WO2021186994A1 - 組成物、組成物前駆体の溶液、組成物の製造方法、基板、及びパターン付き基板の製造方法 - Google Patents

組成物、組成物前駆体の溶液、組成物の製造方法、基板、及びパターン付き基板の製造方法 Download PDF

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WO2021186994A1
WO2021186994A1 PCT/JP2021/005907 JP2021005907W WO2021186994A1 WO 2021186994 A1 WO2021186994 A1 WO 2021186994A1 JP 2021005907 W JP2021005907 W JP 2021005907W WO 2021186994 A1 WO2021186994 A1 WO 2021186994A1
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French (fr)
Japanese (ja)
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祐梨 及川
増渕　毅
山中　一広
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Central Glass Co Ltd
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Central Glass Co Ltd
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Priority to KR1020227034930A priority Critical patent/KR20220155319A/ko
Priority to JP2022508149A priority patent/JPWO2021186994A1/ja
Priority to CN202180019261.6A priority patent/CN115244466A/zh
Publication of WO2021186994A1 publication Critical patent/WO2021186994A1/ja
Priority to US17/944,817 priority patent/US20230039535A1/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/094—Multilayer resist systems, e.g. planarising layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • 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
    • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
    • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
    • H10P76/2041—Photolithographic processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature

Definitions

  • the present disclosure relates to a composition used to form an underlayer film of a photoresist.
  • LSI Large Scale Integration
  • a pattern-forming substrate is formed by dry-etching the substrate with chlorine-based gas or fluorine-based gas via a resist pattern formed by exposure development on the substrate according to lithography and transferring the pattern. Is manufactured.
  • a resin having a chemical structure having etching resistance against these gases is used as the resist.
  • Such resists include a positive type resist in which the exposed part is solubilized by irradiation with high energy rays and a negative type resist in which the exposed part is insolubilized, and either of them is used.
  • the high-energy rays include g-line (wavelength 463 nm) and i-line (wavelength 365 nm) emitted by a high-pressure mercury lamp, ultraviolet rays having a wavelength of 248 nm oscillated by a KrF excimer laser, or ultraviolet rays having a wavelength of 193 nm oscillated by an ArF excimer laser, or extreme ultraviolet rays.
  • Light hereinafter sometimes referred to as UV
  • UV extreme ultraviolet rays
  • a multilayer resist method is known in order to disintegrate the pattern at the time of forming the resist pattern and to improve the etching resistance of the resist.
  • Patent Document 1 has a silicon-containing layer having an antireflection function at the time of exposure in the multilayer resist method, and has a high etching rate with respect to a plasma of a fluorine-based gas and a slow etching rate with respect to a plasma of an oxygen-based gas during dry etching.
  • a silicon-containing layer-forming composition for forming the above a silicon-containing layer-forming composition containing a polysiloxane compound (A) containing a structural unit represented by the formula (A) and a solvent (B) is disclosed. There is. [(R a ) ⁇ R b w SiO x / 2 ] (A) [In the formula, Ra is a group represented by the following formula.
  • R b is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms.
  • ⁇ is an integer of 1 to 3
  • w is an integer of 0 to 2
  • x is an integer of 1 to 3
  • ⁇ + w + x 4.
  • the polysiloxane compound (A) may contain a structural unit represented by the formula (B).
  • R d is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, an alkoxy group having 1 to 3 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms, independently of each other.
  • Y is an integer of 0 to 3
  • z is an integer of 1 to 4
  • y + z 4.
  • Example 4 of Patent Document 1 3- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) -triethoxysilylbenzene, which is a raw material of the above formula (A), is used.
  • Silicate 40 which is a silicate oligomer, is reacted at a molar ratio of 1: 1 in the presence of water and acetic acid. After that, it is disclosed that the desired polysiloxane compound was obtained by distilling off water, acetic acid, and ethanol as a by-product.
  • Patent Document 2 describes a silicon-containing film-forming composition for a resist process capable of forming a silicon-containing film having excellent solvent resistance and oxygen-based gas etching resistance, which comprises a polysiloxane having a predetermined first structural unit and a solvent.
  • a silicon-containing film-forming composition for a resist process contained therein is disclosed.
  • a component forming a Q unit such as tetramethoxysilane or tetraethoxysilane as the raw material of the polysiloxane from the viewpoint of improving the dry etching resistance of the silicon-containing film formed from the film-forming composition.
  • the Q unit means a Si structural unit in which the four bonds of the Si atom are any one of a siloxane bond, a silanol group, and a hydrolyzable group.
  • the polysiloxane compound (A) In the production process (specifically, the solgel polymerization reaction step), a solid may be precipitated to obtain a uniform composition, or the precipitated solid may be removed to obtain a polysiloxane compound (A).
  • the present inventors have found that the Q unit cannot be introduced at a high concentration, and as a result, the Q / (Q + T) ratio may fall below 0.60.
  • the T unit three of the four bonds of the Si atom are any of a siloxane bond, a silanol group, and a hydrolyzable group, and the remaining one bond is Si bonded to the other group. It means a structural unit.
  • the content of Q units is high (specifically, the siloxane structural unit ratio represented by Q units / (Q units + T units) in all Si structural units is 0.60 or more and 1.00.
  • One of the challenges is to provide a composition (less than).
  • composition according to one embodiment of the present invention contains a structural unit represented by the formula (1) and a structural unit represented by the formula (2), and Q unit / (Q unit + T) in all Si structural units. unit) It contains a polysiloxane compound (A) and a solvent (B) having a siloxane structural unit ratio represented by (1) of 0.60 or more and less than 1.00.
  • R 1 is a group represented by the following formula, (A is a number from 1 to 5, and wavy lines indicate that the intersecting line segments are bonds.)
  • R 2 is independently a hydrogen atom, an alkyl group having 1 or more and 3 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 3 or less carbon atoms.
  • R 3 is independently a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms.
  • b is a number of 1 to 3
  • m is a number of 0 to 2
  • l is a number of 0 or more and less than 3
  • n is a number of more than 0 and 3 or less
  • b + m + l + n 4.
  • R 4 is an alkoxy group, a hydroxy group, or a halogen group having 1 or more and 3 or less carbon atoms independently of each other
  • p is a number of 0 or more and less than 4
  • q is a number of more than 0 and 4 or less.
  • A is 1 or 2.
  • R 1 is one of the following. (Wavy lines indicate that the intersecting line segments are bonds.)
  • N 0.5 to 3.
  • the pH at 25 ° C is 1 or more and less than 6.
  • the viscosity at 25 ° C. is 0.5 mPa ⁇ s or more and 30 mPa ⁇ s or less.
  • the solvent (B) contains at least one selected from the group consisting of ester-based, ether-based, alcohol-based, ketone-based, and amide-based solvents.
  • the above composition forms an underlayer film of a photoresist.
  • the etching rate ratio A of the film to be etched formed by the composition is 50 or more, which is obtained by dividing the etching rate under the following condition (1) by the etching rate under the following condition (2). It becomes.
  • CF 4 and CHF 3 are used as fluorine-based gas CF 4
  • CO 2 is used as an oxygen-based gas CO 2 flow rate: 300 sccm Ar flow rate: 100 sccm N 2 flow rate: 100 sccm Chamber pressure: 2Pa Applied power: 400W Temperature: 15 ° C
  • the etching rate ratio B of the film to be etched formed by the composition is 20 or more, which is obtained by dividing the etching rate under the following condition (1) by the etching rate under the following condition (3). It becomes.
  • CF 4 and CHF 3 are used as fluorine-based gas CF 4 Flow rate: 150 sccm CHF 3 flow rate: 50 sccm Ar flow rate: 100 sccm Chamber pressure: 10 Pa Applied power: 400W Temperature: 15 ° C
  • the solution of the composition precursor according to one embodiment of the present invention is copolymerized with at least one selected from the group consisting of chlorosilane, alkoxysilane, and silicate oligomer, which gives a structural unit represented by the following formula (2).
  • the composition precursor contains a structural unit represented by the following formula (3) and also contains.
  • the pH of the solution of the composition precursor at 25 ° C. is 1 or more and 7 or less.
  • R 2 is independently a hydrogen atom, an alkyl group having 1 or more and 3 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 3 or less carbon atoms.
  • R 3 is independently a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms.
  • b is a number of 1 to 3
  • m is a number of 0 to 2
  • s is a number of 0 or more and less than 3
  • t is a number of more than 0 and 3 or less
  • b + m + s + t 4.
  • the weight average molecular weight of the above composition precursor is 300 to 3000.
  • A is 1 or 2.
  • R 1 is one of the following. (Wavy lines indicate that the intersecting line segments are bonds.)
  • the method for producing a composition according to an embodiment of the present invention is a group consisting of a solution of the above composition precursor and a group consisting of chlorosilane, alkoxysilane, and a silicate oligomer giving a structural unit represented by the following formula (2). At least one selected from the above is mixed and copolymerized.
  • R 4 is an alkoxy group, a hydroxy group, or a halogen group having 1 or more and 3 or less carbon atoms independently of each other, p is a number of 0 or more and less than 4, and q is a number of more than 0 and 4 or less.
  • p + q 4.
  • the substrate with a multilayer film according to an embodiment of the present invention has an organic layer on the substrate, a lower layer film of a photoresist which is a cured product of the above composition on the organic layer, and a resist layer on the lower layer film.
  • the resist layer is exposed to a high-energy ray through a photomask on the above-mentioned substrate with a multilayer film, and then the resist layer is developed with a base aqueous solution to form a pattern.
  • the first step to obtain The second step of performing dry etching of the lower layer film through the pattern of the resist layer to obtain a pattern on the lower layer film, and The third step of dry etching the organic layer through the pattern of the underlayer film to obtain a pattern on the organic layer, and The fourth step of dry etching the substrate through the pattern of the organic layer to obtain the pattern on the substrate is included.
  • the underlayer film is dry-etched with a fluorine-based gas.
  • the organic layer is dry-etched with an oxygen-based gas.
  • the substrate is dry-etched with a fluorine-based gas or a chlorine-based gas.
  • High energy rays are ultraviolet rays with a wavelength of 1 nm or more and 400 nm or less.
  • the etching rate ratio A of the lower layer film is 50 or more, which is obtained by dividing the etching rate under the following condition (1) by the etching rate under the following condition (2).
  • CF 4 and CHF 3 are used as fluorine-based gas CF 4
  • CO 2 is used as an oxygen-based gas CO 2 flow rate: 300 sccm Ar flow rate: 100 sccm N 2 flow rate: 100 sccm Chamber pressure: 2Pa Applied power: 400W Temperature: 15 ° C
  • the etching rate ratio B of the lower layer film is 20 or more, which is obtained by dividing the etching rate under the following condition (1) by the etching rate under the following condition (3).
  • CF 4 and CHF 3 are used as fluorine-based gas CF 4
  • the content of Q units is high (specifically, the siloxane structural unit ratio represented by Q units / (Q units + T units) in all Si structural units is 0.60.
  • the above) composition can be provided.
  • composition according to the embodiment of the present invention the method for producing the composition, the solution of the composition precursor, and the method for producing the patterned substrate using the composition will be described in detail.
  • composition contains a structural unit represented by the formula (1) and a structural unit represented by the formula (2), and Q unit / (Q unit + T) in all Si structural units. unit) It is a composition containing a polysiloxane compound (A) and a solvent (B) having a siloxane structural unit ratio represented by (1) of 0.60 or more and less than 1.00.
  • R 1 is a group represented by the following formula.
  • (A is a number from 1 to 5.
  • R 2 is an independent hydrogen atom, an alkyl group having 1 or more and 3 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 3 or less carbon atoms
  • R 3 is an independent hydrogen atom or carbon number. It is an alkyl group of 1 or more and 3 or less.
  • b is a number of 1 to 3
  • m is a number of 0 to 2
  • l is a number of 0 or more and less than 3
  • n is a number of more than 0 and 3 or less
  • b + m + l + n 4.
  • the Q unit is classified into the following five types according to the substituent of the Si atom and the bonding state.
  • Q 0 Unit four bonds, all hydrolysis and polycondensation groups of Si atoms is (halogen group, an alkoxy group, or hydroxy group, can form a siloxane bond group) structure.
  • Q 1 Unit four binding hands of the Si atoms, one of forming a siloxane bond, the remaining all three are the hydrolysis and polycondensation groups structure.
  • Q 2 Unit four binding hands of the Si atoms, two of forming a siloxane bond, the remaining 2 Tsugasubete the hydrolysis and polycondensation groups structure.
  • Q 3 unit four bonds hands of the Si atoms, three to form a siloxane bond, but the remaining one is the above hydrolysis and polycondensation groups structure.
  • Q 4 units all four bonds of Si atoms to form a siloxane bond structure.
  • T unit is classified into the following four types according to the substituent of the Si atom and the bonding state.
  • T 0 unit Of the four bonds of the Si atom, three are groups capable of hydrolyzing and polycondensing (groups capable of forming a siloxane bond, such as a halogen group, an alkoxy group, or a hydroxy group), and the remaining one. A structure in which one is another substituent (a group that cannot form a siloxane bond).
  • T 1 unit A structure in which one of the four bonds of the Si atom forms a siloxane bond, two are the hydrolyzable / polycondensable groups, and one is the other substituent.
  • T 2 unit A structure in which two of the four bonds of the Si atom form a siloxane bond, one is the hydrolyzable / polycondensable group, and one is the other substituent.
  • T 3 unit A structure in which three of the four bonds of the Si atom form a siloxane bond and one is the above-mentioned other substituent.
  • composition according to one embodiment of the present invention is preferably in a solution state in which the polysiloxane compound (A) is dissolved in the solvent (B).
  • the filler may be dispersed in the solution.
  • b, m, l, and n are theoretical values of b being an integer of 1 to 3, m being an integer of 0 to 2, and l being 0 to.
  • An integer of 3 and n are integers of 0 to 3.
  • b + m + l + n 4 means that the total of the theoretical values is 4.
  • b is a decimal number that is rounded to 1 to 3
  • m is rounded to 0 to 2.
  • a decimal number, l may be a decimal number rounded to 0 or more and less than 3, and n may be a decimal number rounded to 0 or more and 3 or less.
  • b is 1 to 3, preferably b is 1 to 2, and more preferably b is 1.
  • n is more than 0 and 3 or less.
  • a is an integer of 1 to 5 as a theoretical value. However, in the value obtained by 29 Si NMR measurement, a may be a decimal number of 1 to 5. Further, in R 1 , a is preferably 1 or 2, and particularly preferably 1.
  • R 1 is preferably any of the following groups. (Wavy lines indicate that the intersecting line segments are bonds.) In particular, the following groups are preferable. (Wavy lines indicate that the intersecting line segments are bonds.)
  • b is preferably 1.
  • n is preferably 0.5 to 3, more preferably n is 0.7 to 3, and particularly preferably n is 0.9 to 3.
  • q is more than 0 and 4 or less.
  • the composition according to the embodiment of the present invention preferably has a pH of 1 or more and less than 6 at 25 ° C., more preferably 2 or more and 5 or less, and particularly preferably 2 or more and 5 or less.
  • the composition according to one embodiment of the present invention preferably has a viscosity at 25 ° C. of 0.5 mPa ⁇ s or more and 30 mPa ⁇ s or less.
  • a viscosity at 25 ° C. 0.5 mPa ⁇ s or more and 30 mPa ⁇ s or less.
  • the number of insoluble matter having a particle size of 0.2 ⁇ m or more in the particle measurement by the light scattering type submerged particle detector in the liquid phase in the composition is 100 or less per 1 mL of the composition. This is because when the number of insoluble matter having a particle size of 0.2 ⁇ m or more is 100 or less per 1 mL of the composition, the smoothness of the coating film is unlikely to be impaired and unevenness / defects in etching are unlikely to occur. It is preferable that the number of particles larger than 0.2 ⁇ m is smaller, but there may be one or more particles per 1 mL of the composition as long as it is within the above content range.
  • the particle measurement in the liquid phase in the composition in the present invention is performed by using a commercially available measuring device in the light scattering type liquid particle measurement method using a laser as a light source.
  • the particle size of the particles means a light scattering equivalent diameter based on PSL (polystyrene latex) standard particles.
  • the above-mentioned particles are particles such as dust, dust, organic solids, and inorganic solids contained as impurities in the raw material, and dust, dust, organic solids, and inorganic substances brought in as contaminants during the preparation of the composition. These include particles such as solids and particles that precipitate during or after the preparation of the composition. As described above, the above-mentioned particles correspond to those that finally exist as particles in the composition without being dissolved.
  • composition of the present invention containing the polysiloxane compound (A) and the solvent (B) provides a solution of the composition precursor and a structural unit represented by the formula (2), such as chlorosilane and alkoxysilane. , And at least one selected from the group consisting of silicate oligomers are mixed and copolymerized.
  • composition precursor solution of
  • the solution of the composition precursor is represented by the following HFIP group-containing aromatic halosilanes represented by the formula (4) (hereinafter, may be referred to as HFIP group-containing aromatic halosilane (4)), or the formula (5).
  • HFIP group-containing aromatic alkoxysilanes represented by () hereinafter, may be referred to as HFIP group-containing aromatic alkoxysilane (5) or a mixture thereof, if necessary, in a reaction solvent. Obtained by condensation.
  • R 5 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms.
  • a group, X is a halogen atom
  • R 6 is a hydrogen atom, or a linear or branched alkyl group having 3 or 4 carbon atoms having 1 to 4 carbon atoms, and all of the hydrogen atoms in the alkyl group. Alternatively, a part may be replaced with a fluorine atom.
  • A is an integer of 1 to 5
  • b is an integer of 1 to 3
  • m is an integer of 0 to 2
  • s is an integer of 1 to 3
  • R 5 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms.
  • the aromatic halosilane (6) used as a raw material has a structure in which a phenyl group and a halogen atom are directly bonded to a silicon atom.
  • the aromatic halosilane (6) may have a group, R 5, which is directly bonded to a silicon atom, and R 5 includes a hydrogen atom, an alkyl group having 1 or more and 3 or less carbon atoms, a phenyl group, a hydroxy group, and carbon.
  • R 5 includes a hydrogen atom, an alkyl group having 1 or more and 3 or less carbon atoms, a phenyl group, a hydroxy group, and carbon.
  • An alkoxy group having a number of 1 or more and 3 or less, or a fluoroalkyl group having 1 or more and 3 or less carbon atoms can be mentioned.
  • Such groups include methyl group, ethyl group, propyl group, butyl group, isobutyl group, t-butyl group, neopentyl group, octyl group, cyclohexyl group, trifluoromethyl group, 1,1,1-trifluoropropyl group.
  • Perfluorohexyl group or perfluorooctyl group can be exemplified. Among them, from the ready availability, a methyl group is preferable as the substituent R 5.
  • halogen atom X in the aromatic halosilane (6) examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • X is preferably a chlorine atom from the viewpoint of availability and stability of the compound. ..
  • the aromatic halosilane (6) the following halosilanes can be preferably exemplified.
  • the Lewis acid catalyst used in this reaction is not particularly limited, and is, for example, aluminum chloride, iron (III) chloride, zinc chloride, tin (II) chloride, titanium tetrachloride, aluminum bromide, boron trifluoride, boron trifluoride. Examples include diethyl ether complex, antimony fluoride, zeolites or composite oxides. Among them, aluminum chloride, iron (III) chloride, and boron trifluoride are preferable, and aluminum chloride is particularly preferable because the reactivity in this reaction is high.
  • the amount of the Lewis acid catalyst used is not particularly limited, but is 0.01 mol or more and 1.0 mol or less with respect to 1 mol of the aromatic halosilane represented by the formula (6).
  • Organic solvent In this reaction, when the raw material aromatic halosilane (6) is a liquid, the reaction can be carried out without using an organic solvent. However, if the aromatic halosilane (6) is solid or highly reactive, an organic solvent may be used.
  • the organic solvent is not particularly limited as long as it is a solvent in which aromatic halosilane (6) is dissolved and does not react with the Lewis acid catalyst and hexafluoroacetone, and pentane, hexane, heptane, octane, acetonitrile, nitromethane, chlorobenzene or nitrobenzene is used. It can be exemplified. These solvents may be used alone or in combination.
  • hexafluoroacetone examples include hydrates such as hexafluoroacetone and hexafluoroacetone trihydrate. When these hydrates are used, it is preferable to use hexafluoroacetone as a gas because the yield decreases when water is mixed during the reaction.
  • the amount of hexafluoroacetone used depends on the number of HFIP groups introduced into the aromatic ring, but is 1 molar equivalent or more and 6 molar equivalents with respect to 1 mol of the phenyl group contained in the aromatic halosilane (6) of the raw material. The following is preferable.
  • the amount of hexafluoroacetone used should be 2.5 mol equivalent or less with respect to 1 mol of phenyl group contained in the aromatic halosilane (6) of the raw material, and the number of HFIP groups introduced into the phenyl group should be 2 or less. It is more preferable to suppress it to.
  • reaction conditions When synthesizing the HFIP group-containing aromatic halosilane (4), hexafluoroacetone has a boiling point of ⁇ 28 ° C., so a cooling device or a sealed reactor should be used to keep hexafluoroacetone in the reaction system. Is preferable, and it is particularly preferable to use a sealed reactor.
  • a sealed reactor autoclave
  • the aromatic halosilane (6) and Lewis acid catalyst are first placed in the sealed reactor, and then the pressure in the sealed reactor exceeds 0.5 MPa. It is preferable to introduce a gas of hexafluoroacetone so as not to be present.
  • the optimum reaction temperature in this reaction varies greatly depending on the type of aromatic halosilane (6) used as the raw material, but it is preferably carried out in the range of ⁇ 20 ° C. or higher and 80 ° C. or lower. Further, it is preferable that the raw material having a higher electron density on the aromatic ring and a higher electrophilicity performs the reaction at a lower temperature. By carrying out the reaction at a low temperature as much as possible, the cleavage of the Ph—Si bond during the reaction can be suppressed, and the yield of the HFIP group-containing aromatic halosilane (4) is improved.
  • the reaction time is not particularly limited, but is appropriately selected depending on the amount of HFIP group introduced, the temperature, the amount of catalyst used, and the like. Specifically, from the viewpoint of sufficiently advancing the reaction, it is preferable that the time is 1 hour or more and 24 hours or less after the introduction of hexafluoroacetone.
  • the Lewis acid catalyst can be removed by means such as filtration, extraction, and distillation to obtain the HFIP group-containing aromatic halosilane (4).
  • filter filtration refers to an operation of passing a mixture of a solid mixed with a liquid through a porous medium (filter medium) having many fine holes to separate solid particles larger than the holes from the liquid. ..
  • HFIP group-containing aromatic halosilane (4) which is a raw material for the composition precursor.
  • the HFIP group-containing aromatic halosilane (4) has a structure in which an HFIP group and a silicon atom are directly bonded to an aromatic ring.
  • the HFIP group-containing aromatic halosilane (4) is obtained as a mixture having a plurality of isomers having different numbers of substitutions and substitution positions of HFIP groups.
  • the types of isomers with different HFIP group substitution numbers and substitution positions and their abundance ratios differ depending on the structure of the raw material aromatic halosilane (6) and the equivalent of the reacted hexafluoroacetone. It has the partial structure. (Wavy lines indicate that the intersecting line segments are bonds.)
  • the HFIP group-containing aromatic halosilane (4) various isomers separated by performing precision distillation or the like on the isomer mixture, or the isomer mixture as it is can be used without separation.
  • R 6 is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and all or a part of hydrogen atoms in the alkyl group may be substituted with fluorine atoms. ..
  • trifluoropropanol, 2,2,3,3-tetrafluoropropanol, 2,2,3,3,3-pentafluoropropanol or 1,1,1,3,3,3-hexafluoroisopropanol. can.
  • Particularly preferred is methanol or ethanol.
  • an alcohol containing a small amount of water it is preferably 5% by mass or less, and more preferably 1% by mass or less.
  • reaction method for synthesizing the HFIP group-containing aromatic alkoxysilane (5) is not particularly limited. As a typical example, there is a method of dropping an alcohol on the HFIP group-containing aromatic halosilane (4) and reacting it, or a method of dropping an HFIP group-containing aromatic halosilane (4) on the alcohol and reacting it.
  • the amount of alcohol used is not particularly limited, but is preferably 1 molar equivalent or more and 10 molar equivalent or less with respect to the Si—X bond contained in the HFIP group-containing aromatic halosilane (4) in that the reaction proceeds efficiently. More preferably, it is 1 molar equivalent or more and 3 molar equivalent or less.
  • the addition time of alcohol or HFIP group-containing aromatic halosilane (4) is not particularly limited, but is preferably 10 minutes or more and 24 hours or less, and more preferably 30 minutes or more and 6 hours or less.
  • the optimum temperature for the reaction during dropping varies depending on the reaction conditions, but specifically, it is preferably 0 ° C. or higher and 70 ° C. or lower.
  • the reaction can be completed by aging while continuing stirring after the completion of dropping.
  • the aging time is not particularly limited, and is preferably 30 minutes or more and 6 hours or less from the viewpoint of sufficiently advancing the desired reaction.
  • the reaction temperature at the time of aging is the same as that at the time of dropping or higher than that at the time of dropping. Specifically, it is preferably 10 ° C. or higher and 80 ° C. or lower.
  • the reactivity of alcohol and HFIP group-containing aromatic halosilane (4) is high, and the halogenosilyl group is rapidly converted to an alkoxysilyl group, but hydrogen halide generated during the reaction is used to promote the reaction and suppress side reactions. It is preferable to remove the above.
  • Methods for removing hydrogen halide include addition of known hydrogen halide trapping agents such as amine compounds, orthoesters, sodium alkoxides, epoxy compounds, and olefins, as well as hydrogen halide gas generated by heating or bubbling dry nitrogen. There is a method to remove the substance from the system. These methods may be performed alone or in combination of two or more.
  • Examples of the hydrogen halide scavenger include ortho ester and sodium alkoxide.
  • Examples of the orthoester include trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthopropionate, and trimethyl orthobenzoate. Trimethyl orthoformate or triethyl orthoformate is preferred because it is easily available.
  • Examples of the sodium alkoxide include sodium methoxide and sodium ethoxide.
  • the reaction between alcohol and HFIP group-containing aromatic halosilane (4) may be diluted with a solvent.
  • the solvent used is not particularly limited as long as it does not react with the alcohol used and the HFIP group-containing aromatic halosilane (4).
  • Examples of the solvent used include pentane, hexane, heptane, octane, toluene, xylene, tetrahydrofuran, diethyl ether, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,4-dioxane and the like. These solvents may be used alone or in combination.
  • HFIP group-containing aromatic halosilane (4) which is a raw material
  • a general-purpose analytical means such as gas chromatography
  • purification is carried out by means such as filtration, extraction and distillation to obtain HFIP group-containing aromatic alkoxysilane (5).
  • the HFIP group-containing aromatic alkoxysilane represented by the formula (5-1) in which b is 1 is prepared from benzene in which the HFIP group and the Y group are substituted according to the production method described in JP-A-2014-156461. It can also be produced by a coupling reaction using alkoxyhydrosilane as a raw material and using a transition metal catalyst such as rhodium, ruthenium, or iridium.
  • R 1A is independently a hydrogen atom, an alkyl group having 1 or more and 3 or less carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 or more and 3 or less carbon atoms, or a fluoroalkyl group having 1 or more carbon atoms and 3 or less carbon atoms.
  • R 2A is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and all or a part of the hydrogen atoms in the alkyl group is a fluorine atom.
  • Y is a chlorine atom, a bromine atom, an iodine atom, an -OSO 2 (p-C 6 H 4 CH 3 ) group, or -OSO 2 CF 3 groups, and aa is an integer of 1 to 5.
  • Mm is an integer of 0 to 2
  • rr is an integer of 1 to 3
  • mm + rr 3)
  • polysiloxane compound (A) contained in the composition according to one embodiment of the present invention is generally used in the semiconductor industry, 3- (2-hydroxy-1,1,1,3,3,3) It preferably contains a structural unit obtained by hydrolyzing and polycondensing -hexafluoroisopropyl) -triethoxysilylbenzene (hereinafter, may be referred to as "HHFIPTESB").
  • FIG. 1 is a flow chart showing a method for producing a composition according to an embodiment of the present invention. As shown in (STEP 1) of FIG. 1, the HFIP group-containing aromatic halosilane (4), the HFIP group-containing aromatic alkoxysilane (5), or a mixture thereof synthesized by the above method is hydrolyzed. By condensation, (a solution of) the composition precursor is obtained.
  • This hydrolysis polycondensation reaction can be carried out by a general method in the hydrolysis and condensation reaction of hydrolyzable silane. Specifically, HFIP group-containing aromatic halosilane (4), HFIP group-containing aromatic alkoxysilane (5), or a mixture thereof is collected in a reaction vessel. Then, water for hydrolysis, if necessary, a catalyst for advancing the polycondensation reaction, and a reaction solvent are added to the reactor and stirred, and if necessary, heating is performed to carry out the hydrolysis and polycondensation reaction. To obtain (a solution of) the composition precursor.
  • composition precursor solution A solution obtained by mixing the composition precursor with the above water by hydrolysis without adding a special reaction solvent and obtaining a uniform solution state is referred to as a “composition precursor solution”.
  • the silanol group of the composition precursor derived from the above-mentioned HFIP group-containing aromatic halosilane (4) and HFIP group-containing aromatic alkoxysilane (5) by hydrolysis is different from that of the above water. It is possible to contribute to mixing. Further, it is considered that the by-produced solvent component (for example, when alkoxysilane is used, the corresponding alcohol is produced as a by-product) contributes to the miscibility of the composition precursor and the above-mentioned water. Further, the same solvent as the reaction solvent described later may be further added to the composition precursor (solution) obtained by performing the above hydrolysis polycondensation.
  • the catalyst for advancing the polycondensation reaction is not particularly limited, and examples thereof include an acid catalyst and a base catalyst.
  • Acid catalysts include hydrochloric acid, nitrate, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, tosylic acid, formic acid, maleic acid, malonic acid.
  • polyvalent carboxylic acids such as succinic acid, or anhydrides of these acids can be exemplified.
  • triethylamine, tripropylamine, tributylamine, trypentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, or sodium carbonate can be used. It can be exemplified.
  • reaction solvent In the hydrolysis and condensation reaction, it is not always necessary to use a reaction solvent, and the raw material compound, water and a catalyst can be mixed and hydrolyzed and polycondensed.
  • the type is not particularly limited. Among them, a polar solvent is preferable, and an alcohol solvent is more preferable, because of its solubility in a raw material compound, water, and a catalyst.
  • the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol.
  • a step of adjusting the pH of the composition precursor solution by extraction, washing with water or the like may be carried out, or the concentration of the composition precursor solution by solvent distillation, concentration, dilution or the like may be carried out. You may carry out the step of adjusting.
  • composition precursor obtained by synthesizing (the solution of) the composition precursor contains a structural unit represented by the following formula (3) and is a solution of the composition precursor.
  • the pH at 25 ° C. is 1 or more and 7 or less.
  • R 1 is a group represented by the following formula.
  • (A is a number from 1 to 5.
  • R 2 is an independent hydrogen atom, an alkyl group having 1 or more and 3 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 3 or less carbon atoms
  • R 3 is an independent hydrogen atom or carbon number. It is an alkyl group of 1 or more and 3 or less.
  • b is a number of 1 to 3
  • m is a number of 0 to 2
  • s is a number of 0 or more and less than 3
  • t is a number of more than 0 and 3 or less
  • b + m + s + t 4.
  • a is an integer of 1 to 5 as a theoretical value. However, in the value obtained by the 29 Si NMR measurement, a may be a decimal number of 1 to 5. Further, in the formula (3), it is preferable that a is 1 or 2.
  • b, m, s, and t are theoretical values of b being an integer of 1 to 3, m being an integer of 0 to 2, and s being 0 to.
  • An integer of 3 and t are integers of 0 to 3.
  • b + m + s + t 4 means that the total of the theoretical values is 4.
  • b is a decimal number that is rounded to 1 to 3
  • m is rounded to 0 to 2.
  • a decimal number, s may be a decimal number rounded to 0 or more and less than 3
  • t may be a decimal number rounded to 0 or more and 3 or less.
  • R 1 is preferably any of the following groups. (Wavy lines indicate that the intersecting line segments are bonds.)
  • the weight average molecular weight of the composition precursor is preferably 300 to 3000, more preferably 300 to 2000, and particularly preferably 300 to 1000. When the weight average molecular weight is 3000 or less, insoluble matter is unlikely to be generated in the subsequent step, which is preferable.
  • the composition according to one embodiment of the present invention contains a solution of the composition precursor described in 1-5 and a structural unit represented by the following formula (2). It is obtained by synthesizing the polysiloxane compound (A) by mixing and copolymerizing with at least one selected from the group consisting of chlorosilane, alkoxysilane, and silicate oligomer.
  • the solvent (B) may be a solvent contained in the solution of the composition precursor, or may be contained in the composition by mixing the solvent (B) if necessary.
  • the polysiloxane compound (A) is dissolved in the solvent (B) and dispersed substantially uniformly.
  • chlorosilane that gives the structural unit represented by the formula (2)
  • Examples of chlorosilane include dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, diphenyldichlorosilane, bis (3,3,3-trifluoropropyl) dichlorosilane, and methyl (3,3,3-trifluoropropyl) dichlorosilane.
  • alkoxysilane examples include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diphenyldimethoxysilane, bis (3,3,3-trifluoropropyl) dimethoxysilane, and methyl (3,3,3-trifluoropropyl) dimethoxy.
  • trimethoxysilane, tetramethoxysilane, or all or part of the methoxy groups of those methoxysilanes are at least one selected from the group consisting of ethoxy group, propoxy group, isopropoxy group, phenoxy group. be able to.
  • the silicate oligomer is an oligomer obtained by hydropolycondensing tetraalkoxysilane.
  • Commercially available products include silicate 40 (average pentamer, manufactured by Tama Chemical Industry Co., Ltd.) and ethyl silicate 40 (average 5 amount).
  • Silicate 45 (average tetramer, manufactured by Tama Chemical Industry Co., Ltd.), M silicate 51 (average tetramer, manufactured by Tama Chemical Industry Co., Ltd.), Methyl silicate 51 (average tetramer, manufactured by Tama Chemical Industry Co., Ltd.) Corcote Co., Ltd.), Methyl silicate 53A (average tetramer, manufactured by Corcote Co., Ltd.), Ethyl silicate 48 (average tetramer, Corcote Co., Ltd.), EMS-485 (mixture of ethyl silicate and methyl silicate, Corcote stock) (Made by company) etc. can be exemplified.
  • Solvent (B) In the composition according to one embodiment of the present invention, a solvent (B) is used in addition to the polysiloxane compound (A).
  • the solvent (B) may not be one that dissolves or disperses and precipitates the polysiloxane compound (A), and examples thereof include ester-based, ether-based, alcohol-based, ketone-based, and amide-based solvents.
  • ester solvent examples include acetic acid esters, basic esters and cyclic esters.
  • acetic acid esters include propylene glycol monomethyl ether acetate (hereinafter, may be referred to as PGMEA), ethyl lactate as basic esters, and ⁇ -butyrolactone as cyclic esters.
  • ether-based solvent examples include butanediol monomethyl ether, propylene glycol monomethyl ether (hereinafter, may be referred to as PGME), ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, and butane.
  • PGME propylene glycol monomethyl ether
  • ethylene glycol monomethyl ether butanediol monoethyl ether
  • propylene glycol monoethyl ether examples include diol monopropyl ether and propylene glycol monopropyl ether.
  • glycols can be mentioned as the alcohol solvent.
  • glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, and 1-propanol-2-propanol.
  • ketone solvent examples include cyclohexanone, which is a cyclic ketone.
  • At least one selected from the group consisting of PGMEA, PGME, and cyclohexanone may be used because it is generally used in the semiconductor industry. preferable.
  • the amount of the solvent (B) contained in the composition according to the embodiment of the present invention is 200 parts by mass or more and 100,000 parts by mass or less, preferably 400 parts by mass, based on 100 parts by mass of the polysiloxane compound (A). More than parts and less than 50,000 parts by mass. If it is 200 parts by mass or more, the polysiloxane compound (A) is difficult to precipitate, and if it is 100,000 parts by mass or less, it is easy to form a film without being too thin.
  • the surfactant improves the defoaming and leveling effects during film formation
  • the silane coupling agent is used with the upper resist layer and the lower organic layer. Adhesion is improved.
  • Organic acids improve the storage stability of the composition, and the addition of water improves lithographic performance.
  • the surfactant is preferably nonionic, and examples thereof include perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, and fluorine-containing organosiloxane compound.
  • a structural unit represented by the following formula (7) can be exemplified. Although specific examples of the monomers are given later, it is natural that a part of the monomers may be in an oligomer state in which a part of the monomers is hydrolyzed and polycondensed. [(R y ) c R 7 e SiO f / 2 ] (7) [In the formula, Ry is a monovalent organic group having 2 to 30 carbon atoms, which contains any one of an epoxy group, an oxetane group, an acryloyl group, a methacryloyl group, and a lactone group.
  • R 7 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms, and c is 1 to 3.
  • the integer of 3 and e are integers of 0 to 3
  • f is an integer of 0 to 3
  • c + e + f 4.
  • the value of c is particularly preferably 1 from the viewpoint of availability.
  • R 7 include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a methoxy group, an ethoxy group, and a propoxy group.
  • the Ry group of the structural unit represented by the formula (7) contains an epoxy group, an oxetane group, or a lactone group
  • the outermost surface of the cured film obtained from the composition is silicon, glass, resin, or the like. It is possible to impart good adhesion to various substrates (including substrates having a multilayer film) and good adhesion to the upper resist layer.
  • the Ry group contains an acryloyl group or a methacryloyl group, a cured film having high curability can be obtained, and good solvent resistance can be obtained.
  • the Ry group contains an epoxy group and an oxetane group
  • the Ry group is preferably a group represented by the following formulas (2a), (2b) and (2c).
  • R g , R h , and R i each independently represent a divalent organic group. The broken line represents a bond).
  • examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, forming an ether bond. It may contain one or more sites. When the number of carbon atoms is 3 or more, the alkylene group may be branched, or distant carbons may be connected to form a ring. When there are two or more alkylene groups, oxygen may be inserted between carbons to form one or more ether bond sites, which are divalent organic groups. This is a preferred example.
  • repeating units of the formula (7) a particularly preferable one is exemplified by the raw material alkoxysilane, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name: KBM-403).
  • the Ry group contains an acryloyl group or a methacryloyl group, it is preferably a group selected from the following formula (3a) or (4a).
  • R j and R k each independently represent a divalent organic group. The broken line represents a bond).
  • R j and R k are divalent organic groups, again those mentioned as preferred groups R h, and R i.
  • a particularly preferable one is exemplified by the raw material alkoxysilane, 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name: KBM-503).
  • 3-Methacryloxypropyltriethoxysilane (same as above, product name: KBE-503), 3-methacryloxypropylmethyldimethoxysilane (same as above, product name: KBM-502), 3-methacryloxypropylmethyldiethoxysilane (same as above, Product name: KBE-502), 3-acryloxypropyltrimethoxysilane (same as above, product name: KBM-5103), 8-methacryloxyoctyltrimethoxysilane (same as above, product name: KBM-5803) and the like.
  • the Ry group contains a lactone group
  • the following formulas (5-1) to (5-20) and formulas (6-1) to (6-7) are used.
  • Formulas (7-1) to (7-28) or groups selected from formulas (8-1) to (8-12).
  • the organic acid it is preferable to add a monovalent or divalent or higher acid having 1 to 30 carbon atoms. Specific examples thereof include formic acid, acetic acid, maleic acid, citric acid, oxalic acid, propionic acid and the like, and acetic acid and maleic acid are particularly preferable. Further, in order to maintain stability, two or more kinds of acids may be mixed and used. The amount of addition is preferably converted to the pH of the composition so that the pH at 25 ° C. is 3 or more and 5 or less.
  • the amount of water added may be 0% by mass or more and less than 50% by mass, 0 to 30% by mass, or even 0 to 20% by mass with respect to the solvent component of the composition.
  • the present invention in the method for producing the above composition, is selected from the group consisting of the above precursor and the group consisting of chlorosilane, alkoxysilane, and silicate oligomer giving the structural unit represented by the above formula (2).
  • a predetermined solvent may be added.
  • the predetermined solvent the solvent species and the solvent (B) listed in ⁇ Reaction solvent> of the above "1-4. Composition precursor (solution)" can be used.
  • the solvent (B) may not be one that dissolves or disperses and precipitates the polysiloxane compound (A), and examples thereof include ester-based, ether-based, alcohol-based, ketone-based, and amide-based solvents.
  • the above ⁇ reaction solvent> and the solvent (B) may be added to the precursor in advance. Further, it may be added in advance to at least one selected from the group consisting of the above-mentioned chlorosilane, alkoxysilane, and silicate oligomer. Further, it may be added at the time of preparation of the above-mentioned copolymerization reaction. Further, it may be added in the middle of the above-mentioned copolymerization reaction.
  • a predetermined solvent to the above-mentioned copolymer raw material in advance, or to add it at the time of preparation of the above-mentioned copolymerization reaction.
  • the above ⁇ reaction solvent> and the solvent (B) may be added together, and the ⁇ reaction solvent> may be distilled off after the above copolymerization.
  • the above ⁇ reaction solvent> may be added, the ⁇ reaction solvent> may be distilled off after the above copolymerization, and the solvent (B) may be added.
  • the HFIP group-containing aromatic halosilane (4) or the HFIP group-containing aromatic alkoxysilane (5) which is the raw material compound of the precursor, is used.
  • the above-mentioned silane coupling agent may be copolymerized.
  • the present invention in the method for producing the above composition, is selected from the group consisting of the precursor and the group consisting of chlorosilane, alkoxysilane, and silicate oligomer giving the structural unit represented by the above formula (2).
  • the above-mentioned silane coupling agent may be added.
  • the silane coupling agent may be added to the precursor solution in advance, or may be added in advance to at least one selected from the group consisting of chlorosilane, alkoxysilane, and silicate oligomer, or both may be mixed. It may be added later.
  • a uniform composition can be obtained without precipitation of solids in the process of copolymerization.
  • the Q unit can be introduced at a high concentration, and the Q / (Q + T) ratio can be 0.6 or more and less than 1.00.
  • the composition is obtained by increasing the compatibility of 2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl group OH when the Q unit is introduced at a high concentration.
  • the polymerization giving the structural unit represented by the formula (1) and the polymerization giving the structural unit represented by the formula (2) do not occur unevenly, but both polymerizations tend to occur uniformly. It is considered that this contributes to the fact that the structural units can exist uniformly and evenly in the composition. In particular, it is considered that an even more remarkable contribution can be obtained in the production method of the present invention via the solution of the composition precursor.
  • silane coupling agent may be further added to the composition obtained by the above production method.
  • the above-mentioned silane coupling agent can be used as the silane coupling agent.
  • specific silane coupling agents will be illustrated.
  • compositions having different Q / (Q + T) ratios may be blended. For example, by blending a composition having a Q / (Q + T) ratio of 0.7 and a composition having a Q / (Q + T) ratio of 0.9, the Q / (Q + T) ratio is 0.6 or more. Compositions less than 00 may be produced. Alternatively, for example, by blending a composition having a Q / (Q + T) ratio of 0.6 or more and less than 1.00 and a composition having a Q / (Q + T) ratio of less than 0.6, Q / (Q + T) A composition having a ratio of 0.6 or more and less than 1.00 may be produced.
  • composition according to one embodiment of the present invention can also be used as a resist layer in a multilayer resist method.
  • a photoacid generator that generates an acid upon exposure, a basic substance that suppresses acid diffusion, and a quinonediazide compound that forms an indencarboxylic acid by exposure.
  • a cross-linking agent or the like that reacts with the base polymer by the action of an acid is added as a further component. In this way, the function as a resist is exhibited by exposure, and the organic layer is combined with the organic layer.
  • a pattern is obtained by exposure to a resist layer containing a composition according to an embodiment of the present invention. After that, dry etching is performed by plasma of oxygen-based gas through the pattern to form a pattern on the organic layer. Then, the substrate on which the desired pattern is formed is obtained by dry etching the substrate with plasma of a fluorine-based gas or a chlorine-based gas through the patterned organic layer.
  • a multilayer film composed of a resist layer (upper layer) and a lower layer film (lower layer) is formed on an organic layer formed on the substrate, and the patterned substrate is formed.
  • the pattern is used as a mask and dry etching is performed on the lower layer film to finally obtain a substrate to which the pattern is transferred.
  • the composition according to one embodiment of the present invention can be used as the underlayer film.
  • the method for producing a patterned substrate according to an embodiment of the present invention includes an organic layer, an underlayer film formed on the organic layer using a cured product of the composition according to the embodiment of the present invention, and a lower layer film.
  • the lower layer film is dry-etched with a fluorine-based gas
  • the organic layer is dry-etched with an oxygen-based gas
  • the fourth step with a fluorine-based gas or a chlorine-based gas. It is preferable to perform dry etching of the substrate.
  • the substrate material to which the above composition is brought into contact is a substrate made of silicon, amorphous silicon, polycrystalline silicon, silicon oxide, silicon nitride, silicon oxide, etc., and on these substrates, tungsten, tungsten-silicon, aluminum, copper, etc. Examples thereof include a substrate on which a metal film is formed, a low-dielectric-constant film, and a substrate on which an insulating film is formed. Further, the substrate may have a multilayer structure, and the outermost surface thereof may be a substrate having the above-mentioned material.
  • the film formed on the substrate usually has a film thickness of 50 nm or more and 20000 nm or less.
  • an organic layer as the multilayer film, a cured product (lower layer film) using the composition according to one embodiment of the present invention on the organic layer, and a resist layer (upper layer) on the cured product are sequentially formed.
  • the substrate with the multilayer film is obtained.
  • Organic layer A film made of a novolak resin, an epoxy resin, a urea resin, an isocyanate resin, or a polyimide resin having a phenol structure, a bisphenol structure, a naphthalene structure, a fluorene structure, a carbazole structure, or the like is formed as an organic layer on the substrate.
  • the organic layer can be formed by applying the organic layer forming composition containing these resins on the substrate by spin coating or the like. Since it is an organic layer having an aromatic ring in its structure, it exhibits an antireflection function when the resist layer is exposed in order to form a pattern on the resist layer.
  • the intermediate layer with the fluorine-based gas is dry-etched through the pattern obtained on the resist layer in the subsequent step, sufficient etching resistance of the fluorine-based gas to plasma is exhibited. In addition, it contributes to the reduction of outgas by containing an aromatic ring with high heat resistance.
  • the thickness of the organic layer varies depending on the etching conditions at the time of dry etching and is not particularly limited, but is usually formed to be 5 nm or more and 20000 nm or less.
  • a coating film of an underlayer film can be formed. After the coating film of the lower layer film, it is preferable to heat it to 100 ° C. or higher and 400 ° C. or lower to cure it in order to prevent mixing of the resist layer and the lower layer film in a subsequent step.
  • the thickness of the underlayer film varies depending on the type of fluorine-based gas used for dry etching and the etching conditions, and is not particularly limited, but is usually formed to be 5 nm or more and 500 nm or less.
  • the underlayer film formed by using the composition according to the embodiment of the present invention has a high content of Q units in the structure. Therefore, the etching resistance of the oxygen-based gas to plasma can be increased.
  • resist layer (upper layer)
  • a multilayer film is completed by forming a resist composition on the lower layer film by spin coating or the like to form a resist layer.
  • the obtained resist layer is exposed to a high-energy ray, for example, the above-mentioned g-line, i-line, KrF excimer laser light, ArF excimer laser, EUV, or the like through a photomask.
  • a high-energy ray for example, the above-mentioned g-line, i-line, KrF excimer laser light, ArF excimer laser, EUV, or the like
  • a tetramethylammonium hydroxide aqueous solution is used as the developing solution.
  • Butyl acetate is used as the developer in the organic solvent development of the negative resist.
  • the resist composition it suffices if a resist layer sensitive to the ultraviolet light can be formed, and the resist composition can be appropriately selected depending on the wavelength of the ultraviolet light.
  • the high energy rays are ultraviolet rays having a wavelength of 1 nm or more and 400 nm or less.
  • the resist composition in addition to the base resin, a known resist to which a photoacid generator that generates an acid by exposure and a basic substance that suppresses the diffusion of the acid can be used can be used.
  • the base resin includes polymethacrylate, a copolymer of cyclic olefin and maleic anhydride, polynorbornene, polyhydroxystyrene, novolak resin, phenol resin, maleimide resin, polyimide, polybenzoxazole, polysiloxane, or polysilsesquioki. Sun can be exemplified.
  • the photoacid generator examples include compounds that generate acids such as sulfonic acid, fluorosulfonic acid, fluorophosphate, and fluoroantimonic acid upon exposure.
  • acids such as sulfonic acid, fluorosulfonic acid, fluorophosphate, and fluoroantimonic acid upon exposure.
  • an additive such as a cross-linking agent that reacts with the base resin by the action of acid is added.
  • the photoacid generator examples include a sulfonium salt, an iodonium salt, a sulfonyldiazomethane, an N-sulfonyloxyimide or an oxime-0-sulfonate. These photoacid generators may be used alone or in combination of two or more.
  • the lower layer film is exposed at the portion dissolved and removed by the developing solution. Dry etching is performed on the exposed portion of the lower layer film by plasma of a fluorine-based gas such as a chlorofluorocarbon-based gas.
  • a fluorine-based gas such as a chlorofluorocarbon-based gas.
  • the underlayer film formed from the composition according to the embodiment of the present invention has a high etching rate of a fluorine-based gas with respect to plasma, and the resist layer forming a pattern has a low etching rate, so that sufficient etching selectivity can be obtained. Is obtained.
  • the pattern formed on the resist layer is used as a mask to transfer the pattern to the lower layer film.
  • the underlayer film formed from the composition according to the embodiment of the present invention has high etching resistance to plasma of an oxygen-based gas. Therefore, sufficient etching selectivity can be obtained.
  • the patterned organic layer is dry-etched with plasma of a fluorine-based gas or a chlorine-based gas to obtain a substrate on which the desired pattern is formed.
  • Examples of the fluorine-based gas or chlorine-based gas used in the method for producing a patterned substrate according to an embodiment of the present invention include CF 4 , CHF 3 , C 3 F 6 , C 4 F 6 , C 4 F 8 , and 3. Chlorine fluoride, chlorine, trichloroborane, and dichloroborane can be exemplified, but are not limited thereto.
  • Examples of the oxygen-based gas include O 2 , CO, and CO 2 , and O 2 , CO, and CO 2 are preferable from the viewpoint of safety.
  • composition according to the embodiment of the present invention has an etching rate ratio A of 50 or more, preferably 60 or more, obtained by dividing the etching rate under the following condition (1) by the etching rate under the following condition (2). More preferably, it is 70 or more.
  • CO 2 is used as an oxygen-based gas CO 2 flow rate: 300 sccm Ar flow rate: 100 sccm N 2 flow rate: 100 sccm Chamber pressure: 2Pa Applied power: 400W Temperature: 15 ° C
  • the composition according to the embodiment of the present invention has an etching rate ratio B of 20 or more, preferably 45 or more, obtained by dividing the etching rate under the following condition (1) by the etching rate under the following condition (3). It is more preferably 50 or more, further preferably 52 or more, and particularly preferably 55 or more.
  • the composition according to one embodiment of the present invention in addition to the lower layer film of the multilayer film, the cured film obtained by increasing the content of the Q unit is excellent in solvent resistance, adhesion, transparency, and heat resistance. .. Therefore, the composition according to one embodiment of the present invention includes a protective film for semiconductors, a protective film for organic EL and liquid crystal displays, a coating agent for image sensors, flattening materials and microlens materials, and an insulating protective film for touch panels. It can be applied to materials, liquid crystal display TFT flattening materials, optical waveguide core and clad forming materials, and the like.
  • composition precursor and composition obtained in this example were analyzed by the following method.
  • the weight average molecular weight (Mw) of the composition precursor described later and the composition was measured as follows.
  • a high-speed GPC apparatus manufactured by Tosoh Corporation, a device name of HLC-8320GPC, TSKgel SuperHZ2000 manufactured by Tosoh Corporation as a column, and tetrahydrofuran (THF) as a solvent were used, and the measurement was carried out by polystyrene conversion.
  • composition precursor [Si-NMR analysis of composition precursor] The composition precursor described later was measured using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., instrument name JNM-ECA400) having a resonance frequency of 400 MHz, using methoxytrimethylsilane as an internal standard.
  • a nuclear magnetic resonance apparatus manufactured by JEOL Ltd., instrument name JNM-ECA400
  • R 1 group, for R 2 groups are groups that do not participate in hydrolysis and polycondensation reaction
  • b is the number of these groups during synthesis of the precursor
  • m is hardly varied. Therefore, for b and m, the ratio of preparation was adopted as it was.
  • the Q / (Q + T) ratio was calculated from the total area of the peaks derived from the T unit and the total area of the peaks derived from the Q unit obtained by the above measurement. Further, l and n of the formula (1) were obtained from the area ratio of each peak derived from the T unit. Further, p and q of the formula (2) were obtained from the area ratio of each peak derived from the Q unit.
  • Example 1 In a 50 mL flask, 3.66 g (9 mmol) of the synthesized 3- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) -triethoxysilylbenzene (HHFIPTESB), water, 0.7 g. (39 mmol), acetic acid, 0.09 g (1.5 mmol) was added, the mixture was heated to 40 ° C., and the mixture was stirred for 1 hour to obtain a solution of the composition precursor which is a uniform solution.
  • HHFIPTESB (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) -triethoxysilylbenzene
  • silicate 40 (average pentamer, manufactured by Tama Chemical Industry Co., Ltd.). : As a pentamer)]) was added, and the mixture was stirred at 40 ° C. for 4 hours. No insoluble matter was generated during stirring, and the reaction solution was in a solution state.
  • PGMEA propylene glycol monomethyl ether acetate
  • Example 2 After adding the silicate 40, the temperature was raised to 70 ° C. and the mixture was stirred for 2 hours to obtain 40 g of a polysiloxane compound solution (composition) having a solid content concentration of 10% by mass in the same procedure as in Example 1.
  • Example 3 Add 3.25 g (8 mmol) of synthesized (HHFIPTESB), ethanol, 4.81 g (100 mmol), water, 1.81 g (100 mmol), acetic acid, 0.12 g (2 mmol) to a 50 mL flask, and heat to 80 ° C. After stirring for 1 hour, a solution of the composition precursor, which is a uniform solution, was obtained.
  • Example 4 To a 200 mL flask was added 4.06 g (10 mmol) of the synthesized (HHFIPTESB), ethanol, 87.38 g (1.9 mol), water, 43.69 g (2.4 mol), maleic acid, 0.58 g (5 mmol). After heating to 80 ° C. and stirring for 1 hour, a solution of the composition precursor which is a uniform solution was obtained.
  • silicate 40 (average pentamer, manufactured by Tama Chemical Industry Co., Ltd.) (90 mmol [SiO 2 conversion contained in silicate 40 (silicate 40 itself is about 18 mmol: 5). As a measure)] was added, and the mixture was stirred at 80 ° C. for 4 hours. No insoluble matter was generated during stirring, and the reaction solution was in a solution state. After stirring, water and by-produced ethanol were distilled off using a rotary evaporator while reducing the pressure at 60 ° C. Then, after adding 80 g of cyclohexanone, the mixture was transferred to a separating funnel, 80 g of water was added, and the first washing with water was performed.
  • Tables 1 and 2 show the details of the above composition precursor (solution) and the structure of the composition and the evaluation results.
  • compositions according to the Examples and Comparative Examples obtained above were filtered through a filter having a pore size of 0.22 ⁇ m and spun on a silicon wafer manufactured by SUMCO Corporation with a diameter of 4 inches and a thickness of 525 ⁇ m at a rotation speed of 250 rpm. After coating, the silicon wafer was fired on a hot plate at 200 ° C. for 3 minutes. In this way, a cured product film of the composition having a film thickness of 0.4 to 0.6 ⁇ m was formed on the silicon wafer.
  • the cured product film on the obtained silicon wafer is dry-etched with a fluorine-based gas (CF 4 and CHF 3 ) and an oxygen-based gas (CO 2 or O 2 ), and the etching rate for each gas is measured to determine the etching selectivity.
  • a fluorine-based gas CF 4 and CHF 3
  • an oxygen-based gas CO 2 or O 2
  • Etching conditions (1) to (3) are shown below (hereinafter, the etching rate may be simply referred to as a velocity, and the etching conditions may be simply referred to as a condition).
  • CO 2 is used as an oxygen-based gas CO 2 flow rate: 300 sccm Ar flow rate: 100 sccm N 2 flow rate: 100 sccm Chamber pressure: 2Pa Applied power: 400W Temperature: 15 ° C
  • Table 3 shows the measured values of the etching rates under the etching conditions (1) to (3) and the etching rate ratios obtained from them.
  • the etching rate ratio A is a value obtained by dividing the measured value of the velocity under the condition (1) by the measured value of the velocity under the condition (2)
  • the etching rate ratio B is a value obtained by dividing the measured value of the velocity under the condition (1) by the condition (3). ) Divided by the measured value of speed.
  • the cured film obtained by using the composition of the example having a Q / (Q + T) ratio of 0.6 or more has the composition of the comparative example having a Q / (Q + T) ratio of less than 0.6. It is superior in O 2 plasma etching resistance to the cured film obtained by using a material (the O 2 etching rate value in condition (3) is smaller). As a result, the cured film according to the example was superior in etching selectivity between the fluorine-based gas and the oxygen-based gas as compared with the cured film according to the comparative example (etch selectivity rate ratios (A) and (B)). Are both larger).
  • Example 1 has a pH of 4
  • Example 1-1 has a pH of 2
  • Example 1-2 has a pH of 3
  • Example 1-3 has a pH of 6
  • Example 1-4 has a pH. Is 9.
  • Example 1 As shown in Table 4, the storage stability of the composition is the best in Example 1 and Example 1-2 in which the pH at 25 ° C. is more than 2 and 5 or less, followed by Example 1 in which the pH is 2.
  • the order was -1, Example 1-3 having a pH of 6, and Example 1-4 having a pH of 9.
  • the compositions of Examples 1-1 and 1-2 were obtained by adding maleic acid to the compositions obtained in Example 1 so as to have pHs of 2 and 3, respectively.
  • the compositions of Examples 1-3 and 1-4 were obtained by adding triethylamine to the composition obtained in Example 1 so that the pH was 6 and 9, respectively.

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