WO2016190221A1 - Composition pour revêtement, et procédé de fabrication de stratifié photorésistant - Google Patents

Composition pour revêtement, et procédé de fabrication de stratifié photorésistant Download PDF

Info

Publication number
WO2016190221A1
WO2016190221A1 PCT/JP2016/064921 JP2016064921W WO2016190221A1 WO 2016190221 A1 WO2016190221 A1 WO 2016190221A1 JP 2016064921 W JP2016064921 W JP 2016064921W WO 2016190221 A1 WO2016190221 A1 WO 2016190221A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
containing compound
coating composition
solvent
group
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2016/064921
Other languages
English (en)
Japanese (ja)
Inventor
龍二郎 山崎
伊藤　昌宏
好彦 坂根
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass 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
Priority claimed from JP2015157194A external-priority patent/JP2018119019A/ja
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2016190221A1 publication Critical patent/WO2016190221A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography

Definitions

  • the present invention relates to a coating composition.
  • the present invention relates to a coating composition useful as a composition for forming an antireflection film in photolithography, and a method for producing a photoresist laminate using the same.
  • TARC method a method of providing an antireflection film on the surface of a photoresist layer
  • resist pattern a photoresist pattern
  • the ideal refractive index of the antireflection film for obtaining a good antireflection effect in the TARC method is the square root ( ⁇ n) of the refractive index n of the photoresist layer (for example, Patent Document 1). Paragraph [0004]).
  • the refractive index at 193 nm of a commonly used resist is 1.6 to 1.8 (for example, paragraph [0006] of Patent Document 1).
  • the refractive index at 193 nm of the antireflection film is desirably closer to the range of 1.265 to 1.342.
  • Patent Document 2 describes a method of forming an antireflection film on a photoresist layer using a fluoropolymer having a hydrophilic group that can be dissolved in water, an aqueous solvent or a developer.
  • a coating composition in which a copolymer of a fluorine-containing monomer having a hydroxyl group at the end of the side chain and tetrafluoroethylene was dissolved in a mixed solvent of water and isopropyl alcohol was obtained to form a film. It is described that the refractive index (193 nm) of the film was 1.39.
  • Patent Document 3 describes a method for realizing an antireflection layer having a low refractive index by a layer mainly composed of fine particles (particle size: 1 to 100 nm). In this method, it is described that the refractive index is lowered by forming voids corresponding to the shape of the fine particles in the antireflection layer, and in Example 8, the refractive index at 193 nm was 1.32.
  • Patent Document 4 a polymer having a ring structure in the main chain, obtained by cyclopolymerization of a fluorine-containing monomer having two polymerizable carbon-carbon double bonds, is reflected on the photoresist layer. A method of forming a protective film is described.
  • the refractive index of the antireflection film is preferably closer to the range of 1.265 to 1.342 at 193 nm, and the coating composition described in Patent Document 2 is insufficient. Since the antireflection film of Patent Document 3 contains fine particles, exposure light may be scattered. When the present inventors measured the refractive index in 193 nm about the antireflection film described in patent document 4 (example 6 mentioned later), it was 1.38 and was inadequate.
  • the present invention provides a coating composition capable of forming an antireflection film having a low refractive index without using fine particles, and a method for producing a photoresist laminate using the same.
  • the present invention provides a coating composition having the following constitutions [1] to [12] and a method for producing a photoresist laminate.
  • a coating composition comprising at least one fluorine-containing compound selected from the following fluorine-containing compound (A1) and the following fluorine-containing compound (A2).
  • Fluorine-containing compound (A1) A polymer comprising only one unit selected from the following units (I), and having a number average molecular weight of 1,000 to 50,000.
  • Unit (I) a unit based on a monomer having only one polymerizable carbon-carbon double bond, composed of only carbon, oxygen and fluorine atoms, and having one or more side chains, The unit in which at least one side chain contains one or more etheric oxygen atoms that do not constitute a ring, and the terminal is —CF 3 .
  • Fluorine-containing compound (A2) A compound having a perfluoropolyether skeleton in the main chain and a number average molecular weight of 1,000 to 50,000.
  • a hydrogen group (wherein the number of etheric oxygen atoms is less than or equal to the number of carbon atoms), and the other is a perfluoro saturated hydrocarbon group having 1 to 12 carbon atoms not containing an etheric oxygen atom that does not form a ring, or Indicates a fluorine atom.)
  • At least one of X 1 , X 2 , X 3 , X 4 is a —O—Rf 1 group (the Rf 1 group is a carbon having 0 to 3 etheric oxygen atoms between carbon-carbon atoms) (4)
  • the fluorine-containing solvent has a fluorine atom content of 65% by mass or more.
  • a method for producing a photoresist laminate in which an antireflection film is provided on the surface of a photoresist layer, the coating being any one of [1] to [11] on the surface of the photoresist layer A method for producing a photoresist laminate, comprising: applying a composition to form a coating film comprising the coating composition; and if the coating film contains a solvent, the solvent is then removed from the coating film.
  • an antireflection film having a low refractive index can be formed without using fine particles.
  • a photoresist laminate in which an antireflection film having a low refractive index and containing no fine particles is formed on the surface of the photoresist layer can be obtained.
  • Fluorine-containing compound means a compound having a fluorine atom in the molecule.
  • the fluorine-containing compound includes a fluorine-containing polymer.
  • the “unit” means a part derived from a monomer that exists in the polymer and constitutes the polymer.
  • the monomer and the unit based thereon are denoted by the same reference numerals.
  • units (I) those based on the monomer (I) are referred to as units (I).
  • a unit (I) that is obtained by chemically converting the structure of the unit (I) after forming the polymer is also referred to as the unit (I).
  • perfluoropolyether skeleton means a molecular chain in which two or more oxyperfluoroalkylene groups are linked.
  • Perfluoro means that all of the hydrogen atoms bonded to the carbon atom are substituted with fluorine atoms.
  • oxyperfluoroalkylene group means a group in which an oxygen atom is bonded to one end of the perfluoroalkylene group, and the chemical formula represents the oxygen atom on the right side of the perfluoroalkylene group.
  • the values of “mass average molecular weight and number average molecular weight of fluorine-containing compound” are polystyrene (PS) equivalent molecular weights determined by gel permeation chromatography (GPC).
  • “Fluorine atom content of fluorine-containing compound (unit: mass%)” is obtained by fluorine atom content analysis and indicates the ratio of the mass of fluorine atoms to the total mass of all atoms constituting the fluorine-containing compound.
  • “Fluorine atom content of fluorine-containing solvent (unit: mass%)” is obtained by fluorine atom content analysis and indicates the ratio of the mass of fluorine atoms to the total mass of all atoms constituting the fluorine-containing solvent.
  • the “molecular weight of the monomer” is a formula weight obtained based on the chemical formula. “Branched” means having a branched chain, and also having a branched chain and including a ring is also called branched.
  • the coating composition of the present invention contains at least one fluorine-containing compound selected from the fluorine-containing compound (A1) and the fluorine-containing compound (A2).
  • fluorine-containing compound (A1) and the fluorine-containing compound (A2) are collectively referred to as “fluorine-containing compound (A)”.
  • the fluorine-containing compound (A) has a molecular structure that contributes to a decrease in the refractive index, and the refractive index at 193 nm can be adjusted to 1.32 to 1.36.
  • the refractive index can be expressed.
  • the refractive index at 193 nm of the film made of the fluorine-containing compound (A) can be set to 1.32 to 1.36.
  • the refractive index of the fluorine-containing compound (A) is not more than the upper limit of the above range, it is preferable because the refractive index is close to the above-described range of 1.265 to 1.342.
  • the refractive index of the fluorine-containing compound (A) is an eigenvalue and is constant regardless of the shape of the film or the like.
  • the fluorine-containing compound (A1) is a homopolymer in which the unit present in the polymer is only one selected from the following units (I).
  • Unit (I) a unit based on a monomer having only one polymerizable carbon-carbon double bond, which is composed of only carbon atoms, oxygen atoms, and fluorine atoms, and has one or more side chains , Wherein at least one side chain includes one or more etheric oxygen atoms that do not constitute a ring, and the terminal is a unit of —CF 3 .
  • a carbon chain (—C—C—) generated by cleavage of one double bond is the main chain of the fluorine-containing compound (A1).
  • the atoms constituting the unit (I) are only carbon atoms, oxygen atoms and fluorine atoms. By not containing other atoms such as hydrogen atoms, the fluorine atom content is increased, which contributes to a decrease in refractive index.
  • Unit (I) has one or more side chains.
  • the number of side chains is 1 to 4, preferably 1 to 3, and particularly preferably 1 to 2. When two or more side chains are present, the structures of the plurality of side chains may be the same or different.
  • At least one of the side chains of the unit (I) contains one or more etheric oxygen atoms that do not form a ring, and the terminal is —CF 3 .
  • the etheric oxygen atom that does not constitute a ring increases the mobility of the molecule and contributes to a decrease in crystallinity of the fluorine-containing compound (A1). As a result, it is thought that it contributes to the fall of the refractive index of a fluorine-containing compound (A1). Note that etheric oxygen atoms present in the ring structure have a small effect of lowering the refractive index. This is probably because there is no molecular end in the ring structure, so even if an etheric oxygen atom is present, the contribution to the mobility of the molecule is small.
  • the upper limit of the number of etheric oxygen atoms that do not constitute a ring present in one side chain is not particularly limited, but is preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less, from the viewpoint of ease of production. preferable.
  • the molecular weight of the unit (I) is preferably 60 or more. When the molecular weight of the unit is not less than the lower limit of the above range, the fluorine atom content increases and the refractive index tends to be low.
  • the upper limit of the molecular weight of the unit (I) is preferably 800 or less, particularly preferably 500 or less, from the viewpoint of ease of production and easy recovery of unreacted monomers.
  • the unit (I) is preferably a unit (i) represented by the following formula (i). -[CX 1 X 2 -CX 3 X 4 ]-(i) (In the formula, at least one of X 1 , X 2 , X 3 , and X 4 independently represents a C 1-12 perfluoro saturated carbon atom containing 1 to 4 etheric oxygen atoms that do not constitute a ring.
  • a hydrogen group (hereinafter also referred to as “side chain 1”) (wherein the number of etheric oxygen atoms is not more than the number of carbon atoms) and the terminal is —CF 3 ;
  • a perfluoro saturated hydrocarbon group having 1 to 12 carbon atoms not containing an etheric oxygen atom that does not constitute a ring (hereinafter also referred to as “side chain 2”) or a fluorine atom.)
  • the side chain 1 is preferably an —O—Rf 1 group (the Rf 1 group is a C 1-12 perfluoro saturated hydrocarbon group containing 0 to 3 etheric oxygen atoms between carbon-carbon atoms).
  • the Rf 1 group may be linear or branched, and is preferably branched from the viewpoint that the refractive index tends to be lower. If there is a branched structure, the fluorine-containing compound (A1) becomes bulky and the density decreases, so the refractive index is considered to be low.
  • the Rf 1 group may contain a ring. When a ring is included, the ring may or may not have an etheric oxygen atom.
  • the Rf 1 group preferably has 3 to 12 carbon atoms. If it is less than or equal to the upper limit, the boiling point does not become too high, and the recovery of unreacted monomers is facilitated.
  • Rf present in 1 group the upper limit of the number of rings does not constitute etheric oxygen atoms is less than or equal to the number of carbon atoms in the Rf 1 group. From the viewpoint of ease of production, it is preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less.
  • Specific examples of the side chain 1 include the following.
  • the side chain 2 is preferably a perfluoro saturated hydrocarbon group having 1 to 12 carbon atoms (hereinafter also referred to as “Rf 2 group”).
  • Rf 2 group may be linear or branched, and is preferably branched from the viewpoint of further reducing the manufacturability and refractive index.
  • the Rf 2 group has 1 to 12 carbon atoms, preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 3.
  • the refractive index of the polymer becomes lower, it becomes easy recovery of unreacted monomers to be less than the upper limit value.
  • Specific examples of the Rf 2 group include —CF 3 and —CF (CF 3 ) CF 3 .
  • one of them is preferably a side chain 1 and the other 3 are fluorine atoms or other 3 It is preferable that one of them is a side chain 2 and the other two are fluorine atoms.
  • the unit (i) one in which one of X 1 , X 2 , X 3 and X 4 is an —O—Rf 1 group and the other three are fluorine atoms is particularly preferable.
  • Preferable specific examples of the unit (i) include the following.
  • both ends of the main chain of the fluorine-containing compound (A1) is not particularly limited.
  • a residue derived from the polymerization initiator or chain transfer agent used in the production of the fluorine-containing compound (A1) may be present.
  • Both end groups may be the same as or different from each other.
  • Specific examples of the terminal group of the main chain include the following.
  • the number average molecular weight of the fluorine-containing compound (A1) is 1,000 to 50,000, preferably 3,000 to 30,000, particularly preferably 3,000 to 10,000.
  • the fluorine-containing compound (A1) can be produced by a known production method. For example, the manufacturing method described in Japanese Patent No. 4962559 can be used.
  • the fluorine-containing compound (A2) is a compound having a perfluoropolyether skeleton in the main chain.
  • an etheric oxygen atom that does not constitute a ring is present in the main chain.
  • the mobility of the whole molecule is easily improved. Therefore, it is considered that the crystallinity of the fluorine-containing compound (A2) is further reduced and the refractive index of the fluorine-containing compound (A2) is further reduced.
  • the oxyperfluoroalkylene group constituting the perfluoropolyether skeleton has 1 to 5 carbon atoms, preferably 1 to 3, and particularly preferably 1 to 2.
  • the oxyperfluoroalkylene group may be linear or branched when it has 3 or more carbon atoms. A branched shape is preferable in that the refractive index of the fluorine-containing compound (A2) tends to be lower. If the branched structure is present, the fluorine-containing compound (A2) becomes bulky and the density decreases, so that the refractive index is considered to be lower.
  • the oxyperfluoroalkylene group may be one type or two or more types. When two or more kinds of oxyperfluoroalkylene groups are linked, the bonding order thereof is not particularly limited. Any of random, block, and alternate may be used, or a combination thereof.
  • a compound represented by the following formula (II) is preferable.
  • Y and Z are each independently a monovalent organic group (wherein Y is not an oxygen atom on the side bonded to —O—, and Z is bonded to — (C n F 2n O) m —)
  • n is an integer of 1 to 5
  • m is an integer of 2 to 200, and when m is 2 or more, a plurality of ( C n F 2n O) may be the same or different from each other.
  • Preferable examples of (C n F 2n O) include the following. A combination of (CF 2 O) and (CF 2 CF 2 O), a combination of (CF 2 CF 2 O) and (CF 2 CF 2 CF 2 O), (CF 2 CF 2 CF 2 O) and (CF 2 CF 2 CF 2 O), (CF (CF 3 ) CF 2 O) alone.
  • M in the formula (II) is preferably 10 to 100, more preferably 10 to 30, further preferably 15 to 25, and particularly preferably 20 to 25.
  • Y and Z are preferably groups having a fluorine atom. Specific examples include —CF 2 CH 2 OH, —CF 2 H, —CF 2 CF 2 CF 3 , —CF 2 CH 2 OCF 2 CHFOCF 2 CF 2 CF 3 .
  • the fluorine-containing compound (A2) can be produced by a known production method. For example, the production method described in International Publication No. 2009/008380 can be used.
  • a commercially available product may be used as the fluorine-containing compound (A2).
  • FLUOROLINK D4000 or FLUOROLINK D10 / H all are product names) manufactured by Solvay Solexis, DENNUM SA (product name) manufactured by Daikin Is mentioned.
  • the fluorine-containing compound (A2) from which Y and Z differ from a commercially available thing can also be manufactured from a commercially available fluorine-containing compound (A2).
  • a fluorine-containing compound in which both Y and Z are —CF 2 CH 2 OH for example, the above FLUOROLINK D4000
  • a fluorine-containing compound in which both ends of Y and Z are perfluoroalkyl groups ( A2) can be produced.
  • perfluoro (alkyl vinyl ether) can be added to the hydroxyl group of —CF 2 CH 2 OH to convert the perfluoro (alkyl vinyl ether) to Y or Z having a perfluoroalkyl moiety at the terminal.
  • the number average molecular weight of the fluorine-containing compound (A2) is 1,000 to 50,000, preferably 3,000 to 30,000, particularly preferably 3,000 to 10,000.
  • it is at least the lower limit of the above range, the influence of the terminal group on the refractive index of the fluorine-containing compound (A2) is small, and it is easy to control the refractive index.
  • it is excellent in film forming property, and it is excellent in the uniformity of the film thickness in a flat part. If it is less than the upper limit value, it is excellent in the ability to follow a step during coating, and if the surface of the resist layer is uneven, the amount of coating required to cover the entire surface of the convex and concave portions can be reduced.
  • the coating composition of this invention contains a solvent as needed.
  • the polymer other than the fluorine-containing compound (A), or other components inevitable in production (unreacted raw materials, by-products, additives used in the production of the polymer) ) May be included.
  • fine particles may be contained. When fine particles are included, care must be taken so that scattering by the fine particles is not excessive.
  • the fluorine-containing compound (A) is preferably dissolved in the solvent.
  • the solvent for the coating composition is preferably a fluorine-containing solvent.
  • the fluorine atom content of the fluorinated solvent is preferably 65% by mass or more, and particularly preferably 70% by mass or more, from the viewpoint that good solubility of the fluorinated compound (A) is easily obtained.
  • a fluorine-containing solvent does not contain polar groups, such as a hydroxyl group and a carboxy group.
  • a solvent having a high boiling point is preferable because the film thickness can be easily increased even at the same polymer concentration.
  • a preferable boiling point is, for example, 95 ° C. or more, and 110 to 150 ° C. is particularly preferable.
  • the solvent of a coating composition does not melt
  • a fluorine-containing solvent is also preferable in this respect.
  • CF 3 CF 2 CF 2 CF 2 CF 2 CH 2 CH 3 (boiling point 114 ° C.), CF 3 CF (CF 3 ) CF (OCH 3 ) CF 2 CF 3 (boiling point 98 ° C.).
  • the temperature for dissolving the fluorine-containing compound (A) in these fluorine-containing solvents is sufficient at room temperature, and for example, stirring may be performed for about 3 hours.
  • the concentration of the total amount of the fluorine-containing compound (A) and the other polymer in the coating composition is preferably 1 to 30% by mass.
  • the ratio of the fluorine-containing compound (A) to the total amount of the fluorine-containing compound (A) and the other polymers in the coating composition is preferably 50% by mass or more, more preferably 70% by mass or more, and 100 Mass% is particularly preferred.
  • the content of the solvent in the coating composition is preferably 70 to 99% by mass.
  • the content of the fluorine-containing solvent in the coating composition is preferably 70 to 99% by mass.
  • the method for producing a photoresist laminate of the present invention is a method for producing a photoresist laminate in which an antireflection film is provided on the surface of a photoresist layer, the coating of the present invention on the surface of the photoresist layer.
  • the coating composition is applied to form a coating film comprising the coating composition, and when the coating film contains a solvent, the solvent is then removed from the coating film.
  • a known method can be used as a method for forming a coating film by applying the coating composition of the present invention on the surface of the photoresist layer.
  • the spin coating method is preferable from the viewpoint of the uniformity and simplicity of the antireflection film.
  • an antireflection film can be obtained by removing the solvent from the coating film after the coating film is formed.
  • drying conditions for example, in the case of a hot plate, conditions of 80 to 150 ° C. and 30 to 200 seconds are preferable.
  • the film thickness of the antireflection film may be set in accordance with a known antireflection theory. The film thickness is set to an odd multiple of “(exposure wavelength) / (4 ⁇ (refractive index of antireflection film))”. Since prevention performance becomes high, it is preferable.
  • the antireflection film formed on the surface of the photoresist layer using the coating composition of the present invention needs to be removed using a top antireflection film removing solvent after exposing the photoresist laminate. . Then, after removing the antireflection film, the photoresist is developed using an alkaline aqueous solution.
  • the solvent for removing the top antireflection film is preferably one having high solubility of the fluorine-containing compound (A), and is the same as the fluorine-containing solvent used in the coating composition including specific examples.
  • the solvent for removing the top antireflection film may be mixed with a non-fluorine solvent in the fluorinated solvent as long as the resist is not dissolved and the top antireflection film can be removed.
  • non-fluorine solvent examples include ketone compounds such as 2-butanone; ether compounds such as diethyl ether, dimethyl ether, tetrahydrofuran, dibutyl ether, and diisoamyl ether, and ether compounds are preferred.
  • the ether compound has an etheric oxygen atom in the same manner as the fluorine-containing compound (A) to be dissolved.
  • the ether compound contains a fluorine-containing solvent mixed with a fluorine-containing solvent ( Since the decrease in the solubility of A) can be further suppressed, a larger amount can be mixed with the fluorinated solvent.
  • Examples 1 to 9 Examples 1 to 5 and 9 are Examples, and Examples 6 to 8 are Comparative Examples.
  • the measurement method and evaluation method used the following methods.
  • a commercially available resist composition (product name: Sumiresist PAR-855S75 (J), manufactured by Sumitomo Chemical Co., Ltd.) was applied to a silicon wafer by spin coating so that the film thickness was about 120 nm, and the temperature was 150 ° C.
  • the resist film was formed by drying for 90 seconds on the adjusted hot plate. Thereafter, several drops of the fluorine-containing compound solution obtained in each example (fluorine-containing compound concentration of 20% by mass) were dropped and allowed to stand for 30 minutes. After 30 minutes, the fluorine-containing compound was removed by flowing a solvent for removing the top antireflection film of the type shown in the table over the substrate, and the resist surface was observed. If there was no change, it was judged as ⁇ (good), and if unevenness or the like occurred, it was judged as x (defect).
  • Example 1 Synthesis and evaluation of fluorine-containing compound (A1-1)] After charging 50 g of the monomer (a) and 0.68 g of the polymerization initiator solution (1) into a 50 mL pressure-resistant glass container, the system was replaced with nitrogen. Subsequently, it stirred while heating so that internal temperature might be 40 degreeC, and the polymerization reaction was performed for 72 hours. After completion of the polymerization reaction, the unreacted raw material was distilled off by vacuum drying at 80 ° C. to obtain 17.4 g of a fluorine-containing compound (A1-1).
  • the fluorine-containing polymer (A1-1) and the solvent (1) are stirred at room temperature for 3 hours to obtain a fluorine-containing compound solution (coating composition) having a concentration of the fluorine-containing compound of 20% by mass.
  • the mass average molecular weight, number average molecular weight, and fluorine atom content of the fluorine-containing compound (A1-1) are shown in Table 1 (hereinafter the same).
  • Table 1 also describes the main manufacturing conditions.
  • Example 2 and 3 Synthesis and evaluation of fluorine-containing compounds (A1-2) and (A1-3)]
  • a fluorine-containing compound solution (coating composition) having a fluorine-containing compound content (concentration) of 20% by mass was obtained in the same manner as in Example 1 except that the polymerization process conditions were changed as shown in Table 1. Evaluation was performed in the same manner as in Example 1.
  • Example 4 Evaluation of fluorine-containing compound (A2-1)
  • the fluorine-containing compound (A2-1) was dissolved in the solvent (1) so that the concentration of the fluorine-containing compound was 20% by mass to obtain a fluorine-containing compound solution (coating composition). Evaluation was performed in the same manner as in Example 1.
  • Example 5 Synthesis and evaluation of fluorine-containing compound (A2-2)
  • the fluorine-containing polymer (A2-1) and the monomer (a) were reacted to replace the hydrogen atoms at both ends of the fluorine-containing compound (A2-1) with —CF 2 CFHCF 2 CF 2 CF 3 .
  • a fluorine-containing compound (A2-2) was obtained.
  • Example 6 Synthesis and evaluation of fluorine-containing compound (D)]
  • a fluorine-containing compound solution (coating composition) having a fluorine-containing compound content (concentration) of 20% by mass was obtained in the same manner as in Example 1 except that the polymerization process conditions were changed as shown in Table 1. Evaluation was performed in the same manner as in Example 1.
  • a chain transfer agent methanol
  • the monomer (d) is a fluorine-containing monomer having a polymerizable carbon-carbon double bond at both ends.
  • the monomer (d) is a unit (d-1) represented by the following formula (d-1) by cyclopolymerization: )
  • Example 7 Synthesis and evaluation of fluorine-containing compound (E)]
  • a fluorine-containing compound solution (coating composition) having a fluorine-containing compound content (concentration) of 20% by mass was obtained in the same manner as in Example 1 except that the polymerization process conditions were changed as shown in Table 1. Evaluation was performed in the same manner as in Example 1. In this example, a chain transfer agent (methanol) was also added when the monomer and the polymerization initiator solution (1) were charged.
  • Example 8 Synthesis and evaluation of fluorine-containing compound (F-1)] After charging 50 g of the monomer (f) and 0.60 g of the polymerization initiator solution (1) into a 50 mL pressure-resistant glass container, the system was replaced with nitrogen. Subsequently, it stirred while heating so that internal temperature might be 40 degreeC, and the polymerization reaction was performed for 72 hours. After completion of the polymerization reaction, unreacted raw materials were distilled off by vacuum drying at 80 ° C. to obtain 19 g of a fluorine-containing compound (F). Fluorine-containing compound (F) and water are charged into a separable flask and hydrolyzed by stirring for 72 hours while maintaining at 80 ° C.
  • the fluorine-containing compound (F-1) is a fluorine-containing polymer in which —COOCH 3 at the terminal of the fluorine-containing compound (F) is hydrolyzed and converted to —COOH.
  • the obtained aqueous solution was dried to remove the solvent to obtain a fluorine-containing compound (F-1).
  • the fluorine-containing compound (F-1) and the solvent (3) are stirred at room temperature for 3 hours to obtain a fluorine-containing compound solution having a concentration of 20% by mass of the fluorine-containing compound (coating composition).
  • the mass average molecular weight and number average molecular weight of the fluorine-containing compound (F-1) can be regarded as the same as the mass average molecular weight and number average molecular weight of the fluorine-containing compound (F). These are shown in Table 1.
  • the obtained fluorine-containing compound (F-1) was evaluated in the same manner as in Example 1.
  • Example 9 In the same manner as in Example 3, a fluorine-containing compound solution (coating composition) having a fluorine-containing compound content (concentration) of 20% by mass was obtained and evaluated.
  • the solvent for removing the top antireflection film used for the resist solubility evaluation of the coating composition was changed as shown in Table 1.
  • the refractive index is 1.36 or less.
  • Monomer (a) and monomer (e) are composed of only C, O, and F, whereas monomer (e) has a hydrogen atom bonded to a carbon atom. It differs in that it is.
  • Example 7 has a slightly higher refractive index of the film. This shows that the refractive index of the film increases when hydrogen atoms are present in the units of the fluoropolymer.
  • the monomer (c) and the monomer (f) differ in the side chain end groups.
  • the terminal group of the side chain of the monomer (c) is —CF 3
  • the terminal group of the side chain of the unit based on the monomer (f) in the fluorine-containing compound (F-1) is a carboxy group-containing group.
  • Example 3 Comparing Example 3 using the fluorinated polymer (A1-3), which is a homopolymer of the monomer (c), and Example 8 using the fluorinated compound (F-1), Example 8 was more The refractive index of the film is much higher. As this factor, it is considered that the carboxy group present in the fluorine-containing compound (F-1) has a property of absorbing light at 193 nm.
  • Monomer (a) has only one polymerizable carbon-carbon double bond, whereas monomer (d) has a polymerizable carbon-carbon double bond at both ends,
  • the fluoropolymer (D) has a unit (d-1) represented by the above formula (d-1).
  • the unit based on the monomer (a) has an etheric oxygen atom that does not form a ring, but the unit (d-1) has an etheric oxygen atom only in the ring structure.
  • Example 1 using the fluorine-containing compound (A1-1), which is a homopolymer of the monomer (a) with Example 6 using the fluorine-containing compound (D), the film of Example 6 is more refracted. The rate is slightly high. This shows that even if it has an etheric oxygen atom, if it exists in the ring structure, the refractive index reducing effect is small.
  • the unit in the polymer is composed only of C, O, and F, has an etheric oxygen atom that does not constitute a ring, and the terminal is —CF 3 . It can be seen that having side chains is important for achieving a low refractive index. It can also be seen that it is preferable in reducing the refractive index that the fluorine-containing polymer does not have a highly polar functional group such as a hydroxyl group or a carboxy group that absorbs light near 193 nm.
  • the fluorine-containing compounds (A2-1) and (A2-2) in Examples 4 and 5 are both compounds having a perfluoropolyether skeleton in the main chain.
  • Example 4 using the fluorine-containing compound (A2-1) whose main chain terminal is a hydroxyl group and Example 5 using the fluorine-containing compound (A2-2) whose main chain terminal is a perfluoroalkyl group refraction A film having a sufficiently low rate of 1.34 was obtained. From these results, it is understood that the fluorine-containing compound having a perfluoropolyether skeleton in the main chain has a low refractive index, and the influence of the main chain end group on the refractive index of the film is small.
  • Example 1 to 7 and 9 using the solvent (1) which is a fluorine-containing solvent are compared with Example 8 using a solvent (3) which is a mixture of water and IPA.
  • the film thickness increased despite the polymer concentration in the coating composition being the same. This is presumably because the boiling point of the solvent (1) is higher than either water or IPA, and the surface tension of the solvent (1) is lower than either water or IPA.
  • the solvent (1) is used as the solvent for the spin coating solution, the spin coating solution tends to spread on the silicon wafer and the spin coating solution spread on the silicon wafer is difficult to evaporate. It is considered that the time that the wafer is covered becomes longer, and as a result, the film thickness increases.
  • Example 8 using the solvent (3) which is a mixture of water and IPA was inferior in storage stability. It can be seen that the fluorine-containing compound (F-1) used in Example 8 has a carboxy group which is a hydrophilic functional group but is not sufficiently soluble in an aqueous solvent (3).
  • the coating composition of the present invention is useful as a composition for forming an antireflection film in photolithography.
  • an antireflection film having a refractive index suitable for photolithography using an ArF excimer laser (193 nm) can be formed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Paints Or Removers (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention fournit une composition pour revêtement qui permet de former un film antireflet à faible indice de réfraction sans mise en œuvre de microparticules. Cette composition pour revêtement comprend au moins une sorte de composé fluoré choisie parmi les composés fluorés (A1) et (A2) suivants. Composé fluoré (A1) : polymère constitué d'une seule sorte d'unité choisie parmi les unités (I), et de masse moléculaire moyenne en nombre de 1000 à 50000. Unités (I) : unités qui sont basées sur un monomère possédant une double liaison carbone-carbone polymérisable, qui sont configurées uniquement par un atome de carbone, un atome d'oxygène et un atome de fluor, qui possèdent au moins une chaîne latérale, au moins une chaîne latérale contenant un ou plusieurs atomes d'oxygène éthéré ne configurant pas un cycle, et qui présentent une terminaison －ＣＦ３. Composé fluoré (A2) : composé possédant un squelette perfluoropolyéther sur sa chaîne principale, et de masse moléculaire moyenne en nombre de 1000 à 50000.
PCT/JP2016/064921 2015-05-28 2016-05-19 Composition pour revêtement, et procédé de fabrication de stratifié photorésistant Ceased WO2016190221A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015108897 2015-05-28
JP2015-108897 2015-05-28
JP2015-157194 2015-08-07
JP2015157194A JP2018119019A (ja) 2015-05-28 2015-08-07 コーティング用組成物およびフォトレジスト積層体の製造方法

Publications (1)

Publication Number Publication Date
WO2016190221A1 true WO2016190221A1 (fr) 2016-12-01

Family

ID=57392750

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/064921 Ceased WO2016190221A1 (fr) 2015-05-28 2016-05-19 Composition pour revêtement, et procédé de fabrication de stratifié photorésistant

Country Status (2)

Country Link
TW (1) TW201708440A (fr)
WO (1) WO2016190221A1 (fr)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59167849A (ja) * 1983-03-11 1984-09-21 Hitachi Maxell Ltd 磁気記録媒体
JPS6262520A (ja) * 1985-09-13 1987-03-19 Hitachi Ltd パタ−ン形成方法
JPH04202278A (ja) * 1990-11-29 1992-07-23 Tosoh Corp コーティング材組成物
JPH05241332A (ja) * 1992-02-26 1993-09-21 Tokyo Ohka Kogyo Co Ltd レジスト材料
JPH0641768A (ja) * 1992-07-23 1994-02-15 Shin Etsu Chem Co Ltd 光反射防止性材料及びこれを用いたレジストパターンの形成方法
JPH0844066A (ja) * 1994-08-01 1996-02-16 Mitsubishi Chem Corp 表面反射防止塗布組成物
WO2003087176A1 (fr) * 2002-04-05 2003-10-23 3M Innovative Properties Company Dispersions contenant des homopolymeres de perfluorovinylether et utilisation de celles-ci
JP2006160988A (ja) * 2004-12-10 2006-06-22 Asahi Glass Co Ltd 含フッ素ポリマーおよびその製造方法ならびにそれを含有するレジスト保護膜組成物
JP2008129519A (ja) * 2006-11-24 2008-06-05 Asahi Glass Co Ltd レジスト保護膜用重合体およびレジストパターンの形成方法
JP2008255328A (ja) * 2007-03-14 2008-10-23 Kanto Denka Kogyo Co Ltd 含フッ素ランダム共重合体及びその製造方法
JP2011170208A (ja) * 2010-02-19 2011-09-01 Dainippon Printing Co Ltd 反射防止フィルム
JP2012173501A (ja) * 2011-02-21 2012-09-10 Asahi Glass Co Ltd 液浸露光用レジスト保護膜用組成物およびレジストパターンの形成方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59167849A (ja) * 1983-03-11 1984-09-21 Hitachi Maxell Ltd 磁気記録媒体
JPS6262520A (ja) * 1985-09-13 1987-03-19 Hitachi Ltd パタ−ン形成方法
JPH04202278A (ja) * 1990-11-29 1992-07-23 Tosoh Corp コーティング材組成物
JPH05241332A (ja) * 1992-02-26 1993-09-21 Tokyo Ohka Kogyo Co Ltd レジスト材料
JPH0641768A (ja) * 1992-07-23 1994-02-15 Shin Etsu Chem Co Ltd 光反射防止性材料及びこれを用いたレジストパターンの形成方法
JPH0844066A (ja) * 1994-08-01 1996-02-16 Mitsubishi Chem Corp 表面反射防止塗布組成物
WO2003087176A1 (fr) * 2002-04-05 2003-10-23 3M Innovative Properties Company Dispersions contenant des homopolymeres de perfluorovinylether et utilisation de celles-ci
JP2006160988A (ja) * 2004-12-10 2006-06-22 Asahi Glass Co Ltd 含フッ素ポリマーおよびその製造方法ならびにそれを含有するレジスト保護膜組成物
JP2008129519A (ja) * 2006-11-24 2008-06-05 Asahi Glass Co Ltd レジスト保護膜用重合体およびレジストパターンの形成方法
JP2008255328A (ja) * 2007-03-14 2008-10-23 Kanto Denka Kogyo Co Ltd 含フッ素ランダム共重合体及びその製造方法
JP2011170208A (ja) * 2010-02-19 2011-09-01 Dainippon Printing Co Ltd 反射防止フィルム
JP2012173501A (ja) * 2011-02-21 2012-09-10 Asahi Glass Co Ltd 液浸露光用レジスト保護膜用組成物およびレジストパターンの形成方法

Also Published As

Publication number Publication date
TW201708440A (zh) 2017-03-01

Similar Documents

Publication Publication Date Title
WO2001037043A1 (fr) Compositions polymeres transparentes aux ultraviolets et aux ultraviolets extremes et leurs utilisations
JP2952962B2 (ja) 汚染防止保護器具
TW500972B (en) Pellicle
TW201422690A (zh) 非晶質含氟樹脂組成物及薄膜製造方法
US6824930B1 (en) Ultraviolet and vacuum ultraviolet transparent polymer compositions and their uses
WO2015002008A1 (fr) Procédé de production d'un polymère contenant du fluor
US6770404B1 (en) Ultraviolet and vacuum ultraviolet transparent polymer compositions and their uses
WO2006011427A1 (fr) Composé contenant du fluor, polymère contenant du fluor, composition de réserve et composition de film protecteur de réserve
WO2002066526A1 (fr) Fluoromonomere d'ethylene contenant un groupe hydroxyle ou fluoroalkylcarbonyle et fluoropolymere obtenu par polymerisation de ce monomere
CN102516459B (zh) 含氟化合物、含氟聚合物和含氟树脂组合物
KR20080108459A (ko) 이머젼 리소그래피용 레지스트 보호막 재료
KR20090122201A (ko) 반사 방지 코팅용 조성물
JPH04226177A (ja) コーティング用含フッ素重合体組成物およびその用途
JP2018119019A (ja) コーティング用組成物およびフォトレジスト積層体の製造方法
JP2016089050A (ja) コーティング用組成物およびフォトレジスト積層体の製造方法
WO2016190221A1 (fr) Composition pour revêtement, et procédé de fabrication de stratifié photorésistant
WO2015080061A1 (fr) Composition de revêtement, et procédé de production de stratifié photorésistant
JP2019085451A (ja) 含フッ素ポリマー及び硬化性組成物
JP5124966B2 (ja) レジストパターン形成法
JP2007086731A (ja) レジスト保護膜用組成物
JP6881452B2 (ja) コーティング用組成物の製造方法およびフォトレジスト積層体の製造方法
JP2019085450A (ja) 含フッ素ポリマー及び硬化性組成物
JP2999503B2 (ja) コーティング用樹脂組成物
JPWO2005095471A1 (ja) 新規な含フッ素重合体、およびその製造方法
JP2929653B2 (ja) 光反応器

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: 16799927

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: 16799927

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP