Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • 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
• • 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
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
• • 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
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
  • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/16—Coating processes; Apparatus therefor
• • 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
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
• • 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
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/38—Treatment before imagewise removal, e.g. prebaking
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • 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
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
  • H10P14/6326—Deposition processes
  • H10P14/6342—Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating
• • 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
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/68—Organic materials, e.g. photoresists
  • H10P14/683—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC
• • 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
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/69—Etching of wafers, substrates or parts of devices using masks for semiconductor materials
  • H10P50/691—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials
• • 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
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
• • 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
  • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
  • H10P95/08—Planarisation of organic insulating materials
• • 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
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
• • 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

Definitions

• the present invention provides a protective film for a semiconductor manufacturing substrate (wafer) end surface, a protective film forming composition for forming the protective film, a semiconductor manufacturing wafer manufactured using the protective film, and the The present invention relates to a semiconductor manufacturing wafer and a manufacturing method of a semiconductor device.
• the manufacturing process becomes more complicated, a method of coating a wafer with a chemical solution containing metal is being studied for the purpose of, for example, improving the etching selectivity.
• the resist film is formed using a resist containing an inorganic metal because the resolution of the resist pattern is increased when exposure is performed using extreme ultraviolet (EUV) and it has high etching resistance. is being considered.
• EUV extreme ultraviolet
• the chemical solution supplied to the front surface of the wafer wraps around the peripheral edge portions of the peripheral edge surface and the back surface of the wafer, resulting in unintended peripheral edge portions of the peripheral edge surface and the back surface.
• metal contamination of these parts may occur because the coating film is formed up to the upper part.
• a wafer processing device such as an exposure device or an etching device or a wafer transfer mechanism
• the wafer is subsequently transferred and processed through these processing devices and transfer mechanisms.
• the wafer may also be contaminated with metals, that is, cross-contamination may occur.
• Patent Document 1 When forming a coating film on the surface of a substrate, a technique has been disclosed in which the coating film can be formed so that the peripheral end face and the back side peripheral edge portion of the substrate do not come into contact with the coating film (Patent Document 1).
• Patent Document 2 A method for manufacturing a semiconductor device in which peeling of a film from a bevel portion of a substrate is suppressed is disclosed.
• the problem to be solved by the present invention is to provide a protective film capable of completely covering the edges of a semiconductor manufacturing substrate (wafer) by a simple coating method in the manufacture of semiconductor devices, and a method for forming the protective film. It is an object of the present invention to provide a composition for forming a protective film, a semiconductor manufacturing wafer manufactured using the protective film, the semiconductor manufacturing wafer, and a method for manufacturing a semiconductor device.
• the present invention includes the following.
• a composition for forming a wafer edge protective film for semiconductor manufacturing comprising a polymer or compound having a crosslinkable group and a solvent.
• the protective film-forming composition according to [1] or [2] which has a viscosity of 100 cps or less at 25°C.
• [4] The protective film-forming composition according to any one of [1] to [3], which is photosensitive.
• [5] [1] to [4] A protective film which is a cured product of a coating film comprising the protective film-forming composition according to any one of [1] to [4].
• [6] The protective film according to [5], having a thickness of 1 nm to 10 ⁇ m.
• [8] The protective film according to any one of [5] to [7], which is cured with light having a wavelength of 170 to 800 nm.
• a semiconductor manufacturing wafer with a protected edge of the wafer which is formed by applying the protective film-forming composition according to any one of [1] to [4] to the edge of the wafer precursor. manufacturing wafers. [10] (A) forming a resist film on a semiconductor substrate; (B) forming a resist pattern by irradiating the resist film with light or an electron beam and then developing; (C) a step of etching the semiconductor substrate; In a method of manufacturing a semiconductor device comprising on the front edge and optionally the bevel and/or the back edge of a semiconductor fabrication wafer, Step (X) of forming a protective film from the protective film-forming composition according to any one of [1] to [4] including, A method of manufacturing a semiconductor device.
• [16] The method of manufacturing a semiconductor device according to [14], including a step (Z) of removing the protective film after the step (Y).
• [17] The method of manufacturing a semiconductor device according to any one of [10] to [16], wherein the resist film contains metal.
• [18] Manufacture of the semiconductor device according to any one of [10] to [17], wherein in the step (X), the protective film-forming composition according to [4] is applied, and a predetermined region is exposed and developed. Method.
• step (Z) is performed by ashing or treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a semiconductor cleaning solution.
• a method for manufacturing a wafer for semiconductor manufacturing A step of applying the protective film-forming composition according to any one of [1] to [4] to the edge of a wafer precursor to manufacture a wafer with the edge protected;
• a method of manufacturing a wafer for semiconductor manufacturing comprising:
• a protective film that can completely cover the edge of a semiconductor manufacturing substrate (wafer) by a simple coating method prevents cross-contamination due to metal contamination in subsequent semiconductor device manufacturing processes. Therefore, the yield of non-defective semiconductor manufacturing equipment can be improved.
• a method for manufacturing a semiconductor device includes: (A) forming a resist film on a semiconductor substrate; (B) forming a resist pattern by irradiating the resist film with light or an electron beam and then developing; (C) processing the semiconductor substrate by etching, or processing the semiconductor substrate by etching through the patterned resist;
• Step (X) of forming a protective film from a composition for forming a wafer edge protective film for semiconductor manufacturing, which contains a polymer or compound having a crosslinkable group and a solvent including, A method for manufacturing a semiconductor device.
• a resist film is formed on a semiconductor substrate.
• Semiconductor substrates are wafers used for the manufacture of semiconductor devices and the like, and include commonly used silicon wafers, germanium wafers, gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.
• a compound semiconductor wafer formed by combining two or more kinds of elements such as They are usually disc-shaped and have sizes of, for example, 4, 6, 8, 12 inches, and the like. Commercial products may be used.
• the inorganic film is formed by, for example, an ALD (atomic layer deposition) method, a CVD (chemical vapor deposition) method, a reactive sputtering method, an ion plating method, or a vacuum deposition method. It is formed by a spin coating method (spin on glass: SOG).
• the inorganic film examples include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium oxynitride film, a tungsten film, a gallium nitride film, and a gallium arsenide film. is mentioned.
• a resist underlayer film, a resist film, etc., having a predetermined thickness are formed on such a semiconductor substrate by an appropriate coating method such as a spray, spinner, or coater.
• an appropriate coating method such as a spray, spinner, or coater.
• each of the resist underlayer film-forming composition, the resist film-forming composition, and the like is supplied through a nozzle or the like from above the central portion of the rotating disk-shaped substrate.
• These films are typically baked using a heating means such as a hot plate.
• the photoresist used for forming the resist film is not particularly limited as long as it is sensitive to the light used for exposure. Both negative and positive photoresists can be used.
• positive photoresist composed of novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester;
• a chemically amplified photoresist comprising a low-molecular compound that decomposes to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and a binder having a group that decomposes with an acid to increase the alkali dissolution rate.
• photoresists composed of low-molecular-weight compounds and photoacid generators that are decomposed by acid to increase the rate of alkali dissolution of photoresists, and resists containing metal elements.
• Examples include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., AR2772 (trade name) and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
• Proc. SPIE Vol. 3999, 330-334 (2000)
• Proc. SPIE Vol. 3999, 357-364 (2000)
• Proc. SPIE Vol. 3999, 365-374 (2000).
• a negative photoresist is preferred.
• the resist film-forming composition used for forming the resist film can contain one or more metals.
• the form of the metal include simple metals, metal salts, metal complexes, and other metal-containing compounds.
• Metal species are not particularly limited, but examples include tin, indium, antimony, bismuth, gallium, germanium, aluminum, zirconium, hafnium, cerium, lanthanum, and cesium.
• Baking conditions for the resist film are appropriately selected from a baking temperature of 70° C. to 400° C. and a baking time of 0.3 minutes to 60 minutes.
• the baking temperature is 80° C. to 350° C.
• the baking time is 0.5 minutes to 30 minutes
• the baking temperature is 90° C. to 300° C.
• the baking time is 0.8 minute to 10 minutes.
• the lower limit of the average thickness of the resist film is preferably 1 nm, more preferably 3 nm, 5 nm and 10 nm.
• the upper limit of the average thickness of the resist film is 5,000 nm, 3,000 nm, 2,000 nm, preferably 1,000 nm, more preferably 200 nm, and more preferably 50 nm.
• Step (X) of forming a protective film The step (X) of forming a protective film from the protective film-forming composition on the front edge and, optionally, the bevel and/or the back edge of the semiconductor manufacturing wafer is performed at any time. In step (X), preferably, a protective film-forming composition is applied, and a predetermined region is exposed and developed. Step (X) may be performed before step (A), between step (A) and step (B), or after step (B) or step (C). good.
• the surface of the substrate on which the device portion such as the resist film is provided is called the front surface, and the opposite surface is called the back surface.
• the front surface edge refers to a region generally having a width of 1 to 10 mm from the edge of the device portion provided on the substrate to the bevel portion, and the bevel portion connects the front surface edge and the back surface edge.
• the bent area is defined as the edge of the rear surface, and the edge of the rear surface of the substrate is the area corresponding to the edge of the front surface of the rear surface of the substrate.
• a protective film-forming composition (to be described later) is applied to a semiconductor substrate on which a resist film or the like has been formed.
• the method of applying the protective film-forming composition is not particularly limited, but known means such as a spin coating method and a spray method can be employed.
• the protective film-forming composition is applied from above or near the edge of the surface of the rotating disk-shaped substrate while rotating the semiconductor substrate on which a resist film or the like is formed at a predetermined rotation speed. Feed through a nozzle.
• the beveled portion and/or the backside edge of the substrate are also fed through the nozzle from the vicinity of each.
• the spin coating conditions can be selected as appropriate and are not limited at all, but typical conditions are as follows.
• ⁇ Viscosity of protective film-forming composition about 100 cps or less
• ⁇ Wafer rotation speed ..
• Exposure is applied to the protective film-forming composition through a mask or through a mask with actinic rays such as ultraviolet rays, visible rays, and radiation (i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), EB (including electron beam)).
• actinic rays such as ultraviolet rays, visible rays, and radiation
• soft baking SB
• post-exposure baking PEB
• the post-exposure heating temperature is preferably 50° C. to 150° C.
• the post-exposure heating time is preferably 1 to 10 minutes.
• the exposed protective film-forming composition is developed.
• Development can be carried out by removing the exposed portion of the protective film-forming composition after exposure with a developer, and the development temperature is appropriately selected from 5° C. to 50° C. and the development time is selected from 10 seconds to 300 seconds.
• organic solvents contained in the developer include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like.
• organic solvent for the developer those containing an ester solvent, a ketone solvent, or a combination thereof are preferable.
• the developer may contain one type of organic solvent alone, or may contain two or more types.
• alcohol solvents examples include aliphatic monoalcohol solvents having 1 to 18 carbon atoms such as 4-methyl-2-pentanol and n-hexanol; alicyclic monoalcohols having 3 to 18 carbon atoms such as cyclohexanol. system solvent; polyhydric alcohol partial ether system solvent having 3 to 19 carbon atoms such as propylene glycol monomethyl ether.
• ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether; cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; and diphenyl ether. and aromatic ring-containing ether solvents such as anisole.
• dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether
• cyclic ether solvents such as tetrahydrofuran and tetrahydropyran
• diphenyl ether diphenyl ether.
• aromatic ring-containing ether solvents such as anisole.
• Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-hexyl ketone.
• di-iso-butyl ketone trimethylnonanone and other chain ketone solvents
• cyclopentanone cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone and other cyclic ketone solvents
• 2,4-pentanedione acetonyl Acetone, acetophenone, and the like.
• amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, Chain amide solvents such as N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide and the like are included.
• ester solvents include monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate; polyhydric alcohol carboxylate solvents such as propylene glycol acetate; polyhydric alcohol partial ether carboxylates such as propylene glycol monomethyl ether acetate; rate-based solvents; polyvalent carboxylic acid diester-based solvents such as diethyl oxalate; and carbonate-based solvents such as dimethyl carbonate and diethyl carbonate.
• monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate
• polyhydric alcohol carboxylate solvents such as propylene glycol acetate
• polyhydric alcohol partial ether carboxylates such as propylene glycol monomethyl ether acetate
• rate-based solvents polyvalent carboxylic acid diester-based solvents
• carbonate-based solvents such as dimethyl carbonate and diethyl carbonate.
• hydrocarbon solvents examples include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as n-pentane and n-hexane; aromatic hydrocarbon solvents having 6 to 16 carbon atoms such as toluene and xylene. mentioned.
• ester-based solvents propylene glycol monomethyl ether acetate is preferred. Cyclohexanone is preferred as the ketone solvent. Propylene glycol monomethyl ether is preferable as the ether solvent.
• the lower limit of the content of the organic solvent in the developer is preferably 80% by mass, more preferably 90% by mass, even more preferably 99% by mass, and particularly preferably 100% by mass.
• the developer may contain a nitrogen-containing compound.
• the developer contains a nitrogen-containing compound, it is possible to further reduce film loss in the formed resist pattern.
• an aqueous developer may be used instead of the organic solvent-based developer described above.
• alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, monoethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide may be used.
• the base concentration of these aqueous solutions is not particularly limited, but can be, for example, 0.1 to 10% by weight.
• alcohols and surfactants can be added to the above developing solution and used. Each of these can be blended in the range of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the developer.
• surfactants include ionic and nonionic fluorine-based surfactants, silicon-based surfactants, and the like.
• Examples of the development method include a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), and a method in which the developer is piled up on the surface of the substrate by surface tension and left stationary for a certain period of time (paddle method). ), a method in which the developer is sprayed onto the surface of the substrate (spray method), and a method in which the developer dispensing nozzle scans the substrate rotating at a constant speed and continuously dispenses the developer (dynamic dispensing method). etc.
• the heating temperature in the heat treatment is usually 150°C or higher and 350°C or lower, preferably 200 to 300°C.
• the heat treatment time is the time required for the protective film-forming composition to harden, and in consideration of productivity, it is preferably less than approximately 30 minutes.
• the lower limits of the average thickness of the protective film are, for example, 1 nm, 3 nm, 5 nm, 10 nm, 30 nm, 50 nm, 80 nm, 100 nm, 150 nm and 200 nm.
• the upper limits of the average thickness of the protective film are, for example, 10 ⁇ m, 8 ⁇ m, 5 ⁇ m, 3 ⁇ m, 1 ⁇ m, 800 nm, 500 nm, and 300 nm.
• the resist film on the protective film can be removed with a remover.
• a remover Similar to the step (X), it is preferable to apply the remover to the front surface edge of the semiconductor manufacturing wafer and, optionally, the bevel portion and/or the back surface edge.
• the resist remover includes, for example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, water, butyl acetate, tetramethylammonium aqueous solution, or mixtures thereof.
• propylene glycol monomethyl ether acetate and water are preferable from the viewpoint of removability of the resist film.
• the protective film can be removed by ashing or treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a cleaning solution for semiconductors. After that, it is preferable to wash with an arbitrary solvent or a commonly used semiconductor cleaning liquid.
• Steps (X), (Y), and (Z) can be performed simultaneously with steps (A), (B), and (C), or at any time before or after each step.
• step (X) when step (X) is included before step (A), step (Y) of removing the resist film above the protective film may be performed between step (A) and step (B). can be performed, and the step (Z) of removing the protective film can be performed between the step (Y) and the step (B).
• step (X) is included between step (A) and step (B) or step (C)
• protection A step (Z) of removing the film can also be performed.
• Step of forming a resist pattern by irradiating a resist film with light or an electron beam and subsequent development, and (C) Step of processing a semiconductor substrate by etching The resist film is exposed through a mask (reticle) for forming a predetermined pattern, for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) is used. .
• a mask for forming a predetermined pattern
• i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) is used.
• soft baking SB
• post-exposure baking PEB
• the post-exposure heating temperature is preferably 50° C. to 150° C.
• the post-exposure heating time is preferably 1 to 10 minutes.
• An alkaline developer is used for development, and the development temperature is appropriately selected from 5°C to 50°C and the development time is 10 seconds to 300 seconds.
• the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, secondary amines such as di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; Aqueous solutions of alkalis such as quaternary ammonium salts, pyrrole, cyclic amines such as piperidine, and the like can be used.
• the base concentration of these aqueous solutions is not particularly limited, but can be, for example, 0.1 to 10% by weight.
• alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants can be added in appropriate amounts to the aqueous solution of alkalis.
• surfactants such as nonionic surfactants
• Each of these can be blended in the range of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the developer.
• Preferred developers among these are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline.
• a surfactant or the like can be added to these developers.
• Parts where the alkali dissolution rate of the photoresist is not improved by developing with a polyhydric alcohol solvent having 2 to 18 carbon atoms such as 1,2-propylene glycol or an organic solvent such as butyl acetate instead of the alkaline developer. can also be used.
• the semiconductor substrate is baked.
• the baking means is not particularly limited, for example, a proximity baking furnace in which a plurality of substrate support pins are used to secure a gap between the substrate and the hot plate is preferably used.
• the baking temperature is usually 40° C. to 300° C., preferably 200° C. to 300° C. for 1 to 30 minutes, but may be set to 90° C. or less if it is necessary to avoid damage to the resist pattern.
• Baking may be performed on the semiconductor substrate after exposure and before development.
• the means and conditions for baking are as described above, but if it is necessary to avoid damage to the resist pattern, the temperature may be set to 90° C. or less.
• the resist underlayer film is etched, preferably dry etched, to form a patterned resist.
• the semiconductor substrate is processed by a method known per se (dry etching method, etc.) using the patterned resist.
• the etching for processing the semiconductor substrate may be a known method.
• the shape processing step is performed by dry etching using a fluorine-based gas such as carbon tetrafluoride.
• it includes a surface treatment step such as removing a silicon nitride film present on the surface of the semiconductor substrate with hot phosphoric acid.
• a semiconductor device can be manufactured through the above processes.
• the method for producing a wafer for semiconductor production according to the present invention is the method for producing a semiconductor device as described above, wherein a composition for forming a wafer edge protection film for semiconductor production containing a polymer or compound having a crosslinkable group and a solvent is used. , applying (or coating) to the front edge and, optionally, the bevel and/or back edge of the semiconductor fabrication wafer precursor to produce a protected semiconductor fabrication wafer.
• a semiconductor manufacturing wafer precursor refers to a product obtained by subjecting a semiconductor substrate to at least one step of a semiconductor device manufacturing method.
• the step of forming an inorganic film, a resist underlayer film, a resist film, etc. on a semiconductor substrate is performed, and the resist film is irradiated with light or an electron beam, and then Examples include materials before being subjected to the step of forming a resist pattern by development of a.
• a polymer or compound having a crosslinkable group and a solvent are added to the front surface edge and optionally the bevel portion and/or the back surface edge of a semiconductor manufacturing wafer precursor obtained through one or more steps of a semiconductor device manufacturing process.
• a composition for forming a wafer edge protection film for semiconductor manufacturing containing the composition is applied by spin coating.
• the semiconductor substrate may then be baked.
• the baking means is not particularly limited, but for example, a proximity baking furnace that secures a gap between the substrate and the hot plate using a plurality of substrate support pins is preferably used.
• the baking temperature is usually 40-300° C., preferably 200-300° C., for 1-30 minutes.
• the end surface of the protective film may be subjected to known treatments in the semiconductor manufacturing process, such as edge bead removal and back rinsing.
• the wafer for semiconductor manufacturing of the present invention is a wafer for semiconductor manufacturing in which the edge of the wafer is protected, and is formed by coating the edge of the wafer with the protective film-forming composition containing a polymer having a crosslinkable group and a solvent. It is a wafer for semiconductor manufacturing.
• the protective film-forming composition of the present invention is a protective film-forming composition used to protect the edge of the surface of a semiconductor manufacturing wafer, and comprises a polymer or compound having a crosslinkable group and a solvent. is.
• a crosslinkable group means a group capable of forming a crosslinked structure by the action of light, electron beams, other electromagnetic waves, radicals, acids, heat, water, oxygen, and the like. Examples include, but are not limited to, epoxy groups, acryl groups, vinyl groups, carboxylic acid groups, thiol groups, silanol groups, cinnamoyl groups, hydroxyl groups (including phenolic hydroxyl groups), and the like.
• polymer or compound having a crosslinkable group examples include, but are not limited to, the following. ⁇ epoxy (meth)acrylate, cinnamic acid grafted epoxy novolak, phenoplasts, thermosetting materials obtained by polycondensation of phenols and aldehydes with removal of water and formation of a three-dimensional network; - For example, melamine resins such as trimethylol melamine and hexamethylol melamine, urea resins such as dimethylol propylene urea, dimethylol ethylene urea, and dimethylol hydroxyl urea, aminoblast resins such as dimethylol urone resin, (blocked) isocyanates, ⁇ vinyl ether, ⁇ Polysiloxane resins and epoxy resins with (meth)acrylic groups.
• melamine resins such as trimethylol melamine and hexamethylol melamine
• urea resins such as di
• solvents contained in the protective film-forming composition of the present invention include water, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, Propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Propyl Ether Acetate, Toluene, Xylene, Methyl Ethyl Ketone, Methyl Isobutyl Ketone, Cyclopentanone, Cyclohexanone, Cycloheptanone, 4-Methyl-2-Pene Tanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl a
• the solvent should be added so that the protective film-forming composition of the present invention has an appropriate viscosity. In general, it is preferably about 100 to 3,000 parts by mass with respect to 100 parts by mass of the polymer or compound having a crosslinkable group.
• the protective film-forming composition of the present invention may optionally contain a radical polymerization initiator (such as a photopolymerization initiator), an acid (catalyst), a thermal acid generator, a photoacid generator, a base (catalyst), Thermal base generator, photobase generator, antioxidant, polymerization inhibitor, cross-linking agent (polyfunctional acrylic, etc.), adhesion improver, adhesion aid (silane coupling agent), surfactant, defoaming agent, Rheology modifiers, pigments, dyes, storage stabilizers, dissolution accelerators such as polyhydric phenols and polyhydric carboxylic acids, sensitizers, and the like can be included.
• Any radical polymerization initiator may be used as long as it can release a substance that initiates radical polymerization upon exposure to light and/or heat.
• photoradical polymerization initiators include benzophenone derivatives, imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azide compounds, titanocene compounds, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives. etc.
• benzophenone 1,3-di(tert-butyldioxycarbonyl)benzophenone, 3,3′,4,4′-tetrakis(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5- isoxazolone, 2-mercaptobenzimidazole, bis(2,4,5-triphenyl)imidazole, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-benzyl- 2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis( ⁇ 5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H -pyrrol-1-yl)-phenyl)titanium) and the like, but are not limited thereto.
• photoradical polymerization initiator examples include IRGACURE (registered trademark) 651, 184, 369, 784 manufactured by BASF.
• commercial products other than the above can also be used.
• thermal radical polymerization initiators include acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, and dilauroyl.
• Peroxides peroxides such as tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate; 2,2′-azobisisobutyronitrile, 2,2′- Azobis(2,4-dimethylvaleronitrile), (1-phenylethyl)azodiphenylmethane, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisiso butyrate, 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(1-cyclohexanecarbonitrile), 2-(carbamoylazo)isobutyronitrile, 2,2′-azobis ( 2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis(2-methylpropane)
• thermal radical polymerization initiators examples include NOF Corporation Perloyl (registered trademark) IB, NPP, IPP, SBP, TCP, OPP, SA, 355, L, Perbutyl (registered trademark) ND, NHP, MA, PV, 355, A, C, D, E, L, I, O, P, Z, Perhexyl (registered trademark) ND, PV, D, I, O, Z, Perocta (registered trademark) ND, Nyper ( Registered trademarks) PMB, BMT, BW, Pertetra (registered trademark) A, Perhexa (registered trademark) MC, TMH, HC, 250, 25B, C, 25Z, 22, V, Perocta (registered trademark) O, Percumyl (registered trademark) ) ND, D, Permenta (registered trademark) H, Nofmar (registered trademark) BC; Wako Pure Chemical Industries, Ltd.
• radical polymerization initiator Only one type of radical polymerization initiator may be used, or two or more types may be used in combination.
• the content of the radical polymerization initiator is preferably 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 50 parts by mass or less, and 20 parts by mass or less with respect to 100 parts by mass of the polymer or compound having a crosslinkable group. It is 10 parts by mass or less.
• a hindered phenol compound may be used, specifically 2,6-diisobutylphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcresol, hydroquinone. , hydroquinone monomethyl ether, N-nitroso-N-phenylhydroxylamine aluminum, pyrogallol, t-butylcatechol, 4-methoxy-1-naphthol, 2,6-di-t-butyl-4-methylphenol, 2,5- Di-t-butyl-hydroquinone, Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, Isooctyl-3-(3,5-di-t-butyl-4-hydroxy phenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-buty
• 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H, 3H,5H)-trione is preferred.
• a commercial product may be used as the polymerization inhibitor, and a specific example thereof is Irganox-3114 (manufactured by BASF Japan Ltd.).
• the content of the polymerization inhibitor is preferably 0.01 to 1 part by mass, more preferably 0.01 to 0.5 part by mass, with respect to 100 parts by mass of the polymer or compound having a crosslinkable group.
• surfactants include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Oxyethylene alkyl allyl ether compounds, polyoxyethylene/polyoxypropylene block copolymer compounds, sorbitan fatty acid ester compounds such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate and sorbitan tristearate, polyoxyethylene Examples include polyoxyethylene sorbitan fatty acid ester compounds such as ethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan tristearate.
• trade names Ftop EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names Megafac F171, F173, R-08, R-30 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), product names Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants and organosiloxane polymers.
• KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.
• the content of the surfactant is preferably 0.1 parts by mass or more, 0.5 parts by mass or more, 5 parts by mass or less, and 2 parts by mass or less with respect to 100 parts by mass of the polymer or compound having a crosslinkable group.
• an acidic compound As the acid catalyst, an acidic compound, a basic compound, or various compounds that generate an acid or base by heat or light can be used.
• a sulfonic acid compound or a carboxylic acid compound can be used as the acidic compound.
• An amine compound or an ammonium hydroxide compound can be used as the basic compound, and urea can be used as the compound that generates a base by heat.
• Amine compounds such as triethanolamine, tributanolamine, trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-n-octylamine, triisopropanolamine, phenyldiethanolamine, stearyl Tertiary amines such as diethanolamine and diazabicyclooctane, aromatic amines such as pyridine and 4-dimethylaminopyridine.
• Amine compounds also include primary amines such as benzylamine and n-butylamine, and secondary amines such as diethylamine and di-n-butylamine.
• ammonium hydroxide compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, cetyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide and phenyltriethylammonium hydroxide.
• thermal acid generators and photoacid generators can be used as acid generators.
• Thermal acid generators include, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium-p-hydroxybenzenesulfonic acid (p-phenolsulfonic acid pyridinium salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid and sulfonic acid compounds such as hydroxybenzoic acid and carboxylic acid compounds.
• K-PURE registered trademark
• CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, and TAG2689 manufactured by King Industries
• SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 manufactured by Sanshin Chemical Industry Co., Ltd.
• photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethanes, N-sulfonyloxyimides, benzoinsulfonate-type photoacid generators, pyrogallol trisulfonate-type photoacid generators, sulfone-type photoacid generators, and glyoxime derivative-type photoacid generators. generators, oxime-O-sulfonate type acid generators, bisoxime sulfonate type acid generators and the like.
• Examples include bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, phenyl-bis(trichloromethyl)-s-triazine, benzoin tosylate, and N-hydroxysuccinimide trifluoromethanesulfonate. be able to.
• thermal base generators include carbamates such as 1-methyl-1-(4-biphenylyl)ethylcarbamate and 2-cyano-1,1-dimethylethylcarbamate; urea, N,N-dimethyl-N'- ureas such as methylurea; guanidines such as guanidine trichloroacetate, guanidine phenylsulfonylacetate and guanidine phenylpropiolate; dihydropyridines such as 1,4-dihydronicotinamide; N-(isopropoxycarbonyl)-2,6-dimethyl Dimethylpiperidines such as piperidine, N-(tert-butoxycarbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)-2,6-dimethylpiperidine; tetramethylammonium phenylsulfonylacetate, tetramethylphenylpropiolate quatern
• the above components can be used alone or in combination of two or more. In that case, the amount is usually 10% by mass or less, preferably 3% by mass or less in the solid content of the protective film-forming composition of the present application. Used.
• the method for preparing the protective film composition of the present invention is not particularly limited. That is, a polymer or compound having a crosslinkable group, a solvent, and other components may be mixed in an arbitrary ratio and in an arbitrary order to form a uniform solution.
• the protective film-forming composition thus prepared in a solution state is preferably used after being filtered using a filter having a pore size of about 0.2 ⁇ m.
• the composition for forming a protective film preferably has a viscosity of about 100 cps or less at 25°C in order to form a protective film having a thickness of about 300 nm by spin coating.
• a viscosity is a measured value by an E-type viscometer.
• the properties of the protective film that covers the edges of semiconductor manufacturing substrates include the ability to prevent metal contamination as described above, as well as dry etching resistance, phosphoric acid resistance, tetramethylammonium hydroxide (TMAH) resistance, and HF removal. resistance to abrasion, good embeddability for stepped substrates, low sublimation amount, affinity for hydrophobic substrates, no crater foreign matter left on the side of the wafer, good edge shape, inner hump (just below the nozzle injection hole) It is desirable to satisfy the function of suppressing the phenomenon that the film-forming composition remains in a lump).
• the protective film-forming composition of the present invention is preferably photosensitive.
• it may be of the negative solvent development type.
• photosensitive protective film-forming composition after applying the photosensitive protective film-forming composition (negative type) to the front surface edge of the substrate and, optionally, the bevel portion and/or the back surface edge. By exposing and developing a portion of the film to be cured, the bevel portion can be accurately covered with the protective film.
• Photosensitivity makes it easy to control the film thickness of the protective film on the wafer edge, remove the inner hump, improve the edge shape, and correct the deviation of the center position during spin coating. has the advantage of
• the protective film-forming composition of the present invention has a partial structure (I) represented by the following formulas (1-1) to (1-7) described in WO2018/190380:
• R 1 , R 1a , R 3 , R 5a and R 6a are each independently an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 40 carbon atoms (the alkylene group and the arylene group optionally substituted with one or more amido or amino groups), an oxygen atom, a carbonyl group, a sulfur atom, —C(O)—NR a —, —NR b —, or Represents a divalent group consisting of a combination of
• Each R 5 is independently a nitrogen atom, or a nitrogen atom and an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 40 carbon atoms (the alkylene group and arylene group are one or more at least one selected from the group consisting of an oxygen atom, a carbonyl group, a sulfur atom, —C(O)—NR a — and —NR b —
• the protective film-forming composition of the present invention may contain polysiloxane.
• the polysiloxane may be a modified polysiloxane in which some of the silanol groups are modified, for example, a modified polysiloxane in which some of the silanol groups are alcohol-modified or acetal-protected.
• Polysiloxane may be, for example, a hydrolytic condensate of a hydrolyzable silane, or a modified product in which at least part of the silanol groups of the hydrolytic condensate is alcohol-modified or acetal-protected (hereinafter referred to as It may be referred to as a “modified product of hydrolytic condensate”.).
• the hydrolyzable silane associated with the hydrolytic condensate can contain one or more hydrolyzable silanes.
• the polysiloxane can have any structure having a cage-type, ladder-type, straight-chain, or branched main chain. Furthermore, commercially available polysiloxanes can be used.
• the "hydrolytic condensate" of the hydrolyzable silane that is, the product of hydrolytic condensation, includes not only the polyorganosiloxane polymer, which is a condensate in which the condensation has been completely completed, but also Also included are polyorganosiloxane polymers that are incomplete partial hydrolytic condensates.
• Such a partially hydrolyzed condensate is also a polymer obtained by hydrolysis and condensation of a hydrolyzable silane, similar to the condensate in which the condensation is completely completed, but it stops at partial hydrolysis and condenses. , and therefore the Si--OH groups remain.
• the polysiloxane of the present invention include hydrolytic condensates of hydrolyzable silanes containing at least one hydrolyzable silane represented by the following formula (1) and modified products thereof.
• R 1 is a group bonded to a silicon atom and independently of each other, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl optionally substituted halogenated alkyl group, optionally substituted halogenated aryl group, optionally substituted halogenated aralkyl group, optionally substituted alkoxyalkyl group, optionally substituted an alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group, an organic group having an acryloyl group, or an organic group having a methacryloyl group; It represents an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, an organic group having a cyano group, or a combination of two or more thereof.
• R 2 is a group
• each group and atom in R 1 in formula (1) and preferred carbon numbers thereof include the groups and carbon numbers described above for R 3 in formulas (A-1) and (A-2) can be mentioned.
• Specific examples of each group and atom in R 2 in formula (1) and their preferred number of carbon atoms include the groups and atoms described above for X in formulas (A-1) and (A-2), and carbon I can name a few.
• hydrolyzable silane represented by Formula (1) includes tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n -butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, ⁇ -glycid
• the protective film-forming composition of the present invention is described in JP-A-2016-003160, (A) a polyfunctional epoxy (meth)acrylate compound, It may contain (B) a polyfunctional thiol compound and (C) a radical polymerization initiator.
• the component (A) may have a molecular weight of 300 to 20,000.
• the component (A) may be a bisphenol-type polyfunctional epoxy (meth)acrylate compound.
• the component (B) may be liquid at 25°C.
• a polymerization inhibitor may be contained. It may have a viscosity of 2,000 to 100,000 mPa ⁇ s at 25°C.
• the protective film-forming composition of the present invention may be a film-forming composition comprising a photopolymerizable substance and a photoinitiator as described in WO2009/104643.
• the photopolymerizable substance may be a compound having at least one cationic polymerizable reactive group, and the cationic polymerization initiator may be a photocationic polymerization initiator.
• the photopolymerizable substance may be a compound having at least one radically polymerizable reactive group, and the photopolymerization initiator may be a radical photopolymerization initiator.
• the photopolymerizable compound may be a sugar compound.
• the sugar compounds may be monosaccharide or disaccharide compounds.
• the sugar compound has the formula (10):
• G 1 represents a sugar skeleton
• T represents a divalent linking group
• R 1 represents a vinyl group or glycidyl group
• R 2 represents a hydrogen atom or a hydroxyl group
• n and L are 0 or 1, respectively.
• p is an integer representing the total number of hydroxyl groups possessed by the sugar
• m is an integer satisfying 1 ⁇ m ⁇ (pm).
• the photopolymerizable compound may be an alicyclic epoxy compound or an alicyclic oxetane compound.
• the alicyclic epoxy compound may be a cycloalkylene oxide derivative.
• the alicyclic epoxy compound is represented by formula (2) or formula (3):
• G2 represents a monovalent to pentavalent linking group having an alkylene group, carbonyloxy group, heterocyclic ring, aromatic ring, or a combination thereof
• G3 represents an alkyl group, an alkylcarbonyl group, a heterocyclic ring, an aromatic an organic group having a ring or a combination thereof, n and m each representing an integer of 1 to 5).
• the molecular weight of the polysiloxane used in the present invention is the molecular weight obtained in terms of polystyrene by GPC analysis.
• GPC measurement conditions are, for example, a GPC device (trade name HLC-8220GPC, manufactured by Tosoh Corporation), GPC columns (TSKgel Super-MultiporeHZ-N (2 columns)), column temperature 40° C., eluent (elution solvent) Tetrahydrofuran, a flow rate (flow rate) of 0.35 mL/min, and polystyrene (manufactured by Sigma-Aldrich) as a standard sample can be used.
• reaction by-products methanol, ethanol and water, were distilled off under reduced pressure and concentrated to obtain a hydrolyzed condensate (polymer) solution.
• propylene glycol monomethyl ether was added to adjust the concentration so that the solvent ratio of 100% propylene glycol monomethyl ether was 20% by mass in terms of solid residue at 150° C., and filtered through a nylon filter (pore size 0.1 ⁇ m). gone.
• the obtained polymer contained a structure represented by the following formula (YY), and had a weight average molecular weight of Mw 3,300 in terms of polystyrene by GPC.
• Epoxy group-containing novolac resin product name: EPPN-201, epoxy value: 192 g/eq., manufactured by Nippon Kayaku Co., Ltd.
• acrylic acid 11.26 g acrylic acid 11.26 g
• tetrabutylphosphonium bromide 1.99 g acrylic acid 11.26 g
• hydroquinone 0 101.11 g of propylene glycol monomethyl ether acetate was added to .09 g, and the mixture was heated and stirred at 100° C. for 18 hours in a nitrogen atmosphere.
• the resulting solution was added with 43 g of a cation exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and an anion exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Corporation). 43 g was added and subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a compound solution was obtained. The obtained compound corresponded to the formula (XX) and had a weight average molecular weight Mw of 6,900 as measured by GPC in terms of polystyrene.
• a cation exchange resin product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.
• an anion exchange resin product name: Amberlite [registered trademark] 15JWET, Organo Corporation
• reaction by-products methanol, ethanol and water, were distilled off under reduced pressure and concentrated to obtain a hydrolyzed condensate (polymer) solution.
• propylene glycol monomethyl ether was added to adjust the concentration so that the solvent ratio of 100% propylene glycol monomethyl ether was 20% by mass in terms of solid residue at 150° C., and filtered through a nylon filter (pore size 0.1 ⁇ m). gone.
• the obtained polymer contained a structure represented by the following formula (ZZ), and had a weight average molecular weight of Mw 3,400 in terms of polystyrene by GPC.
• Irgacure Oxe01 manufactured by BASF Japan Ltd.
• Megafac R-30 Dainippon Ink Kagaku Co., Ltd., trade name
• the protective film-forming compositions prepared in Preparation Examples 1 to 3 were spin-coated on silicon wafers, and then coated using a coater manufactured by Tokyo Electron Co., Ltd. Using a wafer edge exposure module (WEE) from developer LithiusPro, the wafer edge portion was exposed to mercury lamp light at an exposure amount of 36 mJ/cm 2 (254 nm wavelength). After the exposure, development was performed for 30 seconds using OK73 thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a developer to form a pattern on the wafer edge portion.
• WEE wafer edge exposure module
• a protective film capable of completely covering the edges of a semiconductor manufacturing substrate (wafer) by a simple coating method, and a protective film-forming composition for forming the protective film. It is possible to provide a product, a semiconductor manufacturing wafer manufactured using the protective film, the semiconductor manufacturing wafer, and a method of manufacturing a semiconductor device.

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Engineering & Computer Science (AREA)
• Metallurgy (AREA)
• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Paints Or Removers (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=85412301

Family Applications (1)

Country Status (7)

Families Citing this family (2)

Citations (6)

Family Cites Families (4)

• 2022
  • 2022-09-01 JP JP2023545669A patent/JPWO2023033094A1/ja active Pending
  • 2022-09-01 WO PCT/JP2022/032897 patent/WO2023033094A1/ja not_active Ceased
  • 2022-09-01 US US18/688,610 patent/US20250014901A1/en active Pending
  • 2022-09-01 TW TW111133180A patent/TW202321337A/zh unknown
  • 2022-09-01 CN CN202280059405.5A patent/CN117940849A/zh active Pending
  • 2022-09-01 KR KR1020247010865A patent/KR20240055047A/ko active Pending
  • 2022-09-01 EP EP22864676.6A patent/EP4398035A4/en active Pending

Patent Citations (6)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events