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
  • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
  • C08F22/10—Esters
  • C08F22/12—Esters of phenols or saturated alcohols
  • C08F22/20—Esters containing oxygen in addition to the carboxy oxygen
• • 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
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/28—Chemically modified polycondensates
  • C08G8/36—Chemically modified polycondensates by etherifying
• • 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
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • 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
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0384—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the main chain 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
  • G03F7/038—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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—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
• • 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
  • G03F7/2026—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 for the removal of unwanted material, e.g. image or background correction
  • G03F7/2028—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 for the removal of unwanted material, e.g. image or background correction of an edge bead on wafers
• • 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
• • 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
  • G03F7/42—Stripping or agents therefor
• • 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
• • 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
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
  • H10P50/286—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials
  • H10P50/287—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials by chemical means
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/01—Manufacture or treatment
• • 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

Definitions

• the present invention relates to a composition for forming a protective film for forming a protective film on the surface edge and bevel portion of a semiconductor manufacturing substrate (wafer) in a semiconductor device manufacturing process, and a protective film formed using the composition for forming a protective film.
• the present invention relates to a film, a wafer for semiconductor manufacturing manufactured using the protective film, a method for manufacturing the wafer for semiconductor manufacturing, and a semiconductor device.
• the chemical solution supplied to the front surface of the wafer wraps around the periphery of the wafer and the back surface, causing unintended contact with the periphery of the wafer and the back surface.
• these areas may be contaminated with metal due to the formation of a coating film.
• wafer processing equipment such as exposure equipment or etching equipment or a wafer transport mechanism
• the wafer may be transported and processed later through these processing equipment or transport mechanisms.
• the wafer may also be contaminated with metal, that is, cross-contamination may occur.
• Patent Document 1 In 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 edge portion of the substrate, that is, the peripheral end face and the back side peripheral edge portion, do not come into contact with the coating film (Patent Document 1).
• Patent Document 2 A method for manufacturing a semiconductor device is disclosed in which peeling of a film from a beveled portion of a substrate is suppressed.
• the problem to be solved by the present invention is to eliminate abnormal shapes (partial bulges or dents) on the surface edges and bevel portions of semiconductor manufacturing substrates (wafers) using a simple coating method in manufacturing semiconductor devices.
• a composition for forming a protective film that can form a protective film with good film condition a protective film formed from the composition for forming a protective film, a wafer for semiconductor manufacturing manufactured using the protective film, a wafer for semiconductor manufacturing
• An object of the present invention is to provide a method for manufacturing a semiconductor device.
• the present invention includes the following.
• [1] Contains a polymer or compound with a crosslinkable group and a solvent, the solvent includes a first solvent and a second solvent, When the evaporation rate of n-butyl acetate is 1, the evaporation rate of the first solvent is 0.10 or more, and the evaporation rate of the second solvent is 0.05 or less.
• the difference (V1-V2) between the evaporation rate (V1) of the first solvent and the evaporation rate (V2) of the second solvent is 0.10 or more, [1] or [2]
• Constituent elements of the first solvent are carbon, oxygen, and hydrogen
• Constituent elements of the second solvent are carbon, oxygen, and hydrogen
• the protective film according to [9] having a thickness of 1 to 10,000 nm.
• the protective film according to [9] or [10] which is a protective film for preventing metal contamination of the wafer surface edge and bevel portion.
• the protective film according to any one of [9] to [11] which is cured by being irradiated with light having a wavelength of 170 to 800 nm.
• [20] The method for manufacturing a semiconductor device according to [18], including a step (Z) of removing the protective film after the step (Y).
• [21] The method for manufacturing a semiconductor device according to any one of [14] to [20], wherein the resist film contains a metal.
• the composition for forming a protective film on the edge of a wafer for semiconductor manufacturing is photosensitive, From [14], the formation of the protective film in the step (X) is performed by applying the composition for forming a protective film on the edge of a semiconductor manufacturing wafer, exposing a predetermined area to light, and developing the composition. 21].
• the removal of the protective film in the step (Z) is performed by ashing, or by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a cleaning solution for semiconductors, [19] or [20]. ] The method for manufacturing a semiconductor device according to.
• a method for manufacturing a wafer for semiconductor manufacturing comprising: The composition for forming a protective film on the edge of a wafer for semiconductor manufacturing according to any one of [1] to [8] is applied to the edge of the wafer precursor, and the formed protective film protects the surface edge and beveled portion. a process for manufacturing protected wafers;
• a method for manufacturing a wafer for semiconductor manufacturing including:
• the surface edges and bevel parts of semiconductor manufacturing substrates can be coated in a film state without abnormal shapes (partial bulges or dents) using a simple coating method.
• composition for forming a protective film on the edge of a wafer for semiconductor manufacturing (hereinafter sometimes referred to as the "composition for forming a protective film") of the present invention is used to protect the surface edge and bevel portion of a wafer for semiconductor manufacturing.
• composition for forming a protective film contains a polymer or compound having a crosslinkable group and a solvent.
• the solvent includes a first solvent and a second solvent.
• the evaporation rate used in the present invention is the evaporation rate obtained according to ASTM D 3539.
• the numerical value of the evaporation rate used in the present invention is a relative value to the evaporation rate of n-butyl acetate. That is, the evaporation rate value used in the present invention is the evaporation rate of the solvent divided by the evaporation rate of n-butyl acetate.
• the evaporation rate of n-butyl acetate is 1, the evaporation rate of the first solvent is 0.10 or more, and the evaporation rate of the second solvent is 0.05 or less.
• the present inventors have conducted intensive studies to form a protective film in good film condition by a simple coating method on the edges of semiconductor manufacturing wafers (surface edges and beveled areas).
• various solvents were tried as the solvent for the composition for forming a protective film, it was found that the evaporation rate affected the coverage of the surface edge and the film shape of the beveled part.
• a solvent with a high evaporation rate easily evaporates
• the coverage of the surface edges will be good, but the shape of the film on the beveled part will be poor (e.g. , partial bulges or dents occurred).
• the film shape of the edge of the semiconductor manufacturing wafer can be measured using, for example, a scanning electron microscope (with magnifications of 20 to 400 times, 30 to 200 times, 40 to 100 times, 50 times, 80 times, etc.). It can be observed at 100x magnification.
• the above-mentioned abnormal shape is present in 10 or less places, preferably 5 or less places, more preferably 3 or less places, even more preferably 1 place or less, and most preferably an abnormal shape in the field of view in the above-mentioned scanning electron microscope observation. is not observed (zero abnormal locations).
• the first solvent and the second solvent are organic solvents.
• the evaporation rate of the first solvent is 0.10 or more, preferably 0.10 to 0.80, more preferably 0.20 to 0.60, particularly preferably 0.30 to 0.50.
• the evaporation rate of the second solvent is 0.05 or less, preferably 0.04 or less, and more preferably 0.03 or less.
• the difference (V1-V2) between the evaporation rate (V1) of the first solvent and the evaporation rate (V2) of the second solvent is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, the difference (V1-V2) is 0. It is preferably 10 or more, more preferably 0.15 or more, and particularly preferably 0.20 or more. Further, the difference (V1-V2) is preferably 0.70 or less, more preferably 0.60 or less, and particularly preferably 0.50 or less.
• the mass ratio (S1:S2) of the first solvent (S1) and the second solvent (S2) is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is 50:50 to 95:5. is preferable, 60:40 to 93:7 is more preferable, and 70:30 to 90:10 is particularly preferable.
• Constituent elements of the first solvent are, for example, carbon, oxygen, and hydrogen.
• Constituent elements of the second solvent are, for example, carbon, oxygen, and hydrogen.
• the first solvent preferably does not contain nitrogen atoms or halogen atoms as constituent elements.
• the second solvent preferably does not contain nitrogen atoms or halogen atoms as constituent elements.
• the first solvent contains, for example, at least one of an ether bond, an ester bond, and a carbonyl group.
• the second solvent contains, for example, at least one of an ether bond, an ester bond, and a carbonyl group.
• the solvent may contain an organic solvent other than the first solvent and the second solvent.
• the total proportion of the first solvent and the second solvent in the solvent is not particularly limited, but is preferably 50% by mass to 100% by mass, more preferably 75% to 100% by mass, and 90% to 100% by mass. % is particularly preferred.
• the content of the solvent in the composition for forming a protective film is not particularly limited, but is preferably 70% by mass to 99% by mass, more preferably 75% to 98% by mass, and particularly preferably 80% to 95% by mass. .
• the total content of the first solvent and the second solvent in the composition for forming a protective film is not particularly limited, but is preferably 50% by mass to 99% by mass, more preferably 60% by mass to 98% by mass, Particularly preferred is 75% by weight to 95% by weight.
• a crosslinkable group means a group that can form 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, (meth)acrylic groups, vinyl groups, carboxyl groups, thiol groups, silanol groups, cinnamoyl groups, and hydroxyl groups (including phenolic hydroxyl groups).
• polymer and “compound” do not necessarily mean different substances, and a substance containing a polymer is sometimes referred to as a "compound.”
• the protective film (cured film) using the above-mentioned “polymer” and “compound” has, for example, an evaluation based on "[5] Post-exposure curability evaluation” in the Examples described later, with respect to the unexposed part of the film. It exhibits solubility in a developer such that the residual film rate of the cured film in the exposed area is 80% or more, preferably 90% or more.
• Examples of the polymer or compound having a crosslinkable group include, but are not limited to, the following.
• ⁇ Epoxy (meth)acrylate e.g., reaction product of glycidyl ether of cresol novolac resin and (meth)acrylic acid
• ⁇ Cinnamic acid grafted epoxy novolac, -phenoplast a thermosetting material obtained by polycondensation of phenols and aldehydes with removal of water and the formation of a three-dimensional network
• melamine resins such as trimethylolmelamine and hexamethylolmelamine, urea resins such as dimethylolpropylene urea, dimethylolethylene urea, and dimethylolhydroxyne urea
• aminoblast resins such as dimethyloluron resin
• ⁇ (Block) isocyanate ⁇ Vinyl ether, ⁇ Polysiloxane resin with (meth)acrylic group ⁇ Epoxy resin.
• An example of a polymer or compound having a crosslinkable group is a polymer having a structural unit represented by the following formula (1-1).
• Ar represents a benzene ring, a naphthalene ring, or an anthracene ring
• R 1 is a hydroxy group, a mercapto group that may be protected with a methyl group, or an amino group that may be protected with a methyl group.
• n1 represents an integer of 0 to 3
• L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms
• n2 represents 1 or 2
• A represents a group having a (meth)acryloyloxy group
• alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group.
• alkylene groups having 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, cyclopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, cyclo Butylene group, 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group , 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene group, cyclopentylene group, 1-methyl -Cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-d
• C1-C10 alkyl group substituted or interrupted by a heteroatom in R 1 is a C1-C10 alkoxy group.
• alkoxy group having 1 to 10 carbon atoms examples include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n- Pentoxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3- Methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group , 2, 2,
• A is, for example, a group represented by the following formula (A).
• R a is a hydrogen atom or a methyl group. * represents a bond.
• the unit structure represented by formula (1-1) may be one type or a combination of two or more types.
• it may be a copolymer having a plurality of unit structures in which Ar is the same type, or a copolymer in which the types of Ar are different, such as a unit structure in which Ar has a unit structure containing a benzene ring and a unit structure containing a naphthalene ring.
• copolymers having a plurality of unit structures are not excluded from the technical scope of the present application.
• any carbon-carbon atom in the alkylene group shown on the left may be a heteroatom (i.e., in the case of oxygen, an ether bond,
• any carbon-carbon atom in the alkylene group shown on the left may be a heteroatom (i.e., in the case of oxygen, an ether bond
• sulfur it is interrupted by a sulfide bond), ester bond, or amide bond
• 1 carbon atom i.e., methylene group
• heteroatom i.e., in the case of oxygen
• T1 represents a single bond or an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond or an amide bond, but a combination of an ether bond and a methylene group, A combination of an ester bond and a methylene group, or a combination of an amide bond and a methylene group is preferred.
• An alkyl group having 1 to 10 carbon atoms that may be substituted with a hetero atom means that one or more hydrogen atoms of the alkyl group having 1 to 10 carbon atoms are substituted with a hetero atom (preferably a halogeno group). It means that something is being done.
• L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and is preferably represented by the following formula (1-2).
• R 2 and R 3 are independently hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i- represents a butyl group, s-butyl group, t-butyl group, or cyclobutyl group, and R 2 and R 3 may be bonded to each other to form a ring having 3 to 6 carbon atoms).
• both R 2 and R 3 are hydrogen atoms (that is, -(CR 2 R 3 )- is a methylene group)
• halogeno group refers to halogen-X (F, Cl, Br, I) substituted with hydrogen.
• a polymer having a structural unit represented by the formula (1-1) can be obtained by, for example, reacting a polymer having a unit structure represented by the following formula (1-1') with (meth)acrylic acid. can get.
• Ar, R 1 , n1, L 1 , n2, and T 1 are Ar, R 1 , n1, L 1 , n2, and T 1 in formula (1-1).
• E is a group having an epoxy group.
• the polymer having the structural unit represented by formula (1-1') is not particularly limited, for example, as long as it satisfies the unit structure of formula (1-1'). It may be manufactured by a method known per se. Commercially available products may be used. Commercially available products include heat-resistant epoxy novolac resin EOCN (registered trademark) series (manufactured by Nippon Kayaku Co., Ltd.), epoxy novolac resin D.E.N (registered trademark) series (manufactured by Dow Chemical Japan Co., Ltd.), etc. Can be mentioned.
• EOCN registered trademark
• D.E.N registered trademark
• the weight average molecular weight of the polymer having a structural unit represented by formula (1-1') is 100 or more, 500 to 200,000, 600 to 50,000, or 700 to 10,000. It is.
• Examples of the polymer having a structural unit represented by formula (1-1') include those having the following unit structure.
• Me represents a methyl group and Et represents an ethyl group.
• the weight average molecular weight of the polymer or compound having a crosslinkable group is not particularly limited, but is preferably from 2,000 to 50,000, more preferably from 2,500 to 25,000, particularly from 3,000 to 9,000. preferable. Weight average molecular weight can be measured by gel permeation chromatography (GPC).
• the content of the polymer or compound having a crosslinkable group in the composition for forming a protective film is not particularly limited, but is preferably 1% by mass to 30% by mass, more preferably 5% to 25% by mass, and 10% by mass. ⁇ 20% by weight is particularly preferred.
• the content of the polymer or compound having a crosslinkable group in the composition for forming a protective film is not particularly limited, but is preferably 70% to 99% by mass, and 80% to 97% by mass based on the film constituent components. More preferably, 85% by mass to 95% by mass is particularly preferred.
• the film constituent component is a component obtained by removing volatile components (solvent) from the composition for forming a protective film.
• the composition for forming a protective film 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), and a thermal base.
• a radical polymerization initiator such as a photopolymerization initiator
• an acid catalyst
• a thermal acid generator a photoacid generator
• a base catalyst
• thermal base a thermal base.
• Any radical polymerization initiator may be used as long as it is capable of releasing a substance that initiates radical polymerization upon irradiation with light and/or heating.
• a photoradical polymerization initiator 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-hydroxycyclohexylphenylketone, 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 to these.
• photoradical polymerization initiator examples thereof include IRGACURE (registered trademark) 651, 184, 369, and 784 manufactured by BASF Japan.
• IRGACURE registered trademark
• commercially available products other than those mentioned above can also be used, specifically IRGACURE (registered trademark) 500, 907, 379, 819, 127, 500, 754, 250, 1800, 1870, OXE01, DAROCUR manufactured by BASF Japan Co., Ltd.
• 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, dilauroyl Peroxide, 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'-azo
• thermal radical polymerization initiators include, for example, Perloyl (registered trademark) IB, NPP, IPP, SBP, TCP, OPP, SA, 355, L, Perbutyl (registered trademark) ND, NHP, manufactured by NOF Corporation.
• 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, 20 parts by mass or less, per 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-butylphenol, etc.
• -Butyl cresol 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-hydroxyphenyl) propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(2,6-di
• 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 commercially available product may be used as the polymerization inhibitor, and a specific example is Irganox-3114 (manufactured by BASF Japan Co., Ltd.).
• the content of the polymerization inhibitor is preferably 0.01 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, per 100 parts by weight 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; polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol 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, polyoxy Examples include polyoxyethylene sorbitan fatty acid ester compounds such as ethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan tristearate.
• polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and
• the product names are FTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), the product names Megafac F171, F173, R-08, R-30 (manufactured by Dainippon Ink Co., Ltd.), Florado FC430, FC431. (manufactured by Sumitomo 3M Ltd.), product name Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Ltd.) and other fluorine-based surfactants and organosiloxane polymers. Examples include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
• 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, based on 100 parts by mass of the polymer or compound having a crosslinkable group.
• acid catalyst acidic compounds, basic compounds, or various compounds that generate acids or bases when exposed to 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, and as the compound that generates a base by heat, urea can be used.
• amine compounds include triethanolamine, tributanolamine, trimethylamine, triethylamine, trin-propylamine, triisopropylamine, 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.
• ammonium hydroxide compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, cetyltrimethylammonium hydroxide, Examples include phenyltrimethylammonium hydroxide and phenyltriethylammonium hydroxide.
• the acid generator either a thermal acid generator or a photoacid generator can be used.
• thermal acid generators examples include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), and 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 4-hydroxybenzenesulfonic acid
• benzenedisulfonic acid 1-naphthalenesulfonic acid
• citric acid benzoic acid
• 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, TAG2689 manufactured by King Industries
• Examples include SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (all manufactured by Sanshin Kagaku Kogyo Co., Ltd.).
• photoacid generators examples include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloximide, benzoin sulfonate type photoacid generators, pyrogallol trisulfonate type photoacid generators, sulfone type photoacid generators, and glyoxime derivative type photoacid generators.
• acid 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 generator examples include carbamates such as 1-methyl-1-(4-biphenylyl)ethyl carbamate and 2-cyano-1,1-dimethylethyl carbamate; 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, tetramethyl phenylpropiolate Examples include
• U-CAT registered trademark
• SA810, SA831, SA841, and SA851 which are salts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), are also available from San-Apro Co., Ltd. )] etc.
• -2-yl)ethyl N,N-dicyclohexyl carbamate
• dicyclohexylammonium 2-(3-benzoylphenyl) propionate
• 9-anthryl N-cyclohexyl carbamate
• 1-(9,10-anthraquinon-2-yl)ethyl N-Cyclohexyl carbamate
• cyclohexylammonium 2-(3-benzoylphenyl) propionate
• the above components can be used alone or in combination of two or more, and in that case, they are used in an amount of usually 10% by mass or less, preferably 3% by mass or less based on the solid content of the composition for forming a protective film. It will be done.
• the method for preparing the composition for forming a protective film is not particularly limited. That is, a polymer or compound having a crosslinkable group, a solvent, and other components may be mixed in any ratio and in any order to form a uniform solution.
• the composition for forming a protective film in a solution state thus prepared 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, more preferably 50 cps or less, Particularly preferred is 10 cps or less.
• the viscosity is a value measured at 25°C using an E-type viscometer.
• the composition for forming a protective film is photosensitive.
• it may be of a negative solvent development type.
• the composition for forming a photosensitive protective film (negative type) is applied to the front edge, beveled portion, and optionally back edge of the substrate. After that, by exposing and developing the portion of the film to be cured, it becomes possible to accurately cover the beveled portion with the protective film.
• Being photosensitive makes it easy to control the thickness of the protective film at the wafer edge, eliminates inner humps, improves the edge shape, and corrects misalignment of the center position during spin coating. There are advantages such as
• the composition for forming a protective film is a compound ( E).
• the compound (E) is a polymer or compound having a crosslinkable group.
• 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 may be optionally substituted with one or more amide or amino groups), oxygen atom, carbonyl group, sulfur atom, -C(O)-NR a -, -NR b -, or those Represents a divalent group consisting of a combination of R 5 is each 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 (optionally substituted with an amide group or an amino group), an oxygen atom, a carbonyl group, a sulfur atom, -C(O)-NR a - and -NR b - Represents a
• R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
• R b represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkylcarbonyl group having 1 to 10 carbon atoms
• n represents the number of repeating units from 1 to 10
• dotted lines represent chemical bonds with adjacent atoms.
• the composition for forming a protective film may contain polysiloxane.
• the polysiloxane may be a modified polysiloxane in which some of the silanol groups are modified, such as a modified polysiloxane in which some of the silanol groups are alcohol-modified or acetal-protected.
• the polysiloxane may be, for example, a hydrolyzed condensate of a hydrolyzable silane, or a modified product in which at least a portion of the silanol groups of the hydrolyzed condensate are alcohol-modified or acetal-protected (hereinafter referred to as may also be referred to as "modified hydrolyzed condensate").
• the hydrolyzable silane related to the hydrolyzed condensate can contain one or more types of hydrolyzable silane.
• the polysiloxane can have a structure having any of a cage type, ladder type, linear type, and branched type main chain. Furthermore, commercially available polysiloxanes can be used.
• the "hydrolytic condensate" of hydrolyzable silane that is, the product of hydrolytic condensation, includes not only a polyorganosiloxane polymer that is a condensate that has completely completed condensation, but also a polyorganosiloxane polymer that is a condensate that has completely completed condensation. Also included are polyorganosiloxane polymers that are incompletely partially hydrolyzed condensates. Similar to completely condensed condensates, such partially hydrolyzed condensates are also polymers obtained by hydrolysis and condensation of hydrolyzable silanes, but only partially hydrolyzed and condensed. Therefore, the Si--OH group remains.
• Examples of the polysiloxane of the present invention include hydrolyzed condensates of hydrolyzable silanes containing at least one type of hydrolyzable silane represented by the following formula (1), or modified products thereof.
• R 1 is a group bonded to a silicon atom, which independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group.
• group optionally substituted halogenated alkyl group, optionally substituted halogenated aryl group, optionally substituted halogenated aralkyl group, optionally substituted alkoxyalkyl group, optionally substituted an organic group representing a good alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or having an epoxy group, an organic group having an acryloyl group, 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 or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• a represents an integer from 0 to 3.
• each group and atom in R 1 in formula (1) and their preferred carbon numbers 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 and carbon atoms described above for X in formulas (A-1) and (A-2). I can list a number of them.
• hydrolyzable silanes represented by formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n.
• -butoxysilane methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, Methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxy Silane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -g
• composition for forming a protective film is described in JP-A No. 2016-003160,
• (A) polyfunctional epoxy (meth)acrylate compound may contain (B) a polyfunctional thiol compound and (C) a radical polymerization initiator.
• (A) The polyfunctional epoxy (meth)acrylate compound is a polymer or compound having a crosslinkable group.
• the molecular weight of component (A) may be 300 to 20,000.
• the component (A) may be a bisphenol type polyfunctional epoxy (meth)acrylate compound.
• the above component (B) may be liquid at 25°C.
• (D) a polymerization inhibitor may be contained.
• the viscosity at 25° C. may be 2,000 to 100,000 mPa ⁇ s.
• the composition for forming a protective film may be a film-forming composition containing a photopolymerizable substance and a photopolymerization initiator, as described in WO2009/104643.
• Photopolymerizable substances are polymers or compounds with crosslinkable groups.
• the photopolymerizable substance may be a compound having at least one cationically 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 reactive group capable of radical polymerization, and the photopolymerization initiator may be a radical photopolymerization initiator.
• the photopolymerizable substance may be a sugar compound.
• the sugar compound may be a monosaccharide or a disaccharide compound.
• the sugar compound has 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 each 0 or 1 p is an integer and is the total number of hydroxyl groups that the sugar has;
• m is an integer satisfying 1 ⁇ m ⁇ (pm).
• the photopolymerizable substance 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 has formula (2) or formula (3):
• G 2 represents an alkylene group, carbonyloxy group, heterocycle, aromatic ring, or a monovalent to pentavalent linking group having a combination thereof
• G 3 represents an alkyl group, an alkylcarbonyl group, a heterocycle, an aromatic ring. It may be an organic group having a ring or a combination thereof, where n and m each represent an integer of 1 to 5).
• the protective film of the present invention is a cured product of a coating film made of the composition for forming a protective film of the present invention.
• Examples of the method for forming the protective film include step (X) in the method for manufacturing a semiconductor device, which will be described later.
• the protective film is, for example, a protective film for preventing metal contamination of the wafer surface edge and bevel portion.
• the lower limit of the thickness of the protective film is, for example, 1 nm, 3 nm, 5 nm, 10 nm, 30 nm, 50 nm, 80 nm, 100 nm, 200 nm, 500 nm, 800 nm, 1,000 nm, 1,500 nm, 1,700 nm.
• the upper limit of the thickness of the protective film is, for example, 10,000 nm, 9,000 nm, 8,000 nm, 7,000 nm, 6,000 nm, 5,000 nm, 4,000 nm, 3,800 nm, 3,700 nm, 3,600 nm, 3 , 500nm, 3,300nm, 3,000nm, 2,500nm, 2,000nm, 1,500nm, 1,000nm, 800nm, 500nm, and 300nm.
• the protective film is, for example, a protective film that is cured by being irradiated with light having a wavelength of 170 to 800 nm (for example, 254 nm).
• the characteristics of the protective film that covers the surface edges and bevels of semiconductor manufacturing substrates include the ability to prevent metal contamination, as well as dry etching resistance, phosphoric acid resistance, tetramethylammonium hydroxide (TMAH) resistance, HF removability, scratch resistance, good embedding into stepped substrates, low amount of sublimation, affinity for hydrophobic substrates, no crater foreign matter left on the wafer side (bevel part), good edge shape, inner hump ( It is desirable to satisfy the function of suppressing the phenomenon in which the film-forming composition remains in the form of a bump directly under the injection hole of the nozzle.
• TMAH tetramethylammonium hydroxide
• the method for manufacturing a semiconductor device includes: (A) a step of forming a resist film on the semiconductor substrate; (B) forming a resist pattern by irradiating the resist film with light or electron beam and subsequent development; (C) Processing the semiconductor substrate by etching using the resist pattern as a mask; In a method of manufacturing a semiconductor device including, A step (X) of forming a protective film using the composition for forming a protective film of the present invention on the front edge, the bevel part, and optionally the back edge of a wafer for semiconductor manufacturing; This is a method for manufacturing a semiconductor device.
• step (A) a resist film is formed on the semiconductor substrate.
• Semiconductor substrates are wafers used for manufacturing semiconductor devices, etc., and include commonly used silicon wafers and germanium wafers, as well as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.
• Compound semiconductor wafers made by combining two or more types of elements, such as, can be used. These are usually disc-shaped and have dimensions of, for example, 4, 6, 8, or 12 inches. Commercially available products may be used.
• the inorganic film can be 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 evaporation method. method, 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-Phosphosilicate Glass) film, a titanium nitride film, a titanium nitride oxide film, a tungsten film, a gallium nitride film, and a gallium arsenide film.
• a polysilicon film a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phosphosilicate Glass) film
• titanium nitride film a titanium nitride oxide film
• tungsten film a gallium nitride film
• gallium arsenide film examples include a gallium arsenide film.
• a resist underlayer film, a resist film, etc. of a predetermined thickness are formed using an appropriate coating method such as a spray, a spinner, or a coater.
• an appropriate coating method such as a spray, a spinner, or a coater.
• each of the resist underlayer film forming composition, the resist film forming composition, etc. is supplied from above the center of a rotating disc-shaped substrate through a nozzle or the like.
• these films are baked using a heating means such as a hot plate.
• the photoresist used to form the resist film is not particularly limited as long as it is sensitive to the light used for exposure. Note that in this specification, electron beam resist is also included in photoresist. Both negative photoresists and positive photoresists can be used.
• a positive photoresist consisting of a novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified photoresist consisting of a binder having a group that decomposes with acid and increases the rate of alkali dissolution, and a photoacid generator;
• a chemically amplified photoresist comprising a low molecular weight 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 consisting of a photoacid generator and a low-molecular compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, and resists containing metal elements.
• Examples include product name V146G manufactured by JSR Corporation, product name APEX-E manufactured by Shipley, product name PAR710 manufactured by Sumitomo Chemical Co., Ltd., and product names AR2772 and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd.
• Proc. SPIE Vol. 3999, 330-334 (2000)
• Examples include fluorine-containing atom polymer photoresists such as those described in 3999, 365-374 (2000). Preferably it is a negative photoresist.
• the resist film forming composition used to form 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.
• the metal species is not particularly limited, but examples include tin, indium, antimony, bismuth, gallium, germanium, aluminum, zirconium, hafnium, cerium, lanthanum, and cesium.
• the resist film forming composition used for forming the resist film may be a metal-containing resist.
• the metal-containing resist is also called a metal oxide resist (metal oxide resist (MOR)), and a typical example is a tin oxide resist.
• metal oxide resist materials include coating compositions containing metal oxo-hydroxo networks having organic ligands through metal carbon bonds and/or metal carboxylate bonds, as described in JP-A-2019-113855. .
• metal-containing resist uses peroxo ligands as radiation-sensitive stabilizing ligands. The peroxo-based metal oxo-hydroxo compound is explained in detail in, for example, the patent document described in paragraph [0011] of Publication No.
• Patent Documents include, for example, US Patent No. 9,176,377B2, US Patent Application Publication No. 2013/0224652A1, US Patent No. 9,310,684B2, and US Patent Application Publication No. 2016. /0116839A1 and US Patent Application Publication No. 15/291738.
• the baking conditions for the resist film are appropriately selected from baking temperatures of 70° C. to 400° C. and baking times of 0.3 minutes to 60 minutes.
• the baking temperature is 80°C to 350°C and the baking time is 0.5 to 30 minutes, more preferably the baking temperature is 90°C to 300°C, and the baking time is 0.8 to 10 minutes.
• the lower limit of the average thickness of the resist film is preferably 1 nm, more preferably 3 nm, 5 nm, or 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 from the composition for forming a protective film of the present invention on the front edge, beveled part, and optionally back edge of a wafer for semiconductor manufacturing is performed at any time.
• step (X) preferably, a composition for forming a protective film is applied, and a predetermined area is exposed to light 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 a device portion such as a resist film is provided is referred to as the front surface, and the surface opposite thereto is referred to as the back surface.
• the front edge refers to an area with a width of usually 1 to 10 mm from the edge of the device section provided on the board to the bevel
• the bevel refers to the area that connects the front edge and the back edge.
• the curved area (side surface of the wafer) is referred to as the backside edge
• the backside edge is the area corresponding to the frontside edge of the backside of the substrate.
• a composition for forming a protective film is applied to a semiconductor substrate.
• the method for applying the composition for forming a protective film is not particularly limited, and for example, known means such as a spin coating method, a spray method, etc. can be employed.
• the protective film forming composition is supplied through a nozzle from above or near the surface end of the rotating disk-shaped substrate while rotating the semiconductor substrate at a predetermined rotation speed.
• the bevel portion and/or the back end of the substrate are also supplied through nozzles from near each.
• the conditions for spin coating can be selected as appropriate and are not limited in any way, but typical conditions are as follows.
• ⁇ Viscosity of the composition for forming a protective film Approximately 100 cps or less ⁇ Wafer rotation speed: ...When supplying the composition for forming a protective film: 50 to 500 rpm ⁇ During shaking off: 700 to 2,000 rpm ⁇ Protective film thickness: 300nm
• the protective film forming composition is exposed to light. Exposure is performed by applying actinic rays such as ultraviolet rays, visible rays, and radiation to the composition for forming a protective film through a mask or without a mask (i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), This can be done by irradiating with EB (including electron beam).
• actinic rays such as ultraviolet rays, visible rays, and radiation
• EB including electron beam
• soft baking SB
• PEB post-exposure heating
• the temperature of post-exposure heating is preferably 50° C. to 150° C.
• the time of post-exposure heating is preferably 1 minute to 10 minutes.
• the protective film forming composition after exposure is developed.
• Development can be carried out by removing the exposed area of the composition for forming a protective film after exposure with a developer, and the development temperature is appropriately selected from 5° C. to 50° C. and the developing time from 10 seconds to 300 seconds.
• Examples of the organic solvent contained in the developer include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, and hydrocarbon solvents.
• the organic solvent of the developer preferably contains an ester solvent, a ketone solvent, or a combination thereof.
• the above-mentioned developer may contain one type of organic solvent alone, or may contain two or more types of organic solvents.
• alcoholic solvents include aliphatic monoalcohols 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; Solvents include polyhydric alcohol partial ether solvents 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; 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 and aromatic ring-containing ether solvents such as anisole.
• ketone solvents include 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.
• ketone solvents cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, and other cyclic ketone solvents: 2,4-pentanedione, acetonyl Examples include acetone and acetophenone.
• amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, Examples include chain amide solvents such as N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.
• ester solvents include monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate; polyhydric alcohol carboxylate solvents such as propylene glycol acetate; and polyhydric alcohol partial ether carboxylic acid solvents such as propylene glycol monomethyl ether acetate.
• rate solvents include rate solvents; polyhydric carboxylic acid diester solvents such as diethyl oxalate; carbonate 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. Can be mentioned. Among these, ester solvents, ketone solvents, ether solvents, and combinations thereof are preferred, and ester solvents, ketone solvents, and combinations thereof are more preferred.
• ester solvent propylene glycol monomethyl ether acetate is preferred.
• ketone solvent cyclohexanone is preferred.
• ether solvent propylene glycol monomethyl ether is preferred.
• 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.
• 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 mass.
• alcohols and surfactants may be added to the developer.
• Each of these can be blended in an amount 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.
• the surfactant include ionic and nonionic fluorine-based surfactants, silicon-based surfactants, and the like.
• Development methods include, for example, a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and the substrate is 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 is continuously applied while scanning the developer application nozzle at a constant speed onto a rotating substrate (dynamic dispensing method). etc.
• the heating temperature in the heat treatment is usually in the range of 150°C or higher and 350°C or lower, preferably 200 to 300°C.
• the heat treatment time is the time until the composition for forming a protective film is cured, and in consideration of productivity, it is preferably less than 30 minutes.
• the lower limit of the thickness of the protective film is preferably 1 nm, more preferably 3 nm.
• the upper limit of the thickness of the protective film is preferably 500 nm, more preferably 300 nm.
• step (X) is performed before step (A). Then, for example, in step (A), a resist film is formed on at least a portion of the protective film. In that case, a step (Y) of removing the resist film above the protective film is performed. In step (Y), the resist film above the protective film can be removed using a removal solution. At this time, as in step (X) above, it is preferable to apply the removal liquid to the front end, bevel part, and optionally back end of the semiconductor manufacturing wafer.
• Examples of the resist removing liquid include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, water, butyl acetate, an aqueous tetramethylammonium solution, or a mixture thereof.
• propylene glycol monomethyl ether acetate and water are preferred from the viewpoint of resist film removability.
• step (Z) of removing the protective film is performed.
• the protective film is preferably removed by ashing, or the protective film is preferably removed by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a cleaning solution for semiconductors. This is done by Thereafter, it is preferable to wash with any solvent or a conventional semiconductor cleaning solution.
• 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).
• a step (Z) of removing the protective film can be performed between the step (Y) and the step (B).
• protective A step (Z) of removing the film can also be performed.
• step (B) a resist pattern is formed by irradiating the resist film with light or an electron beam and subsequent development.
• the resist film is irradiated with light or electron beams through a mask (reticle) for forming a predetermined pattern. ) is used.
• a mask reticle
• soft baking SB
• PEB post-exposure heating
• the temperature of post-exposure heating is preferably 50° C. to 150° C.
• the time of post-exposure heating is preferably 1 minute to 10 minutes.
• an alkaline developer is used, and the development temperature is appropriately selected from 5° C. to 50° C. and the developing time from 10 seconds to 300 seconds.
• alkaline developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and 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, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc.
• Aqueous solutions of alkalis such as quaternary ammonium salts, pyrrole, cyclic amines such as piperidine, etc. can be used.
• the base concentration of these aqueous solutions is not particularly limited, but can be, for example, 0.1 to 10% by mass.
• an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the aqueous solution of the alkali.
• an alcohol such as isopropyl alcohol or a nonionic surfactant
• Each of these can be blended in an amount 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 are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline.
• surfactants and the like can also be added to these developers.
• an alkaline developer develop 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 to remove areas where the alkali dissolution rate of the resist has not improved.
• a method of developing can also be used.
• the semiconductor substrate subjected to the above exposure and development is baked.
• the baking means is not particularly limited, for example, a proximity baking oven that uses a plurality of substrate support pins to ensure 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 lower 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 baking means and conditions 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 lower.
• step (C) the semiconductor substrate is processed by etching using the resist pattern as a mask.
• a semiconductor substrate is processed by etching using the formed resist pattern as a mask.
• the resist underlayer film is etched, preferably dry etched, to form a patterned resist.
• the semiconductor substrate is processed using the patterned resist using a method known per se (dry etching method, etc.).
• the etching for processing the semiconductor substrate may be a known method.
• the semiconductor substrate is a silicon substrate
• a step of processing the shape by dry etching using a fluorine-based gas such as carbon tetrafluoride may be used.
• a surface treatment process such as removing the silicon nitride film present on the surface of the semiconductor substrate with hot phosphoric acid.
• a semiconductor device can be manufactured through the above steps.
• the method for manufacturing a wafer for semiconductor manufacturing of the present invention includes applying the composition for forming a protective film of the present invention to the edge of a wafer precursor, and producing a wafer whose surface edge and bevel portion are protected by the formed protective film. Including the process of manufacturing.
• the protective film-forming composition is applied, for example, to the front edge, the bevel, and optionally the back edge of the wafer precursor.
• a wafer precursor is one obtained by subjecting a semiconductor substrate to at least one step of a method for manufacturing a semiconductor device.
• a process of forming an inorganic film, a resist lower layer film, a resist film, etc. on a semiconductor substrate is performed, and for example, the resist film is irradiated with light or an electron beam.
• Examples include materials before being subjected to a step of forming a resist pattern by subsequent development.
• the composition for forming a protective film of the present invention is applied to the front edge, bevel portion, and optionally back edge of a wafer precursor obtained through one or more steps of a semiconductor device manufacturing process. Apply by spin coating.
• the semiconductor substrate may be baked.
• the baking means is not particularly limited, but for example, a proximity baking oven that uses a plurality of substrate support pins to ensure a gap between the substrate and the hot plate is preferably used.
• the baking temperature is usually 40°C to 300°C, preferably 200 to 300°C, for 1 to 30 minutes.
• the end face of the protective film may be subjected to known treatments in semiconductor manufacturing processes, 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 wafer edge is protected, and is formed by coating the wafer edge with the composition for forming a protective film of the present invention. be.
• the equipment and conditions used to analyze the physical properties of the samples are as follows.
• the molecular weight used in the present invention is the molecular weight obtained in terms of polystyrene by GPC analysis.
• GPC measurement was performed using a GPC device (trade name: HLC-8320GPC, manufactured by Tosoh Corporation), GPC columns (TSKgel Super-Multipore HZ-N (2 pieces)), column temperature: 40°C, eluent (elution solvent): tetrahydrofuran, The flow rate (flow rate) was 0.35 mL/min, and the standard sample was polystyrene (manufactured by Sigma-Aldrich).
• the evaporation rate used in the present invention is the evaporation rate obtained according to ASTM D 3539.
• the numerical value of the evaporation rate used in the present invention is a relative value to the evaporation rate of n-butyl acetate. That is, the evaporation rate value used in the present invention is the evaporation rate of the solvent divided by the evaporation rate of n-butyl acetate.
• Propylene glycol monomethyl ether (evaporation rate 0.71) Propylene glycol monomethyl ether acetate (evaporation rate 0.34) Ethyl lactate (evaporation rate 0.23) Dipropylene glycol methyl ether (evaporation rate 0.03) 1,3-butylene glycol diacetate (evaporation rate 0.01 or less)
• ⁇ Synthesis example 2> Add 48.76 g of propylene glycol monomethyl ether (PGME) to 15.00 g of product name EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), 4.98 g of acrylic acid, 0.88 g of tetrabutylphosphonium bromide, and 0.04 g of hydroquinone. The mixture was heated and stirred at 100° C. for 18 hours under a nitrogen atmosphere.
• PGME propylene glycol monomethyl ether
• EOCN-104S product name
• good coverage means that the thickness of the protective film at a point 500 ⁇ m inside from the outermost edge of the wafer surface is 80% or more of the thickness of the protective film at a point 1500 ⁇ m inner from the outermost edge.
• Slightly poor coverage means that the thickness of the protective film at a point 500 ⁇ m inside from the outermost edge of the wafer surface is 30% or more and less than 80% of the thickness of the protective film at a point 1500 ⁇ m inside from the outermost edge.
• Point. Poor coverage means that the thickness of the protective film at a location 500 ⁇ m inside from the outermost edge of the wafer surface is less than 30% of the thickness of the protective film at a location 1500 ⁇ m inner from the outermost edge.
• Viscosity measurement The viscosity of each protective film forming composition was measured using an E-type viscometer (TVE-22L (manufactured by Toki Sangyo Co., Ltd.), sample volume 1.1 mL, cone rotor 1° 34', R24). , measured at 25°C. The results are shown in Table 2.
• N/A indicates that the film thickness after coating was too thin to be evaluated.

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