyl group a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable.
  • the partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the completely halogenated alkyl group means that all the hydrogen atoms are halogen atoms. It means an alkyl group substituted by.
  • Halogen atoms include fluorine, chlorine, odor Elementary atoms, iodine atoms and the like can be mentioned, and fluorine atoms are particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group! /.
  • the aryl group is preferably 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, more preferably LO.
  • a partially or completely halogenated aryl group is particularly preferable.
  • a partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and a completely halogenated aryl group means that all hydrogen atoms are halogenated.
  • R 31 is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.
  • organic group for R 32 a linear, branched or cyclic alkyl group, aryl group or cyan group is preferable.
  • alkyl group and aryl group for R 32 include the same alkyl groups and aryl groups as those described above for R 31 .
  • R 32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.
  • oxime sulfonate-based acid generator More preferred are those represented by the following general formula (
  • Examples thereof include compounds represented by B-2) or (B-3).
  • R 34 -C N— 0— S0 2 R 35
  • R 33 represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group.
  • R 34 is an aryl group.
  • R 35 represents an alkyl group having no substituent or a halogenated alkyl group.
  • R db represents a cyano group, an alkyl group having no substituent, or a halogenal. Kill group.
  • R 37 is a divalent or trivalent aromatic hydrocarbon group.
  • R 38 is an alkyl group having no substituent or a halogenated alkyl group.
  • p ' is 2 or 3.
  • the alkyl group or the halogenated alkyl group has 1 to L carbon atoms.
  • a preferred carbon number of 1-8 is more preferred.
  • a carbon number of 1-6 is most preferred.
  • R 33 is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
  • the fluorinated alkyl group in R 33 is preferably fluorinated with 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more. I like it! /
  • the aryl group of R 3 includes an aromatic carbon such as a phenol group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, and a phenanthryl group.
  • Etc Among these, a fluorenyl group is preferable.
  • the aryl group of R 34 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group.
  • the alkyl group or halogenated alkyl group in the substituent preferably has 1 to 4 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the halogenated alkyl group is preferably a fluorinated alkyl group.
  • the alkyl group or halogenated alkyl group having no substituent of R 35 preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Most preferred.
  • R 35 is most preferably a partially or fully fluorinated alkyl group, preferably a halogenated alkyl group! / ⁇ .
  • the fluorinated alkyl group in R 35 preferably has 50% or more of the hydrogen atoms of the alkyl group fluorinated, more preferably 70% or more, and even more preferably 90% or more. This is preferable because the strength of the acid is increased. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.
  • R 36 having no substituent, an alkyl group or halogen
  • alkyl group include those similar to the alkyl group or halogenalkyl group that do not have the substituent of R.
  • Examples of the divalent or trivalent aromatic hydrocarbon group for R 37 include groups in which the aryl group strength of R 34 is one or two hydrogen atoms removed.
  • P ′ ′ is preferably 2.
  • oxime sulfonate-based acid generators include ⁇ (p-toluenesulfo-oxyximino) monobenzyl cyanide, a-(p-chlorobenzene-sulfo-luoximino) —benzyl cyanide, a-(4-nitro Benzenesulfo-loxyimino) -benzyl cyanide, ichiichi (4-troo 2 trifluoromethylbenzenesulfo-loxyimino) benzyl cyanide, a- (benzenesulfo-loxyimino) —4-cyclobutenyl cyanide-a, benzene Sulfo-Luoxyimino) — 2, 4 Dichlorobenzil cyanide, a — (Benzenesulfo-Luoxyimino) — 2, 6 Dichlorobenzil cyanide, a (Benzenesulfo-
  • bisalkyl or bisarylsulfol-diazomethanes include bis (isopropylsulfol) diazomethane, bis (p toluenesulfol) diazomethane, bis (1, Examples thereof include 1-dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, and bis (2,4 dimethylphenylsulfol) diazomethane.
  • diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552 and JP-A-11-035573 can also be suitably used.
  • Poly (bissulfol) diazomethanes include, for example, 1,3 bis (phenylsulfol diazomethylsulfol) pronone, 1,4 bis disclosed in JP-A-11 322707.
  • one type of these acid generators may be used alone, or two or more types may be used in combination.
  • (B) component the general formula (I): "In SO- [formula (I), R 4" R 4 is a linear, branched or
  • an alkyl salt-based acid generator (hereinafter, also referred to as component (B1)) having a key-on moiety represented by the formula: I like it.
  • R 4 ′′ in the above general formula (I) is a linear or branched alkyl group having 4 carbon atoms.
  • the component (B1) which is a fluorinated alkyl group is particularly preferable because the resist pattern shape is improved. The reason for the strong effect is not clear, but the acid generated from component (B) is less than the number of carbon atoms in R 4 ′′ is 3 or less, for example, the number of carbon atoms in R 4 ′′ is 1. This is presumably because it is difficult to diffuse in the resist film. In addition, it is superior in safety with less impact on the environment, etc. than R 4 "with 5 or more carbon atoms.
  • the proportion of the component (B1) is preferably 10 to: LOO mass%, more preferably 50 to: LOO mass%, and most preferably 100 mass% for the effect of the present invention. It is.
  • the content of the component (B) in the positive resist composition of the present invention is excellent in the effect of the present invention.
  • the power of the component (A) is 100 parts by mass of the component (A). It is preferably within the range of 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass. By setting it within the above range, a resist pattern having a good shape can be formed. In addition, it is preferable because a uniform solution is obtained and storage stability is good.
  • the positive resist composition of the present invention preferably contains a nitrogen-containing organic compound (D) (hereinafter referred to as component (D)) as an optional component. This further improves the effect of the present invention. In addition, the post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer is improved.
  • D nitrogen-containing organic compound
  • aliphatic amines particularly secondary aliphatic amines and tertiary aliphatic amines, can be used arbitrarily from known ones. Is preferred.
  • the aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have from 12 to 12 carbon atoms.
  • Aliphatic amines contain at least one hydrogen atom of ammonia NH and have 12 or more carbon atoms.
  • Examples include amines substituted with the lower alkyl group or hydroxyalkyl group (alkylamines or alkylalcoholamines), cyclic amines, and the like.
  • alkylamines and alkylalcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-no-lamine, n-decylamine; jetylamine, di- dialkylamines such as n-propylamine, di-n-heptylamine, di-n-octylamine, dicyclohexylamine; Noreamine, triethinoleamine, Tory n-propylamine, Tory n-butynoleamine, Tory n monohexylamine, Tory n-pentylamine, Tory n-heptylamine, Tory n-otatylamin, Tori n-no-lamine, Torione Trialkylamines such as n-de-ramine, tri-n-dodecylamine; diethanolamine, triethanolamine, diiso
  • tertiary aliphatic amines such as trialkylamines and tri (alkyl alcohol) amines are preferable, and in particular, trialkylamines having a total carbon number of 5 to 10 and Z or total carbon numbers. Is preferably a tri (alkyl alcohol) amine having 5-10.
  • Examples of the cyclic amine include a heterocyclic compound containing a nitrogen atom as a hetero atom.
  • the heterocyclic compound may be monocyclic (aliphatic monocyclic ammine) or polycyclic (aliphatic polycyclic ammine).
  • aliphatic monocyclic amine examples include piperidine and piperazine.
  • Aliphatic polycyclic amines having 6 to 10 carbon atoms are preferred, such as 1, 5 — diazabicyclo [4. 3. 0] — 5-nonene, 1, 8 — diazabicyclo [5 4. 0] — 7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane.
  • the content of the component (D) is usually in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the component (A). Since it is excellent in effect, it is preferably within the range of 0.01 to 0.3 parts by mass, more preferably 0.01 to 0.2 parts by mass.
  • the positive resist composition of the present invention further includes an organic carboxylic acid as an optional component for the purpose of preventing sensitivity deterioration and improving the resist pattern shape, stability with time, etc.
  • component (E) selected from the group power consisting of phosphorus oxoacid and its derivative power.
  • organic carboxylic acid for example, acetic acid, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
  • phosphorus oxoacids and derivatives thereof include phosphoric acid, phosphonic acid, and phosphinic acid. Among these, phosphonic acid is particularly preferred.
  • Examples of derivatives of phosphorus oxoacids include esters in which the hydrogen atom of the oxoacid is substituted with a hydrocarbon group.
  • Examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and a carbon number of 6 ⁇ 15 aryl groups and the like.
  • phosphoric acid derivatives examples include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
  • Examples of the phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid diol n-butenoresestenole, phenolinophosphonic acid, phosphonic acid diphenolinoestenole, and phosphonic acid dibenzyl ester.
  • phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid diol n-butenoresestenole, phenolinophosphonic acid, phosphonic acid diphenolinoestenole, and phosphonic acid dibenzyl ester.
  • phosphinic acid derivatives include phosphinic acid esters such as phenylphosphinic acid.
  • one type may be used alone, or two or more types may be used in combination.
  • the component (E) an organic carboxylic acid is preferred, and salicylic acid is particularly preferred.
  • the content of the component (E) is usually in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the component (A). From the viewpoint of excellent effect, it is preferably within the range of 0.01 to 0.3 parts by mass, more preferably 0.01 to 0.15 parts by mass.
  • the positive resist composition of the present invention if desired, there are further miscible additives such as an additional resin for improving the performance of the resist film, and a surface activity for improving the coating property.
  • an agent, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like can be appropriately added.
  • a dissolution inhibitor it is particularly preferable to contain a dissolution inhibitor.
  • a dissolution inhibitor By using a dissolution inhibitor, the difference in solubility (dissolution contrast) between the exposed and unexposed areas is improved, and the resolution and resist pattern shape are improved.
  • the dissolution inhibitor is not particularly limited, and conventionally, for example, for KrF excimer laser, Ar
  • dissolution inhibitors for resist compositions for F excimer laser, etc. medium strength can be selected and used as appropriate.
  • the dissolution inhibitor for example, part or all of the hydrogen atoms of the phenolic hydroxyl group in the polyhydric phenolic compound having two or more phenolic hydroxyl groups are substituted with acid dissociable dissolution inhibiting groups. And a compound (a compound in which a phenolic hydroxyl group is protected by an acid dissociable, dissolution inhibiting group).
  • Examples of the acid dissociable, dissolution inhibiting group include the same groups as those listed above for the structural unit (a2).
  • Examples of the polyhydric phenol compound in which the phenolic hydroxyl group is protected with an acid dissociable, dissolution inhibiting group include compounds represented by the following general formula (f1).
  • R 1 to R b are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, and may contain a hetero atom in the structure thereof; d and g are Each is independently an integer of 1 or more, h is 0 or an integer of 1 or more, and d + g + h is 5 or less; e is an integer of 1 or more, i, and j are independent And e + i + j is 4 or less; f and k are each independently an integer of 1 or more, 1 is an integer of 0 or 1 and f + k + l is 5 or less; m is an integer from 1 to 20]
  • the alkyl group for R 21 to R 26 is a linear or branched lower alkyl group having 1 to 5 carbon atoms, which may be linear, branched or cyclic, or a cyclic alkyl group having 5 to 6 carbon atoms. preferable.
  • the aromatic hydrocarbon group in R 21 to R 26 is preferably a phenyl group, tolyl group, xylyl group, mesityl group, phenethyl group, naphthyl group, etc., preferably having 6 to 15 carbon atoms. .
  • the alkyl group or aromatic hydrocarbon group may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom in the structure.
  • d and g are each independently an integer of 1 or more, preferably 1 or 2, h is 0 or 1 or more, preferably an integer not exceeding 2, and d + g + h is 5 or less is there.
  • e is an integer of 1 or more, preferably 1 or 2, i ,; j is independently 0 or 1 or more, preferably an integer not exceeding 2, and e + i + j is 4 or less. is there.
  • f and k are each independently an integer of 1 or more, preferably 1 or 2, 1 is 0 or 1 or more, preferably an integer not exceeding 2, and f + k + 1 is 5 or less. .
  • n is an integer of 1 to 20, preferably 2 to 10.
  • Examples of the dissolution inhibitor include cross-linkable polybutyl ether compounds.
  • a compound having two or more butyl ether groups in which atoms are bonded to carbon atoms By containing such a compound, the rectangularity of the resist pattern is improved.
  • the crosslinkable polyvinyl ether compound is presumed to exhibit the above effect by acting as a crosslinking agent for the component (A). That is, the crosslinkable polyvinyl ether compound undergoes a crosslinking reaction with the component (A) by heating during pre-beta, and forms an alkali-insoluble resist layer on the entire surface of the substrate. Thereafter, the crosslinking is decomposed by the action of the acid generated from the component (B) during exposure, and the exposed portion changes to alkali-soluble, and the unexposed portion remains alkaline-insoluble, so that the dissolution contrast is estimated to improve.
  • the crosslinking is decomposed by the action of the acid generated from the component (B) during exposure, and the exposed portion changes to alkali-soluble, and the unexposed portion remains alkaline-insoluble, so that the dissolution contrast is estimated to improve.
  • crosslinkable polyvinyl ether compound examples include JP-A-6-148889, JP-A-6-230574, etc., and any one of these may be selected and used. Can do.
  • a part of the hydroxyl group of the alcohol represented by the following general formula (f2) preference is given to compounds which are all etherified by replacing their hydrogen atoms with vinyl groups!
  • Rb is a group obtained by removing b hydrogen atoms from a straight chain, branched or cyclic alkane (preferably an alkane having 1 to L0 carbon atoms) and having a substituent. Also good. Also, there may be oxygen bonds (ether bonds) in the alkanes. b represents an integer of 2, 3 or 4.
  • ethylene glycol dibutyl ether triethylene glycol dibutyl ether, 1,3 butanediol divinyl ether, tetramethylene glycol divinino enotenole, neopentino glycinoresinobi-nore ethenore, trimethylono replon trivinyl ether, Trimethylolethane tribule ether, hexanediol dibule ether, 1,4-cyclohexanediol divininole ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol tert-butyl ether, cyclohexanedimethanol di Examples include butyl ether. Among these, crosslinkable divinyl ether compounds are preferred.
  • crosslinkable polyvinyl ether compound those represented by the following general formula (f 3) are also preferred.
  • R 27 is a branched or linear alkylene group having 1 to 10 carbon atoms, or a group represented by the following general formula (f 4).
  • R 27 may have a substituent or may contain an oxygen bond (ether bond) in the main chain.
  • each independently represents a branched or linear alkylene group having 1 to 10 carbon atoms which may have a substituent, and the alkylene group is The main chain contains an oxygen bond (ether bond)!
  • Each c is independently 0 or 1.
  • R 28 in the general formula (f-4) is an alkylene group having 1 carbon atom.
  • (Methylene group), wherein c is 1 (cyclohexane dimethanol dibutyl ether [hereinafter abbreviated as CHDVE]) Is preferred.
  • the positive resist composition of the present invention can be produced by dissolving the material in the component (S).
  • the preferred range of viscosity is the force required by the film thickness required in the process.
  • the viscosity of the positive resist composition (solution) is preferably 500 cp or less, more preferably 200 cp or less. 150 cp or less is more preferable.
  • the lower limit of the viscosity of the positive resist composition is not particularly limited, but considering the ease of forming a thick resist film having a film thickness of 1 to 15 / ⁇ ⁇ , production efficiency, etc., 30 cp or more is preferable 50 cp More preferred is 80 cp or more.
  • the viscosity of the positive resist composition (solution) adjusts the composition of the (S) component to be used (PGME content, (S2) type and Z or content), and the (S) component usage.
  • PGME content, (S2) type and Z or content the composition of the (S) component to be used
  • S2 component usage the composition of the (S) component to be used
  • the positive resist composition of the present invention is used for forming a thick resist film having a film thickness of 1 to 15 m on a support, and is a thick resist film having a film thickness of 15 m or less.
  • a thick resist film having excellent in-plane uniformity of film thickness can be formed.
  • the resist pattern formed on the thick resist film has a good shape.
  • the resist pattern formed on a thick resist film having a thickness of 1 ⁇ m or more can be used for various applications such as the manufacture of MEMS, which will be described later, and is formed using the positive resist composition of the present invention.
  • the film thickness of the resist film is preferably 2 to 10 ⁇ m, more preferably 3 to 8 ⁇ m.
  • the positive photoresist composition of the present invention is suitably used for the thick film resist laminate and the resist pattern forming method of the present invention described later. [0126] ⁇ Thick film resist laminate>
  • the thick film resist laminate of the present invention is obtained by laminating a thick film resist film having a thickness of 1 to 15 m, which serves as the positive resist composition of the present invention, on a support.
  • the support is not particularly limited, and a conventionally known one can be used.
  • Examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed.
  • Examples of the substrate include a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, aluminum, gold, and nickel, and a glass substrate.
  • As a material for the wiring pattern for example, copper, solder, chromium, aluminum, nickel, gold or the like is used.
  • a substrate having an organic or inorganic antireflection film provided on the surface of the substrate (between the substrate and the positive resist composition coating layer) as described above may be used. Tochidaru.
  • the material of the support surface on which the thick resist film is formed is the above-described material, for example, a trailing phenomenon at the interface between the pattern and the support is difficult to form.
  • a resist pattern with excellent perpendicularity can be obtained.
  • the thick film resist laminate can be produced using a conventionally known method except that the positive resist composition of the present invention is used.
  • a solution of the positive resist composition is used as a support. It can be manufactured by applying a thick film on top to form a coating film and then removing the organic solvent from the coating film by heat treatment (post applied bake (PAB) treatment). .
  • PAB post applied bake
  • the method for applying the positive resist composition solution onto the support is not particularly limited, and methods such as spin coating, slit coating, roll coating, screen printing, and applicator can be employed. .
  • the prebeta treatment conditions after coating the positive resist composition of the present invention on the support vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc. (Preferably 70 to 140 °, 0.5 to 60 minutes (preferably 1 to 30 minutes, more preferably 1 to 10 minutes).
  • the film thickness of the thick resist film in the thick film resist laminate is as described above. [0128] ⁇ Method for forming resist pattern>
  • a step of forming a thick resist film having a film thickness of 1 to 15 m on the support using the positive resist composition of the present invention, a step of selectively exposing the thick film resist film, and the above thickness A step of forming a resist pattern by alkali-developing the resist film.
  • the resist pattern forming method of the present invention can be performed, for example, as follows.
  • a thick resist film is formed on a support. This step can be performed by the same method as described in the method for producing the thick film resist laminate.
  • the formed thick resist film is selectively exposed (for example, KrF excimer laser light is selectively exposed through a desired mask pattern by a KrF exposure apparatus or the like), and then P EB (post-exposure heating) is performed.
  • PEB treatment conditions vary depending on the type of each component in the composition, blending ratio, coating film thickness, etc. Normally 60 to 150 ° C (preferably 70 to 140 ° C), 0.5 to 60 About 1 minute (preferably 1 to 50 minutes).
  • the PEB-treated thick film resist laminate is developed using an alkaline developer, for example, a 0.1 to 10% by weight tetramethyl ammonium hydroxide aqueous solution.
  • an alkaline developer for example, a 0.1 to 10% by weight tetramethyl ammonium hydroxide aqueous solution.
  • the wavelength used for exposure is not particularly limited, ArF excimer laser, KrF excimer laser, F excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam),
  • the positive resist composition according to the present invention is particularly effective for a KrF excimer laser.
  • the positive resist composition of the present invention can be used as a low-viscosity solution that can be used in mass-production equipment, and even when a strong low-viscosity solution is used, it has a film thickness of 1 to 15 m.
  • a thick resist film can be formed.
  • the resist formed on the support is excellent when the positive resist composition is coated on the support (for example, silicon eno) having excellent in-plane film thickness uniformity.
  • the reason for the strong effect of forming a thick resist film is not clear, but it is low by including a specific content of PGME as component (S). Viscosity is possible and the combined use of PGME and solvent (S2) prevents volatilization of the (S) component in the coating during PAB. Presumably because it can be stopped.
  • PGME reduces the viscosity of the solution obtained when the same amount of component (A) is dissolved, compared to the organic solvent (eg, PGMEA) generally used in conventional resist compositions. Presumed to have an action.
  • the solvent (S2) is presumed to have an effect of improving problems that occur when PGME is used alone (for example, variations in resist film thickness, storage, etc.). Then, it is presumed that by using the powerful PGME and the solvent (S2) in combination, it is possible to obtain a concentration suitable for forming a thick resist film while maintaining a low viscosity.
  • the resist pattern to be formed is also excellent in rectangularity in which the verticality of the side walls is high, and the height of the pattern (that is, the film of the resist film). (Thickness) also has a good shape such as high uniformity!
  • a resist pattern having a favorable shape as described above is useful as a frame when performing etching, a mask when performing etching, and the like. Therefore, the positive resist composition of the present invention has a thickness
  • the film resist laminate and the resist pattern forming method can be used for various applications. One of the most powerful applications is the production of MEMS (Micro Electro Mechanical Systems) in which a plating process or an etching process is performed.
  • MEMS Micro Electro Mechanical Systems
  • MEMS is an advanced small system that integrates various fine structures (such as functional elements such as sensors, conductor structures such as wiring and connection terminals) on a substrate using micromachining technology. is there.
  • MEMS magnetic heads of magnetic recording media, perpendicular magnetic heads, MRA M [(Magnetic Random Access Memory): GMR (giant magnetoresistive) film or TMR (tunnel magnetoresistive) film with magnetoresistance effect Examples are V, non-volatile memory], CCD (charge coupled device), microlens, etc.
  • GMR giant magnetoresistive
  • TMR tunnel magnetoresistive film with magnetoresistance effect
  • V non-volatile memory
  • CCD charge coupled device
  • microlens etc.
  • the shape of the resist pattern deteriorates when heated at a high temperature, for example, about 130 ° C. There is.
  • the component (A) includes a styrenic structural unit such as the structural unit (al) or (a3) described above, or a component having Mw of 20000 or more, it is formed by the present invention.
  • the heat resistance of the resist pattern is improved and it is useful for the above processes.
  • the positive resist composition, thick film resist laminate and resist pattern forming method of the present invention can form a thick resist film having a good shape, and thus are useful for an ion implantation process. .
  • an impurity diffusion layer is formed on the support surface.
  • the formation of the impurity diffusion layer is usually performed in two stages, introduction and diffusion of impurities.
  • impurities such as phosphorus and boron are ionized in a vacuum and accelerated by a high electric field.
  • implantation! / ion implantation
  • the resist pattern is used as a mask when the impurity ions are selectively implanted into the support surface by implantation. Therefore, the resist pattern used in the implantation process is required to have excellent shape characteristics in order to implant ions into a desired portion of the support.
  • a resist pattern used in a high energy implantation process that is higher in energy than a normal implantation process is required to have a thick film for resistance to the process.
  • the present invention can form a thick resist pattern having a good shape, and is therefore useful for an implantation process, particularly for a high energy implantation process.
  • FIGS. 1A, IB and 1C An example of a MEMS manufacturing process using the present invention will be described below with reference to FIGS. 1A, IB and 1C.
  • FIG. 1A, FIG. IB, and FIG. 1C are schematic views (side sectional views) showing respective steps of manufacturing a write portion (write head portion) of a magnetic head.
  • a fine trench type resist pattern is formed, and the resist pattern is used as a frame to perform the plating. More specifically, a technique for forming a fine magnetic film pattern is used. More specifically, as shown in FIG. 1A, a seed layer 11 is formed on the upper surface of a base material (not shown) on which a desired laminated structure is formed. Then, a slit-like resist pattern 12 having a substantially rectangular cross section is obtained by the conventional lithography described above.
  • a magnetic film 13 ′ is formed by applying plating to the trench (recessed portion) surrounded by the obtained resist pattern 12.
  • each component shown in Table 1 was mixed and dissolved to prepare a positive resist composition.
  • the unit of the compounding amount shown in [] is part by mass.
  • the numerical value in parentheses for the component (s) indicates the ratio (mass%) of each solvent in the component (S).
  • Example 1 and Comparative Examples 1 to 2 or the positive resist compositions of Example 2 and Comparative Example 2 are used! Then, by changing the blending amount of the component (S), a thick resist film having a thickness of 5. or 9.0 m was formed under the following resist film formation conditions, and the in-plane uniformity was evaluated. It was.
  • a positive resist composition with a viscosity of 5.0 m can be formed under the above resist film formation conditions, using the spinner on the Si substrate, and the same conditions as the above resist film formation conditions. Then, a resist film was formed.
  • the resist film thickness (nm) at 10 measurement points shown in FIG. 2 was measured using a resist film thickness measuring device Nanospec (manufactured by Nanometrics). From the results, the average film thickness (nm), the range from the minimum film thickness to the maximum film thickness (nm), and 3 ⁇ were obtained. The results are shown in Table 2.
  • 3 ⁇ is a value (3 ⁇ ) that is three times the standard deviation ( ⁇ ) calculated for the measurement result force at 10 locations. As this 3 ⁇ is smaller, the in-plane variation of the film thickness is smaller. This means that a resist film with high in-plane uniformity was obtained.
  • Example 1 can be used as it is with a mass production apparatus, such as a commercially available coater, whose viscosity is as low as 116 cp at which a resist film having a thickness of 5.0 ⁇ m is formed under the above conditions. It was about a viscosity. In addition, in-plane uniformity with little variation in film thickness was high.
  • the viscosity at which the resist film was formed was very high at 155 cp. In Comparative Example 1, although the viscosity could be reduced, the in-plane uniformity of the resist film was insufficient.
  • Example 2 The positive resist compositions of Example 2 and Comparative Example 2 were evaluated in the same manner as in the above (1), except that the thickness of the resist film to be formed was 9. ⁇ . The results are shown in Table 3.
  • the positive resist composition of the present invention using a mixed solvent of PGME and the other solvent (S2) is used, for example, when PGMEA is used alone. Even if the viscosity was low, a thick resist film having a thickness of 5.0 to 9.0 m could be formed.
  • the thick resist film also has good in-plane uniformity of film thickness, and in any example, the difference between the minimum film thickness and the maximum film thickness and the average film thickness is ⁇ 3% of the average film thickness. 7 within the range.
  • a thick film resist film formed using the positive resist composition of the present invention has excellent in-plane uniformity, and as a result, a resist pattern formed on the thick film resist film. In this case, variations in pattern dimensions are suppressed, and the resist pattern shape and focal depth range are also improved.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

La présente invention concerne une composition de réserve positive destinée à être utilisée dans la formation d'un film de réserve épais de 1 à 15μm. La composition comporte un constituant de résine (A) dont la solubilité alcaline peut être accrue par l'action d'un acide et un constituant générateur d'acide (B) qui peut générer un acide lorsqu'il est exposé à la lumière, les deux étant dissous dans un solvant organique (S). Dans la composition, le solvant organique (S) est un mélange de 10 à 95% en poids d'éther monométhylique de propylène glycol et de 5 à 90% en poids d'un autre solvant (S2).
PCT/JP2007/052555 2006-03-15 2007-02-14 Composition de réserve positive de formation de film de réserve épais, stratifié de réserve épais, et procédé de formation de motif de réserve WO2007108253A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-070927 2006-03-15
JP2006070927A JP4954576B2 (ja) 2006-03-15 2006-03-15 厚膜レジスト積層体およびその製造方法、レジストパターン形成方法

Publications (1)

Publication Number Publication Date
WO2007108253A1 true WO2007108253A1 (fr) 2007-09-27

Family

ID=38522290

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/052555 WO2007108253A1 (fr) 2006-03-15 2007-02-14 Composition de réserve positive de formation de film de réserve épais, stratifié de réserve épais, et procédé de formation de motif de réserve

Country Status (3)

Country Link
JP (1) JP4954576B2 (fr)
TW (1) TWI349164B (fr)
WO (1) WO2007108253A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022248524A1 (fr) * 2021-05-28 2022-12-01 Merck Patent Gmbh Composition de réserve à film épais et procédé de fabrication de film de réserve l'utilisant
WO2024104940A1 (fr) * 2022-11-15 2024-05-23 Merck Patent Gmbh Composition de résine photosensible de type positif chimiquement amplifié à film épais et procédé de fabrication de film de résine photosensible l'utilisant

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102220063B1 (ko) 2016-09-30 2021-02-25 후지필름 가부시키가이샤 패턴 형성 방법, 전자 디바이스의 제조 방법, 및 감활성광선성 또는 감방사선성 조성물
JP7317704B2 (ja) 2016-10-12 2023-07-31 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 化学増幅型ポジ型フォトレジスト組成物およびそれを用いたパターンの形成方法
JP6979077B2 (ja) 2017-08-31 2021-12-08 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、固体撮像素子の製造方法
KR20200036899A (ko) 2017-09-29 2020-04-07 후지필름 가부시키가이샤 패턴 형성 방법, 이온 주입 방법, 고체 촬상 소자의 제조 방법, 다층 레지스트막, 감활성광선성 또는 감방사선성 수지 조성물
WO2021199823A1 (fr) 2020-03-30 2021-10-07 富士フイルム株式会社 Procédé de production de composition de résine sensible aux rayons actiniques ou sensible aux rayonnements, procédé de formation de motif et procédé de fabrication de dispositif électronique

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001042533A (ja) * 1999-07-26 2001-02-16 Fuji Photo Film Co Ltd 遠紫外線露光用ポジ型フォトレジスト組成物
JP2001183837A (ja) * 1999-12-22 2001-07-06 Fuji Photo Film Co Ltd 遠紫外線露光用ポジ型フォトレジスト組成物
JP2001356478A (ja) * 2000-06-12 2001-12-26 Fuji Photo Film Co Ltd ポジ型フォトレジスト組成物
JP2003206315A (ja) * 2002-01-10 2003-07-22 Daicel Chem Ind Ltd フォトレジスト用高分子化合物の製造方法、及びフォトレジスト用樹脂組成物
JP2005091433A (ja) * 2003-09-12 2005-04-07 Mitsui Chemicals Inc ポジ型感光性樹脂組成物、およびその用途
WO2006003824A1 (fr) * 2004-07-01 2006-01-12 Tokyo Ohka Kogyo Co., Ltd. Composition chimiquement amplifiée pour réserve et procédé pour former le motif de la réserve

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3798552B2 (ja) * 1998-04-23 2006-07-19 東京応化工業株式会社 化学増幅型ホトレジスト
JP3934816B2 (ja) * 1999-03-18 2007-06-20 東京応化工業株式会社 ディフェクト抑制ポジ型レジスト塗布液
JP4549911B2 (ja) * 2004-03-31 2010-09-22 東京応化工業株式会社 リフトオフ用ポジ型レジスト組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001042533A (ja) * 1999-07-26 2001-02-16 Fuji Photo Film Co Ltd 遠紫外線露光用ポジ型フォトレジスト組成物
JP2001183837A (ja) * 1999-12-22 2001-07-06 Fuji Photo Film Co Ltd 遠紫外線露光用ポジ型フォトレジスト組成物
JP2001356478A (ja) * 2000-06-12 2001-12-26 Fuji Photo Film Co Ltd ポジ型フォトレジスト組成物
JP2003206315A (ja) * 2002-01-10 2003-07-22 Daicel Chem Ind Ltd フォトレジスト用高分子化合物の製造方法、及びフォトレジスト用樹脂組成物
JP2005091433A (ja) * 2003-09-12 2005-04-07 Mitsui Chemicals Inc ポジ型感光性樹脂組成物、およびその用途
WO2006003824A1 (fr) * 2004-07-01 2006-01-12 Tokyo Ohka Kogyo Co., Ltd. Composition chimiquement amplifiée pour réserve et procédé pour former le motif de la réserve

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022248524A1 (fr) * 2021-05-28 2022-12-01 Merck Patent Gmbh Composition de réserve à film épais et procédé de fabrication de film de réserve l'utilisant
WO2024104940A1 (fr) * 2022-11-15 2024-05-23 Merck Patent Gmbh Composition de résine photosensible de type positif chimiquement amplifié à film épais et procédé de fabrication de film de résine photosensible l'utilisant

Also Published As

Publication number Publication date
JP4954576B2 (ja) 2012-06-20
TW200745760A (en) 2007-12-16
TWI349164B (en) 2011-09-21
JP2007248727A (ja) 2007-09-27

Similar Documents

Publication Publication Date Title
JP4937594B2 (ja) 厚膜レジスト膜形成用のポジ型レジスト組成物、厚膜レジスト積層体およびレジストパターン形成方法
JP4485922B2 (ja) ネガ型レジスト組成物
TW554256B (en) Positive photoresist composition and forming metho
WO2006027997A1 (fr) Composition de résist pour faisceau d’électrons ou uv extrêmes (ultraviolets extrêmes) et procédé de formation de motifs de résist
WO2006082740A1 (fr) Composition de résist à fonctionnement positif et procédé de formation de motif de résist
WO2007108253A1 (fr) Composition de réserve positive de formation de film de réserve épais, stratifié de réserve épais, et procédé de formation de motif de réserve
WO2005101128A1 (fr) Composition de resist positif et procede d’elaboration de motifs de resist
KR100852376B1 (ko) 레지스트 조성물, 적층체, 및 레지스트 패턴 형성 방법
JP4772288B2 (ja) ホトレジスト組成物用樹脂、ホトレジスト組成物、およびレジストパターン形成方法
WO2006008914A1 (fr) Composition pour enduit protecteur et procédé de formation du motif de l’enduit protecteur
TWI333594B (en) Positive resist composition, process for forming resist pattern, and process for ion implantation
WO2005081061A1 (fr) Composition photoresistante et procede de formation dee la structure résistante
WO2006051769A1 (fr) Procede de formation d’un motif de reserve
WO2005057287A1 (fr) Composition de reserve positive et procede de formation d'un motif de reserve
KR20070022334A (ko) 포지티브형 레지스트 조성물 및 레지스트 패턴 형성 방법
WO2007148492A1 (fr) Composition de résine positive et procédé de formation d'un motif de résine
WO2006080151A1 (fr) Procédé de formation d’un motif de réserve
US8097396B2 (en) Positive resist composition and method for forming resist pattern
WO2006003824A1 (fr) Composition chimiquement amplifiée pour réserve et procédé pour former le motif de la réserve
JP2004175981A (ja) 樹脂の製造方法、樹脂、レジスト組成物、レジストパターン形成方法
JP4347110B2 (ja) 電子線又はｅｕｖ用ポジ型レジスト組成物
WO2007055272A1 (fr) Composition de resist positif et procede de formation de motif de resist
WO2006061975A1 (fr) Procede de formation d'un modele d’enduit de protection
WO2006085419A1 (fr) Formule de photorésine positive et méthode de formation d'un motif sur la photorésine
JP4308125B2 (ja) レジストパターンの形成方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07714133

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07714133

Country of ref document: EP

Kind code of ref document: A1