WO2022050405A1 - ウェハー処理方法 - Google Patents
ウェハー処理方法 Download PDFInfo
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- WO2022050405A1 WO2022050405A1 PCT/JP2021/032640 JP2021032640W WO2022050405A1 WO 2022050405 A1 WO2022050405 A1 WO 2022050405A1 JP 2021032640 W JP2021032640 W JP 2021032640W WO 2022050405 A1 WO2022050405 A1 WO 2022050405A1
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- 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
- H10P74/00—Testing or measuring during manufacture or treatment of wafers, substrates or devices
- H10P74/20—Testing or measuring during manufacture or treatment of wafers, substrates or devices characterised by the properties tested or measured, e.g. structural or electrical properties
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- 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
- H10P74/00—Testing or measuring during manufacture or treatment of wafers, substrates or devices
- H10P74/20—Testing or measuring during manufacture or treatment of wafers, substrates or devices characterised by the properties tested or measured, e.g. structural or electrical properties
- H10P74/203—Structural properties, e.g. testing or measuring thicknesses, line widths, warpage, bond strengths or physical defects
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70483—Information management; Active and passive control; Testing; Wafer monitoring, e.g. pattern monitoring
- G03F7/70605—Workpiece metrology
- G03F7/70608—Monitoring the unpatterned workpiece, e.g. measuring thickness, reflectivity or effects of immersion liquid on resist
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
- G03F7/70908—Hygiene, e.g. preventing apparatus pollution, mitigating effect of pollution or removing pollutants from apparatus
- G03F7/70925—Cleaning, i.e. actively freeing apparatus from pollutants, e.g. using plasma cleaning
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- 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
- H10P70/00—Cleaning of wafers, substrates or parts of devices
- H10P70/10—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H10P70/15—Cleaning before device manufacture, i.e. Begin-Of-Line process by wet cleaning only
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- 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
- H10P74/00—Testing or measuring during manufacture or treatment of wafers, substrates or devices
- H10P74/23—Testing or measuring during manufacture or treatment of wafers, substrates or devices characterised by multiple measurements, corrections, marking or sorting processes
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- 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
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- 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
- H10P90/00—Preparation of wafers not covered by a single main group of this subclass, e.g. wafer reinforcement
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- 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
- H10P90/00—Preparation of wafers not covered by a single main group of this subclass, e.g. wafer reinforcement
- H10P90/12—Preparing bulk and homogeneous wafers
Definitions
- the present application relates to a wafer processing method such as a method for detecting impurities on the surface of a silicon wafer for semiconductor manufacturing, a method for manufacturing a wafer for semiconductor manufacturing from which impurities on the surface of the wafer have been removed, and a method for selecting a wafer for semiconductor manufacturing.
- Wafers made of materials such as silicon used in semiconductor manufacturing are required to reduce impurities such as surface foreign substances as much as possible.
- Patent Document 1 a reflective subject having a photoresist coating film formed on a semiconductor substrate such as a silicon substrate can be used to detect foreign substances embedded in the photoresist coating film with high reliability.
- the foreign matter detection method that can be done is described.
- a method for detecting impurities on the surface of a silicon wafer for semiconductor manufacturing which cannot be detected by a conventional inspection method, a method for manufacturing a wafer for semiconductor manufacturing from which impurities on the surface of the wafer have been removed, and a method for selecting a wafer for semiconductor manufacturing. That is.
- the present invention includes the following.
- a method for detecting impurities on the surface of a wafer for semiconductor manufacturing comprises a step of applying a film forming composition to the surface of the wafer and firing the film to form a film, and then a step of detecting impurities by a wafer inspection device.
- a method for manufacturing a wafer for semiconductor manufacturing from which impurities on the wafer surface have been removed A step of heating the wafer (I) for manufacturing a crude semiconductor to 100 ° C. to 500 ° C. and / or a step of cleaning with ultrapure water (A).
- the number of defects existing on the surface thereof is reduced by 80% or more as compared with the wafer for crude semiconductor manufacturing (I).
- a method for manufacturing a wafer for semiconductor manufacturing from which impurities on the wafer surface have been removed which comprises the step (C) for selecting (IV).
- a method for selecting wafers for semiconductor manufacturing A step of heating the wafer (I) for manufacturing a crude semiconductor to 100 ° C. to 500 ° C. and / or a step of cleaning with ultrapure water (A).
- the semiconductor manufacturing wafers (III) that have undergone the step (B) the number of defects existing on the surface thereof is reduced by 80% or more as compared with the crude semiconductor manufacturing wafer (IV).
- the number of defects existing on the surface of the wafer (III) for semiconductor manufacturing that has undergone the step (B) is reduced by 80% or more as compared with the wafer (I) for crude semiconductor manufacturing.
- the wafer (IV) for semiconductor manufacturing is divided into the wafer for semiconductor manufacturing (IV) and the wafer for semiconductor manufacturing (V), which is reduced by less than 80% as compared with the wafer for crude semiconductor manufacturing (I), and the wafer for semiconductor manufacturing (IV) is selected. including, A method for selecting wafers for semiconductor manufacturing.
- the method of the present application it is possible to detect the presence of impurities present on the surface of the wafer for semiconductor manufacturing, which are removed by heating and / or performing ultrapure water cleaning treatment.
- This impurity may contain fluorine atoms. It is possible to manufacture and sort wafers for semiconductor manufacturing (so-called bare wafers) from which impurities that cannot be detected without this detection method are removed.
- the method for detecting impurities on the surface of a wafer for semiconductor manufacturing of the present application is as follows. It includes a step of applying a film forming composition to the wafer surface and firing to form a film, and then a step of detecting impurities with a wafer inspection device.
- the impurities may contain fluorine atoms.
- Wafers for semiconductor manufacturing are wafers used for manufacturing semiconductor devices, etc., and in addition to commonly used silicon wafers and germanium wafers, gallium arsenide, indium phosphate, gallium nitride, indium nitride, and aluminum nitride. Examples thereof include compound semiconductor wafers formed by bonding two or more types of elements such as the above. It is usually disk-shaped and has a size of, for example, 4, 6, 8, 12 inches or the like. Commercially available products may be used.
- the film-forming composition (organic film-forming composition, inorganic film-forming composition) described below is applied onto the semiconductor manufacturing wafer by an appropriate coating method such as a spinner or a coater. Then, a film (organic film, inorganic film) is formed by baking using a heating means such as a hot plate.
- the baking conditions are appropriately selected from a baking temperature of 100 ° C. to 400 ° C. and a baking time of 0.3 minutes to 60 minutes.
- the baking temperature is 120 ° C. to 400 ° C.
- the baking temperature is 120 ° C. to 350 ° C.
- the baking time is 0.5 minutes to 30 minutes
- the baking temperature is 150 ° C.
- the film thickness to be formed is 0.01 ⁇ m (10 nm) to 2 ⁇ m (2,000 nm), 0.02 ⁇ m (20 nm) to 1 ⁇ m (1,000 nm), 0.025 ⁇ m (25 nm) to 1 ⁇ m (1,000 nm). ), 0.02 ⁇ m (20 nm) to 0.9 ⁇ m (900 nm), 0.025 ⁇ m (25 nm) to 0.9 ⁇ m (900 nm), 0.02 ⁇ m (20 nm) to 0.8 ⁇ m (800 nm), or 0.025 ⁇ m (25 nm). ) To 0.8 ⁇ m (800 nm).
- This film thickness is preferably uniform within the wafer surface (for example, the median film thickness is within ⁇ 20%, within ⁇ 10%, within ⁇ 5%, within ⁇ 3%, and within ⁇ 1%).
- a commercially available product may be used as the wafer inspection device.
- a specific example is the Surfscan series of wafer inspection systems manufactured by KLA Tencor Co., Ltd.
- the film-forming composition used in the present application is not particularly limited as long as it is a composition capable of uniformly forming the film thickness.
- Either the organic film-forming composition or the inorganic film-forming composition may be used, but impurities contained in the film to the extent possible for the impurity detection method, the semiconductor manufacturing wafer manufacturing method, and the semiconductor manufacturing wafer selection method of the present application. It is preferable to use a coating film forming composition for lithography used in a lithography process at the time of manufacturing a semiconductor device, which is capable of forming a film with a constant film thickness in the wafer surface.
- the film-forming composition contains a resin.
- the resin is also referred to as a polymer, a polymer, a copolymer, a polymer compound or the like.
- the resin of the present application may be either an organic resin or an inorganic resin (for example, a hydrolyzed condensate of a silane compound, polysiloxane, etc.).
- the coating film forming composition for lithography used in the present application is, for example, a known photoresist composition described below, a known resist underlayer film forming composition (containing an organic compound and / or an inorganic compound), and when processing a semiconductor substrate.
- Known protective film-forming compositions for protecting substrates from etching agents lower layer film-forming compositions for known self-assembled films, upper layer film-forming compositions for known self-assembled films, and known resists. Examples thereof include, but are not limited to, an upper layer film forming composition.
- the exposure wavelength in the lithography step may be i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet rays) or EB (electron beam). It is preferable that the coating film forming composition for lithography corresponds to these exposure wavelengths.
- the coating film forming composition for lithography As specific examples of the coating film forming composition for lithography, the resist upper layer film forming composition for the resist upper layer film described in International Publication No. 2014/115843, International Publication No. 2015/129486, etc., International Publication No. 2013
- coating film forming composition for lithography examples include International Publication No. 2009/09634, Japanese Patent Application Laid-Open No. 2009-053704, International Publication No. 2010/147155, and International Publication No. 2011/102470.
- a resist underlayer forming composition a silicon-containing resist underlayer film forming composition, and the like.
- the solid content of the coating film forming composition for lithography according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass, and preferably 0.1 to 40% by mass.
- the solid content is the content ratio of all the components excluding the solvent from the coating film forming composition for lithography.
- the proportion of the polymer in the solid content is, for example, 30 to 100% by mass, 50 to 100% by mass, 60 to 100% by mass, 70 to 100% by mass, 80 to 100% by mass, 60 to 99.9% by mass, 60 to 60 to 99% by mass, 60-98% by mass, 60-97% by mass, 60-96% by mass, 60-95% by mass, 70-99.9% by mass, 70-99% by mass, 70-98% by mass, 70- It is 97% by mass, 70 to 96% by mass, or 70 to 95% by mass.
- the resist underlayer film forming composition is preferable, and as a suitable specific example, the resist underlayer film forming containing the triaryldiamine-containing novolak resin to which the aromatic vinyl compound described in International Publication No. 2019/163834 is added.
- the composition is preferred.
- This resist underlayer film forming composition comprises an aromatic ring of an aromatic compound (A) containing at least two amino groups and three aromatic rings having 6 to 40 carbon atoms, and an aromatic vinyl compound (B). It contains a novolak resin containing a structural group (C) formed by a reaction with a vinyl group.
- the structural group (C) has the following formula (1): [In equation (1), R 1 is a divalent group containing at least two amino groups and at least three aromatic rings with 6-40 carbon atoms. R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof, and the alkyl group.
- the aryl group and the heterocyclic group are a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, an alkoxy group, or It is an organic group that may be substituted with a hydroxy group, and R 2 and R 3 may form a ring together with the carbon atom to which they are attached.
- T 1 is an arylene group having 6 to 40 carbon atoms.
- T 3 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxy group, a cyano group, and a nitro group.
- a group, an amino group, a carboxyl group, an acetyl group, a hydroxymethyl group, a halogenomethyl group, a —YZ group, a halogen atom, or a combination thereof is shown.
- Y represents an oxygen atom, a sulfur atom, a carbonyl group, or an ester group
- Z represents an alkyl group having 1 to 10 carbon atoms.
- T 2 represents a hydrogen atom, a methyl group, or a phenyl group.
- n indicates the degree of condensation of the aromatic ring constituting the arylene group, which is the definition of T 1 .
- m1 is an integer of 2 to 3600. ] Is preferable.
- the R 1 is the following formula (2): [In equation (2), Ar 1 , Ar 2 , and Ar 3 independently represent a benzene ring or a naphthalene ring, respectively.
- R 6 , R 7 and R 8 are independent substituents on these rings, and are a halogen atom, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, and 2 carbon atoms. It is selected from the group consisting of an alkenyl group to 10, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group and the aryl group are an ether bond, a ketone bond or an ester.
- R 4 and R 5 each independently consist of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof.
- Selected from the group, the alkyl group, the alkenyl group and the aryl group represent an organic group which may contain an ether bond, a ketone bond or an ester bond.
- n1, n2, and n3 are 0 or more, respectively, and R6 , R7 , and R8 are integers up to the maximum number that can be replaced.
- the structural group (C) has the following formula (1-1): [In equation (1-1), R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof, and the alkyl group.
- the aryl group and the heterocyclic group are a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, an alkoxy group, or It is an organic group that may be substituted with a hydroxy group, and R 2 and R 3 may form a ring together with the carbon atom to which they are attached.
- T 2 represents a hydrogen atom, a methyl group, or a phenyl group.
- m1 is an integer of 2 to 3600. ] Is preferable.
- the resist underlayer film forming composition is preferably a resist underlayer film forming composition for lithography containing a resin containing an aliphatic ring and an aromatic ring described in International Publication No. 2011/021555.
- This resist underlayer film forming composition for lithography is a reaction product (C') of an alicyclic epoxy polymer (A') with a fused cyclic aromatic carboxylic acid and a monocyclic aromatic carboxylic acid (B'). It is a resist underlayer film forming composition containing.
- T represents a repeating unit structure having an aliphatic ring in the main chain of the polymer
- E is an epoxy group or an organic group having an epoxy group.
- It is preferably a certain resist underlayer film forming composition.
- T represents a repeating unit structure having an aliphatic ring in the main chain of the polymer
- Q is a linking group of T and an aromatic fused ring and an aromatic monocycle
- Ar is an aromatic condensed. It is preferably a polymer represented by a ring and an aromatic monocycle.
- the reaction product (C') is the following formula (13), formula (14), and formula (15) :.
- the total number of repeating unit structures contained in the reaction product (C') is 1.0, the number of repeating unit structures in equation (13) a and the number of repeating unit structures in equation (14).
- b for the number c of the repeating unit structure of the formula (15), 0 ⁇ a ⁇ 0.2, 0.3 ⁇ b ⁇ 0.7, 0.3 ⁇ c ⁇ 0.7, 0.5 ⁇ b + c ⁇ 1 It is preferably a polymer satisfying 0.0.
- X is the following formula (22), formula (23) or formula (24):
- R 1 to R 5 are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 2 to 6 carbon atoms, respectively.
- R1 and R2 , and R3 and R4 are bonded to each other to form a ring having 3 to 6 carbon atoms. It may represent a group represented by).
- a 1 to A 6 independently represent a hydrogen atom, a methyl group or an ethyl group, respectively.
- Q1 represents a divalent group containing a disulfide bond, preferably a divalent group containing an alkylene group having 1 to 6 carbon atoms at both ends of the disulfide bond.
- n is the number of repeating unit structures and represents an integer of 5 to 100. ] It is preferable to have a unit structure represented by.
- the resin (polymer) of the present application includes, for example, a polymer described in International Publication No. 2009/09634 and a bifunctional or higher functional compound having at least one disulfide bond described in International Publication No. 2019/151471. Examples include, but are not limited to, reaction products with more than functional compounds.
- the polymer is a reaction product of a bifunctional compound (A ") having at least one disulfide bond and a bifunctional compound (B") different from the compound (A "), it is contained in the polymer. There is a disulfide bond in the main chain of.
- the polymer may have a repeating unit structure represented by the following formula (31):
- R 1 is an alkyl group having 0 to 1 carbon atom
- n is the number of repeating unit structures, represents an integer of 0 to 1
- m represents an integer of 0 or 1.
- Z 1 represents a group represented by the following formula (32), formula (33) or formula (34):
- X represents a group represented by the following formula (44), formula (45) or formula (46):
- R2 to R61 R2 , R3 , R4 , R51 and R61
- R2 to R61 are independently hydrogen atom and carbon atom number 1.
- a 1 to A 6 independently represent a hydrogen atom, a methyl group or an ethyl group, respectively.
- Q1 represents an alkylene group having 1 to 10 carbon atoms interrupted by a disulfide bond.
- l is the number of repeating unit structures and represents an integer of 5 to 100.
- Q 1 is preferably an alkylene group having 2 to 6 carbon atoms interrupted by a disulfide bond.
- ring having 3 to 6 carbon atoms examples include cyclopropane, cyclobutane, cyclopentane, cyclopentadiene and cyclohexane.
- the formula (31) is the following formula (55): [In the above formula (55), X represents a group represented by the above formula (44), the formula (45) or the above formula (46), and R 6 and R 7 are independently alkylenes having 1 to 3 carbon atoms, respectively. Represents a group or direct bond p is the number of repeating unit structures and represents an integer of 5 to 100. ] It may be represented by.
- the polymer is preferably represented by the following (formula P-6) to (formula P-8).
- the resin (polymer) is synthesized by reacting a bifunctional or higher compound (A ′′) having at least one disulfide bond and a bifunctional or higher functional compound (B ′′) by a method known per se. It is preferably a product.
- cross-linking agent examples include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, and 1,3,4,6-tetrakis (methoxymethyl) glycol uryl (tetramethoxymethyl glycol).
- Uril (POWDERLINK® 1174), 1,3,4,6-tetrakis (butoxymethyl) glycol uryl, 1,3,4,6-tetrakis (hydroxymethyl) glycol uryl, 1,3-bis (hydroxy) Methyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) urea and 2,4,6-tris [bis (methoxymethyl) amino]- Examples thereof include 1,3,5-triazine ((trade name) Cymel [registered trademark] -303, Nicarac [registered trademark] MW-390).
- cross-linking agent is described in International Publication No. 2014/208542 with the following formula (71) or formula (72) :.
- Q 1 represents a single-bonded or m1-valent organic group
- R 1 and R 4 are alkyl groups having 2 to 10 carbon atoms or 1 to 10 carbon atoms, respectively.
- R 2 and R 5 each represent a hydrogen atom or a methyl group
- R 3 and R 6 indicate an alkyl group having 1 to 10 carbon atoms, respectively. It shows an aryl group having 6 to 40 carbon atoms.
- n1 is an integer of 1 ⁇ n1 ⁇ 3
- n2 is an integer of 2 ⁇ n2 ⁇ 5
- n3 is an integer of 0 ⁇ n3 ⁇ 3
- n4 is an integer of 0 ⁇ n4 ⁇ 3
- n5 is an integer of 1 ⁇ n5 ⁇ 3
- n6 is an integer of 1 ⁇ n6 ⁇ 4
- n7 is an integer of 0 ⁇ n7 ⁇ 3
- n8 is an integer of 0 ⁇ n8 ⁇ 3
- m1 represents an integer of 2 to 10.
- the crosslinkable compound represented by the above formula (71) or (72) is a compound represented by the following formula (73) or formula (74) and a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. It may be obtained by a reaction.
- Q2 represents a single bond or m2 - valent organic group ;
- R8, R9, R11 and R12 represent hydrogen atoms or methyl groups, respectively, and
- R7 and R 10 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms, respectively.
- n9 is an integer of 1 ⁇ n9 ⁇ 3
- n10 is an integer of 2 ⁇ n10 ⁇ 5
- n11 is an integer of 0 ⁇ n11 ⁇ 3
- n12 is an integer of 0 ⁇ n12 ⁇ 3
- n13 is an integer of 1 ⁇ n13 ⁇ 3
- n14 is an integer of 1 ⁇ n14 ⁇ 4
- n15 is an integer of 0 ⁇ n15 ⁇ 3
- n16 is an integer of 0 ⁇ n16 ⁇ 3
- m2 represents an integer of 2 to 10.
- the reaction of the compound represented by the following formula (73) or formula (74) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms may be carried out in the presence of an acid catalyst.
- the crosslinkable compounds represented by the formulas (71) and (72) used in the present invention can be exemplified below, for example.
- cross-linking agent is a nitrogen-containing compound described in International Publication No. 2017/187969, which has 2 to 6 substituents represented by the following formula (61) that bind to a nitrogen atom in one molecule. You may.
- R 1 represents a methyl group or an ethyl group.
- the nitrogen-containing compound having 2 to 6 substituents represented by the formula (61) in one molecule may be a glycoluril derivative represented by the following formula (1A).
- each of the four R 1s independently represents a methyl group or an ethyl group
- R 2 and R 3 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, respectively.
- Examples of the glycoluril derivative represented by the formula (1A) include compounds represented by the following formulas (1A-1) to (1A-6).
- the compound represented by the formula (1A) is represented by a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (62) that binds to a nitrogen atom in one molecule and the following formula (63). It can be obtained by reacting with at least one compound to produce a nitrogen-containing compound having 2 to 6 substituents represented by the above formula (61) in one molecule.
- R 1 represents a methyl group or an ethyl group
- R 4 represents an alkyl group having 1 to 4 carbon atoms.
- the glycoluril derivative represented by the formula (1A) is obtained by reacting the glycoluril derivative represented by the following formula (2A) with at least one compound represented by the formula (63).
- the nitrogen-containing compound having 2 to 6 substituents represented by the formula (62) in one molecule is, for example, a glycoluril derivative represented by the following formula (2A).
- R 2 and R 3 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R 4 independently represents an alkyl group having 1 to 4 carbon atoms. Represents a group.
- Examples of the glycoluril derivative represented by the formula (2A) include compounds represented by the following formulas (2A-1) to (2A-4).
- examples of the compound represented by the above formula (63) include compounds represented by the following formulas (2A-5) and (2A-6).
- the contents of the nitrogen-containing compound having 2 to 6 substituents represented by the above formula (61) bonded to the nitrogen atom are incorporated in the present application in full disclosure of WO2017 / 187969. Will be done.
- the content ratio of the cross-linking agent is, for example, 1% by mass to 50% by mass, preferably 5% by mass to 30% by mass, based on the organic resin.
- the method for manufacturing a wafer for semiconductor manufacturing from which impurities on the wafer surface of the present application have been removed is a step of heating the wafer for crude semiconductor manufacturing (I) to 100 ° C to 500 ° C and / or a step of cleaning with ultra-pure water (A).
- the surface of the wafer (II) for semiconductor manufacturing that has undergone the step (A) is inspected by the impurity detection method, and the wafer (III) for semiconductor manufacturing that has undergone the step (B).
- the step (C) of selecting a wafer for semiconductor manufacturing (IV) in which the number of defects existing above is reduced by 80% or more as compared with the wafer for manufacturing crude semiconductor is included.
- the crude semiconductor manufacturing wafer (I) refers to an untreated semiconductor manufacturing wafer before the step of heating the wafer for semiconductor manufacturing and / or the step of cleaning with ultrapure water.
- the step of heating the wafer is performed in the range of 100 ° C. to 500 ° C., but 120 ° C. to 500 ° C., 120 ° C. to 400 ° C., 150 to 400 ° C., 200 to 400 ° C., 200 ° C. It is preferably to 500 ° C. and 300 ° C. to 500 ° C.
- the heating time is usually 0.5 to 30 minutes.
- the heating is usually performed in the atmosphere, but may be performed in an inert gas such as a nitrogen atmosphere.
- the method of cleaning the wafer with ultrapure water is not particularly limited, and examples thereof include batch cleaning and single-wafer cleaning.
- the temperature of the ultrapure water is, for example, 5 ° C to 50 ° C, and the cleaning time is, for example, 1 minute to 1 hour. It may be performed in combination with ultrasonic cleaning. The above heating step and the ultrapure water cleaning step may be combined. Either order does not matter.
- the method for selecting a wafer for semiconductor manufacturing in the present application includes a step of heating the wafer for manufacturing crude semiconductor (I) to 100 ° C. to 500 ° C. and / or a step of washing with ultra-pure water (A) and the above-mentioned step (A). From the step (B) of inspecting the passed semiconductor manufacturing wafer (II) by the impurity detection method and the semiconductor manufacturing wafer (III) passed through the step (B), the number of defects existing on the surface thereof is determined. It includes a step (C) of selecting a wafer (IV) for semiconductor manufacturing, which is reduced by 80% or more as compared with the wafer (I) for manufacturing crude semiconductor.
- the number of defects existing on the surface of the semiconductor manufacturing wafer (III) that has undergone the step (B) is reduced by 80% or more as compared with the crude semiconductor manufacturing wafer (I).
- the wafer (IV) for semiconductor manufacturing is divided into the wafer for semiconductor manufacturing (IV) and the wafer for semiconductor manufacturing (V) which is reduced by less than 80% as compared with the wafer for crude semiconductor manufacturing (I), and the wafer for semiconductor manufacturing (IV) is selected.
- the mixture was allowed to cool to room temperature and then reprecipitated using a mixed solvent of methanol (1000 g, manufactured by Kanto Chemical Co., Inc.), ultrapure water 1000 g, and 30% aqueous ammonia (100 g, manufactured by Kanto Chemical Co., Inc.). ..
- the obtained precipitate was filtered and dried in a vacuum drier at 80 ° C. for 24 hours to obtain 136.68 g of the target polymer represented by the formula (a).
- the weight average molecular weight Mw measured in terms of polystyrene was 1400, and the polydispersity Mw / Mn was 1.29.
- This reaction product contains a polymer compound having a structural unit represented by the following formula (c-1).
- Example 1 The resist underlayer film forming composition obtained in Preparation Example 1 was applied onto a 12-inch silicon wafer using a coating apparatus CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron Limited. The coated film was fired at 240 ° C. for 60 seconds and then further fired at 400 ° C. for 60 seconds to obtain a 12-inch silicon wafer on which a coating film having a film thickness of 800 nm was formed.
- Example 2 The resist underlayer film forming composition obtained in Preparation Example 2 was applied onto a 12-inch silicon wafer using a coating apparatus CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron Limited. The coated film was fired at 205 ° C. for 60 seconds to obtain a 12-inch silicon wafer on which a coating film having a film thickness of 200 nm was formed.
- ⁇ Reference example 1> A 12-inch silicon wafer was heat-treated by firing a 12-inch silicon wafer at 400 ° C. for 60 seconds using a coating device CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron Limited.
- PGME Propylene glycol monomethyl ether
- CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron Limited.
- the coated film was fired at 205 ° C. for 60 seconds to obtain a 12-inch silicon wafer on which the coated film was formed.
- ⁇ Reference example 3> A 12-inch silicon wafer was fired at 400 ° C. for 60 seconds using a coating device CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron. The resist underlayer film forming composition obtained in Preparation Example 1 was applied to the fired 12-inch silicon wafer. The coated film was fired at 240 ° C. for 60 seconds and then further fired at 400 ° C. for 60 seconds to obtain a 12-inch silicon wafer on which a coating film having a film thickness of 800 nm was formed.
- ⁇ Reference example 4> A 12-inch silicon wafer was fired at 205 ° C. for 60 seconds using a coating device CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron. The resist underlayer film forming composition obtained in Preparation Example 2 was applied to the fired 12-inch silicon wafer. The coated film was fired at 25 ° C. for 60 seconds to obtain a 12-inch silicon wafer on which a coating film having a film thickness of 200 nm was formed.
- ⁇ Reference example 5> The resist underlayer film forming composition obtained in Preparation Example 3 was applied onto a 12-inch silicon wafer using a coating apparatus CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron Limited. The coated film was fired at 205 ° C. for 60 seconds to obtain a 12-inch silicon wafer on which a coating film having a film thickness of 25 nm was formed.
- FIGS. 2 and 3 show the results of performing the shape and elemental analysis of the defects detected in Examples 1 and 2 with the defect review SEM RS6000 manufactured by Hitachi High-Tech Co., Ltd.
- Examples 1 and 2 in which a resist underlayer film forming composition was applied to an untreated 12-inch silicon wafer showed a characteristic defect distribution on the outer peripheral portion of the wafer.
- impurities are present on the surface of the 12-inch silicon wafer, and the impurities are components that are removed by firing treatment.
- the 12-inch silicon wafer is fired as it is or volatilized after firing and is placed on the wafer. It was shown that the impurities cannot be detected by the treatment of applying a non-residual solvent.
- the impurities could not be detected in the coating film having a film thickness of 25 nm, and it was shown that the film thickness of the coating film must be 25 nm or more.
- Example 3 A 12-inch silicon wafer was fired at 205 ° C. for 60 seconds using a coating device CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron.
- the resist underlayer film forming composition obtained in Preparation Example 2 was applied to the fired wafer using a coating device CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron Limited.
- the coated film was fired in the atmosphere at 205 ° C. for 60 seconds to obtain a 12-inch silicon wafer on which a coating film having a film thickness of 200 nm was formed.
- Example 4 While rotating a 12-inch silicon wafer using a spin cleaner MSC-5000NC manufactured by Sanmasu Semiconductor Industry, ultrapure water at 23 ° C. was discharged to the wafer surface at 1.5 L / min for 60 seconds to clean the wafer surface. ..
- the resist underlayer film forming composition obtained in Preparation Example 2 was applied to the washed wafer using a coating device CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron Limited. The coated film was fired in the atmosphere at 205 ° C. for 60 seconds to obtain a 12-inch silicon wafer on which a coating film having a film thickness of 200 nm was formed.
- Example 5 A 12-inch silicon wafer was fired at 400 ° C. for 60 seconds using a coating device CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron.
- the resist underlayer film forming composition obtained in Preparation Example 1 was applied to the fired wafer using a coating device CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron Limited.
- the coated film was fired in the atmosphere at 240 ° C. for 60 seconds and then further fired in the atmosphere at 400 ° C. for 60 seconds to obtain a 12-inch silicon wafer on which a coating film coating film having a film thickness of 800 nm was formed. rice field.
- ⁇ Comparative Example 1> The resist underlayer film forming composition obtained in Preparation Example 2 was applied onto a 12-inch silicon wafer using a coating apparatus CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron Limited. The coated film was fired in the atmosphere at 205 ° C. for 60 seconds to obtain a 12-inch silicon wafer on which a coating film having a film thickness of 200 nm was formed.
- ⁇ Comparative Example 2> The resist underlayer film forming composition obtained in Preparation Example 1 was applied onto a 12-inch silicon wafer using a coating apparatus CLEAN TRACK Lithius Pro AP manufactured by Tokyo Electron Limited. The coated film was fired in the atmosphere at 240 ° C. for 60 seconds and then further fired in the atmosphere at 400 ° C. for 60 seconds to obtain a 12-inch silicon wafer on which a coating film having a film thickness of 800 nm was formed.
- the silicon wafers obtained in Examples 3 to 5 were measured for film surface defects using the wafer inspection system Surfscan SP2XP manufactured by KLA Tencor Co., Ltd.
- the defect distribution in the wafer is shown in FIG. 4, and the number of defects is shown in Table 2.
- Examples 3 to 5 in which the resist underlayer film forming composition was applied to a 12-inch silicon wafer subjected to ultrapure water cleaning and firing treatment are the outer peripheral portions of the wafer as shown in Comparative Examples 1 and 2. No characteristic defect distribution was confirmed, and the number of defects of 70 nm or less was reduced to 1/5. From this, it was shown that impurities are present on the surface of the 12-inch silicon wafer, and the impurities are components that are removed by performing ultrapure water washing or firing treatment. This indicates that it is possible to form a coating film without being affected by impurities on the wafer surface by performing ultrapure water cleaning and firing treatment before coating the resist underlayer film on the wafer. rice field.
- the method of the present application it is possible to detect the presence of impurities present on the surface of the wafer for semiconductor manufacturing, which are removed by heating and / or performing ultrapure water cleaning treatment.
- This impurity may contain fluorine atoms. It is possible to provide a method for manufacturing and sorting a wafer for semiconductor manufacturing (so-called bare wafer) from which impurities that cannot be detected without using this detection method are removed.
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Abstract
Description
該ウェハー表面に膜形成組成物を塗布し、焼成して、膜を形成する工程、次いでウェハー検査装置にて不純物を検出する工程を含む、半導体製造用ウェハー表面の不純物検出方法。
100℃~500℃に粗半導体製造用ウェハー(I)を加熱する工程及び/又は超純水で洗浄する工程(A)と、
前記工程(A)を経た半導体製造用ウェハー(II)を[1]~[5]何れか1項に記載の不純物検出方法で検査する工程(B)と、
前記工程(B)を経た半導体製造用ウェハー(III)の中から、その表面上に存在する欠陥個数が、粗半導体製造用ウェハー(I)に比較し、80%以上低減された半導体製造用ウェハー(IV)を選択する工程(C)と
を含む、ウェハー表面の不純物が除去された半導体製造用ウェハーの製造方法。
100℃~500℃に粗半導体製造用ウェハー(I)を加熱する工程及び/又は超純水で洗浄する工程(A)と、
前記工程(A)を経た半導体製造用ウェハーを[1]~[5]何れか1項に記載の不純物検出方法で検査する工程(B)と、
前記工程(B)を経た半導体製造用ウェハー(III)の中から、その表面上に存在する欠陥個数が、粗半導体製造用ウェハーに比較し、80%以上低減された半導体製造用ウェハー(IV)を選択する工程(C)と
を含み、
前記工程(C)が、前記工程(B)を経た半導体製造用ウェハー(III)を、その表面上に存在する欠陥個数が、粗半導体製造用ウェハー(I)に比較し、80%以上低減された半導体製造用ウェハー(IV)と、粗半導体製造用ウェハー(I)に比較し、80%未満低減された半導体製造用ウェハー(V)とに分け、半導体製造用ウェハー(IV)を選択することを含む、
半導体製造用ウェハーの選別方法。
本願の半導体製造用ウェハー表面の不純物検出方法は、
該ウェハー表面に膜形成組成物を塗布し、焼成して、膜を形成する工程、次いでウェハー検査装置にて不純物を検出する工程を含む。
本願で使用される膜形成組成物は、前記膜厚を均一に形成できる組成物であれば特に限定されない。有機膜形成組成物、無機膜形成組成物何れであってもよいが、本願の不純物検出方法、半導体製造用ウェハーの製造方法及び半導体製造用ウェハーの選別方法が可能な程度に膜が含有する不純物が少なく、ウェハー面内で一定膜厚での膜形成が可能である、半導体装置製造時におけるリソグラフィー工程で使用されるリソグラフィー用塗布膜形成組成物を使用することが好ましい。
[式(1)中、
R1は少なくとも2つのアミノ基と少なくとも3つの炭素原子数6~40の芳香族環とを含む2価の基であり、
R2及びR3はそれぞれ独立して、水素原子、炭素原子数1~10のアルキル基、炭素原子数6~40のアリール基、複素環基、又はそれらの組み合わせであり、かつ、該アルキル基、該アリール基及び該複素環基は、ハロゲン原子、ニトロ基、アミノ基、炭素原子数1~10のアルキル基、炭素原子数6~40のアリール基、ホルミル基、カルボキシル基、アルコキシ基、又はヒドロキシ基で置換されていても良い有機基であり、そしてR2とR3はそれらが結合する炭素原子と一緒になって環を形成していても良く、
T1は炭素原子数6~40のアリーレン基であり、
T3は炭素原子数1~10のアルキル基、炭素原子数2~10のアルケニル基、炭素原子数2~10のアルキニル基、炭素原子数6~40のアリール基、ヒドロキシ基、シアノ基、ニトロ基、アミノ基、カルボキシル基、アセチル基、ヒドロキシメチル基、ハロゲノメチル基、-Y-Z基、ハロゲン原子、またはそれらの組み合わせを示す。Yは酸素原子、硫黄原子、カルボニル基、又はエステル基を示し、Zは炭素原子数1~10のアルキル基を示す。
nはT1の定義であるアリーレン基を構成する芳香環の縮合度を示し、
m1は2~3600の整数である。]であることが好ましい。
[式(2)中、
Ar1、Ar2、及びAr3はそれぞれ独立して、ベンゼン環、又はナフタレン環を示し、
R6、R7、及びR8はそれぞれ独立して、これら環上の置換基であり、ハロゲン原子、ニトロ基、アミノ基、ヒドロキシ基、炭素原子数1~10のアルキル基、炭素原子数2~10のアルケニル基、炭素原子数6~40のアリール基、及びそれらの組み合わせからなる群より選択され、かつ、該アルキル基、該アルケニル基及び該アリール基は、エーテル結合、ケトン結合、若しくはエステル結合を含んでいても良い有機基を表し、
R4及びR5はそれぞれ独立して、水素原子、炭素原子数1~10のアルキル基、炭素原子数2~10のアルケニル基、炭素原子数6~40のアリール基、及びそれらの組み合わせからなる群より選択され、かつ、該アルキル基、該アルケニル基及び該アリール基は、エーテル結合、ケトン結合、若しくはエステル結合を含んでいても良い有機基を表し、
n1、n2、n3はそれぞれ0以上であり、かつR6、R7、及びR8が置換可能な最大数までの整数である。]で示される化合物の芳香族環から2個の水素原子を取り除いた2価の有機基であることが好ましい。
[式(1-1)中、
R2及びR3はそれぞれ独立して、水素原子、炭素原子数1~10のアルキル基、炭素原子数6~40のアリール基、複素環基、又はそれらの組み合わせであり、かつ、該アルキル基、該アリール基及び該複素環基は、ハロゲン原子、ニトロ基、アミノ基、炭素原子数1~10のアルキル基、炭素原子数6~40のアリール基、ホルミル基、カルボキシル基、アルコキシ基、又はヒドロキシ基で置換されていても良い有機基であり、そしてR2とR3はそれらが結合する炭素原子と一緒になって環を形成していても良い。
m1は2~3600の整数である。]であることが好ましい。
(式(11)中、Tはポリマーの主鎖に脂肪族環を有する繰り返し単位構造を示し、Eはエポキシ基又はエポキシ基を有する有機基である。)で示される繰り返し単位構造を有するものであるレジスト下層膜形成組成物であることが好ましい。
(式(12)中、Tはポリマーの主鎖に脂肪族環を有する繰り返し単位構造を示し、QはTと芳香族縮合環及び芳香族単環との連結基であり、Arは芳香族縮合環及び芳香族単環である。)で示されるポリマーであることが好ましい。
の繰り返し単位構造が、反応生成物(C’)に含まれる単位構造の総数を1.0とした時に、式(13)の繰り返し単位構造の数a、式(14)の繰り返し単位構造の数b、式(15)の繰り返し単位構造の数cについて、0≦a≦0.2、0.3≦b≦0.7、0.3≦c≦0.7、0.5≦b+c≦1.0を満たすポリマーであることが好ましい。
〔上記式(21)中、Xは下記式(22)、式(23)又は式(24):
(上記式(22)、式(23)、式(24)中、R1~R5はそれぞれ独立に、水素原子、炭素原子数1~6のアルキル基、炭素原子数2~6のアルケニル基、ベンジル基又はフェニル基を表し、前記フェニル基は、炭素原子数1~6のアルキル基、ハロゲン原子、炭素原子数1~6のアルコキシ基、ニトロ基、シアノ基及び炭素原子数1~6のアルキルチオ基からなる群から選ばれる少なくとも1つの基で置換されていてもよく、またR1とR2、R3とR4は互いに結合して炭素原子数3~6の環を形成していてもよい。)で表される基を表し、
A1~A6はそれぞれ独立に、水素原子、メチル基又はエチル基を表し、
Q1はジスルフィド結合を含む2価の基を表し、好ましくはジスルフィド結合の両端に各々炭素原子数1~6のアルキレン基を含む2価の基を表し、
nは繰り返し単位構造の数であって、5ないし100の整数を表す。〕
で表される単位構造を有することが好ましい。
(上記式(31)中、R1は炭素原子数0~1のアルキル基、nは繰り返し単位構造の数であって、0ないし1の整数を表し、mは0又は1の整数を表し、
Z1は下記式(32)、式(33)又は式(34)で表される基を表し:
上記式(33)中、Xは下記式(44)、式(45)又は式(46)で表される基を表し:
上記式(44)、式(45)、式(46)中、R2~R61(R2、R3、R4、R51及びR61)はそれぞれ独立に、水素原子、炭素原子数1~6のアルキル基、炭素原子数3~6のアルケニル基、ベンジル基又はフェニル基を表し、前記フェニル基は、炭素原子数1~6のアルキル基、ハロゲン原子、炭素原子数1~6のアルコキシ基、ニトロ基、シアノ基及び炭素原子数1~6のアルキルチオ基からなる群から選ばれる少なくとも1つの基で置換されていてもよく、またR2とR3、R4とR5は互いに結合して炭素原子数3~6の環を形成していてもよい。
Q1はジスルフィド結合で中断されている炭素原子数1~10のアルキレン基を表し、
lは繰り返し単位構造の数であって、5ないし100の整数を表す。)
Q1はジスルフィド結合で中断されている炭素原子数2から6のアルキレン基であることが好ましい。
〔上記式(55)中、Xは前記式(44)、式(45)又は式(46)で表される基を表し、R6及びR7はそれぞれ独立に炭素原子数1~3のアルキレン基又は直接結合を表し、
pは繰り返し単位構造の数であって、5ないし100の整数を表す。〕
で表されてもよい。
本発明の膜形成組成物に任意成分として含まれる架橋剤としては、例えば、ヘキサメトキシメチルメラミン、テトラメトキシメチルベンゾグアナミン、1,3,4,6-テトラキス(メトキシメチル)グリコールウリル(テトラメトキシメチルグリコールウリル)(POWDERLINK〔登録商標〕1174)、1,3,4,6-テトラキス(ブトキシメチル)グリコールウリル、1,3,4,6-テトラキス(ヒドロキシメチル)グリコールウリル、1,3-ビス(ヒドロキシメチル)尿素、1,1,3,3-テトラキス(ブトキシメチル)尿素、1,1,3,3-テトラキス(メトキシメチル)尿素及び2,4,6-トリス[ビス(メトキシメチル)アミノ]-1,3,5-トリアジン((商品名)Cymel〔登録商標〕-303,ニカラック〔登録商標〕MW-390)が挙げられる。
n1は1≦n1≦3の整数、n2は2≦n2≦5の整数、n3は0≦n3≦3の整数、n4は0≦n4≦3の整数、3≦(n1+n2+n3+n4)≦6の整数を示す。
n5は1≦n5≦3の整数、n6は1≦n6≦4の整数、n7は0≦n7≦3の整数、n8は0≦n8≦3の整数、2≦(n5+n6+n7+n8)≦5の整数を示す。m1は2~10の整数を示す。)で示される架橋性化合物を含んでよい。
上記式(71)又は式(72)で示される架橋性化合物が、下記式(73)又は式(74)で示される化合物と、ヒドロキシル基含有エーテル化合物又は炭素原子数2~10のアルコールとの反応によって得られるものであってよい。
n9は1≦n9≦3の整数、n10は2≦n10≦5の整数、n11は0≦n11≦3の整数、n12は0≦n12≦3の整数、3≦(n9+n10+n11+n12)≦6の整数を示す。
n13は1≦n13≦3の整数、n14は1≦n14≦4の整数、n15は0≦n15≦3の整数、n16は0≦n16≦3の整数、2≦(n13+n14+n15+n16)≦5の整数を示す。m2は2~10の整数を示す。)
下記式(73)又は式(74)で示される化合物と、ヒドロキシル基含有エーテル化合物又は炭素原子数2~10のアルコールとの反応が酸触媒の存在下で行われてよい。
本発明に用いられる式(71)及び式(72)で示される架橋性化合物は例えば以下に例示することができる。
(式(1A)中、4つのR1はそれぞれ独立にメチル基又はエチル基を表し、R2及びR3はそれぞれ独立に水素原子、炭素原子数1~4のアルキル基、又はフェニル基を表す。)
前記式(1A)で表されるグリコールウリル誘導体として、例えば、下記式(1A-1)~式(1A-6)で表される化合物が挙げられる。
前記式(1A)で表される化合物は、窒素原子と結合する下記式(62)で表される置換基を1分子中に2~6つ有する含窒素化合物と下記式(63)で表される少なくとも1種の化合物とを反応させて前記式(61)で表される置換基を1分子中に2~6つ有する含窒素化合物を製造することで得られる。
(式(62)、式(63)中、R1はメチル基又はエチル基を表し、R4は炭素原子数1~4のアルキル基を表す。)
前記式(1A)で表されるグリコールウリル誘導体は、下記式(2A)で表されるグリコールウリル誘導体と前記式(63)で表される少なくとも1種の化合物とを反応させることにより得られる。
(式(2A)中、R2は及びR3はそれぞれ独立に水素原子、炭素原子数1~4のアルキル基、又はフェニル基を表し、R4はそれぞれ独立に炭素原子数1~4のアルキル基を表す。)
前記式(2A)で表されるグリコールウリル誘導体として、例えば、下記式(2A-1)~式(2A-4)で表される化合物が挙げられる。さらに前記式(63)で表される化合物として、例えば下記式(2A-5)及び式(2A-6)で表される化合物が挙げられる。
上記窒素原子と結合する上記式(61)で表される置換基を1分子中に2~6つ有する含窒素化合物に係る内容は、国際公開第2017/187969号公報の全開示が本願に援用される。
本願のウェハー表面の不純物が除去された半導体製造用ウェハーの製造方法は、100℃~500℃に粗半導体製造用ウェハー(I)を加熱する工程及び/又は超純水で洗浄する工程(A)と、前記工程(A)を経た半導体製造用ウェハー(II)を前記不純物検出方法で検査する工程(B)と、前記工程(B)を経た半導体製造用ウェハー(III)の中から、その表面上に存在する欠陥個数が、粗半導体製造用ウェハーに比較し、80%以上低減された半導体製造用ウェハー(IV)を選択する工程(C)を含む。
本願の半導体製造用ウェハーの選別方法は、100℃~500℃に粗半導体製造用ウェハー(I)を加熱する工程及び/又は超純水で洗浄する工程(A)と、前記工程(A)を経た半導体製造用ウェハー(II)を前記不純物検出方法で検査する工程(B)と、前記工程(B)を経た半導体製造用ウェハー(III)の中から、その表面上に存在する欠陥個数が、粗半導体製造用ウェハー(I)に比較し、80%以上低減された半導体製造用ウェハー(IV)を選択する工程(C)とを含む。
300mL四口フラスコにN,N’-ジフェニル-1,4-フェニレンジアミン(41.98g、0.161mol、東京化成工業(株)製)、4-アミルオキシベンズアルデヒド(31.02g、0.161mol、東京化成工業(株)製)、4-(tert-ブトキシ)スチレン(94.75g、0.537mol、和光純薬工業(株)製)、プロピレングリコールモノメチルエーテル(172.37g、関東化学(株)製)を仕込みメタンスルホン酸(4.65g、0.048mol、東京化成工業(株)製)を加えて撹拌し、135℃まで昇温し溶解させ重合を開始した。18時間後室温まで放冷後、メタノール(1000g、関東化学(株)製)、超純水1000gおよび30%アンモニア水(100g、関東化学(株)製)の混合溶媒を用いて再沈殿させた。得られた沈殿物をろ過し、減圧乾燥機で80℃、24時間乾燥し、式(a)で表される目的とするポリマー136.68gを得た。ポリスチレン換算で測定される重量平均分子量Mwは1400であり、多分散度Mw/Mnは1.29であった。
式(b-1)の化合物(ダイセル化学工業(株)製、商品名:EHPE3150)40.0gと9-アントラセンカルボン酸20.3gと安息香酸13.7gをプロピレングリコールモノメチルエーテル302.0gに溶解させた後、ベンジルトリエチルアンモニウム1.5gを加え、24時間還流し反応させた。反応後溶液をイオン交換法を用いて精製し、式(b-2)のポリマー溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は4100であった。
モノアリルジグリシジルイソシアヌル酸(四国化成工業(株)製)800g、3,3’-ジチオジプロピオン酸(堺化学工業(株)製、商品名:DTDPA)608g、及び触媒として第4級ホスホニウム塩であるトリフェニルモノエチルホスホニウムブロミド53gを、プロピレングリコールモノメチルエーテル2191gに溶解させ、加熱後120℃に保ちながら窒素雰囲気下で4時間撹拌した。得られた反応生成物を、プロピレングリコールモノメチルエーテル3652gにて希釈したワニス溶液のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は約7800であった。この反応生成物は、下記式(c-1)で表される構造単位を有する高分子化合物を含む。
前記合成例1で合成したポリマー17.64gに架橋剤として式(d-1)で示す2,2-ビス[3,5-ビス[(2-メトキシ-1-メチルエトキシ)メチル]-4-ヒドロキシフェニル]プロパンの4個のメチロール基が、それぞれプロピレングリコールモノメチルエーテルと脱水縮合して得られた化合物であるPGME-BIP-Aと略される式(d-2)で示した化合物を3.53g、架橋触媒としてピリジニウム-p-フェノールスルホネートを0.58g、界面活性剤としてDIC(株)製のメガファック〔商品名〕R-30Nを0.02g、溶媒としてプロピレングリコールモノメチルエーテルを23.47g、プロピレングリコールモノメチルエーテルアセテートを54.76gを添加してレジスト下層膜形成組成物を調製した。
前記合成例2で得られたポリマー溶液31.49g(ポリマーの固形分は16質量%)に、架橋剤として日本サイテックインダストリーズ(株)製のテトラメトキシメチルグリコールウリル(POWDERLINK(登録商標)1174)を1.26g、架橋触媒としてピリジニウム-p-トルエンスルホナートを0.04g、界面活性剤としてDIC(株)製のメガファック〔商品名〕R-30Nを0.004g、溶媒としてプロピレングリコールモノメチルエーテルを57.63g、プロピレングリコールモノメチルエーテルアセテート9.58gを添加してレジスト下層膜形成組成物を調製した。
前記合成例2で得られたポリマー溶液3.58g(ポリマーの固形分は20質量%)に日本サイテックインダストリーズ(株)製のテトラメトキシメチルグリコールウリル(POWDERLINK(登録商標)1174)を0.18g、架橋触媒として4-ヒドロキシベンゼンスルホン酸(PSA)を0.02g、添加剤としてビスフェノールSを0.01g、界面活性剤としてDIC(株)製のメガファック〔商品名〕R-30Nを0.01g、プロピレングリコールモノメチルエーテル86.30g及びプロピレングリコールモノメチルエーテルアセテート9.91gを添加してレジスト下層膜形成組成物を調製した。
調製例1で得られたレジスト下層膜形成組成物を東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて12インチシリコンウェハー上に塗布した。塗布後の膜を240℃、60秒で焼成した後さらに400℃、60秒で焼成することで膜厚が800nmの塗布膜が形成された12インチシリコンウェハーを得た。
調製例2で得られたレジスト下層膜形成組成物を東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて12インチシリコンウェハー上に塗布した。塗布後の膜を205℃、60秒で焼成することで膜厚が200nmの塗布膜が形成された12インチシリコンウェハーを得た。
東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて12インチシリコンウェハーを400℃、60秒で焼成することで加熱処理を実施した12インチシリコンウェハーを得た。
レジスト下層膜形成組成物に使用されている溶剤であるプロピレングリコールモノメチルエーテル(PGME)を東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて12インチシリコンウェハー上に塗布した。塗布後の膜を205℃、60秒で焼成することで塗布膜が形成された12インチシリコンウェハーを得た。
東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて12インチシリコンウェハーを400℃、60秒で焼成した。前記焼成した12インチシリコンウェハーに調製例1で得られたレジスト下層膜形成組成物を塗布した。塗布後の膜を240℃、60秒で焼成した後さらに400℃、60秒で焼成することで膜厚が800nmの塗布膜が形成された12インチシリコンウェハーを得た。
東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて12インチシリコンウェハーを205℃、60秒で焼成した。前記焼成した12インチシリコンウェハーに調製例2で得られたレジスト下層膜形成組成物を塗布した。塗布後の膜を25℃、60秒で焼成することで膜厚が200nmの塗布膜が形成された12インチシリコンウェハーを得た。
調製例3で得られたレジスト下層膜形成組成物を東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて12インチシリコンウェハー上に塗布した。塗布後の膜を205℃、60秒で焼成することで膜厚が25nmの塗布膜が形成された12インチシリコンウェハーを得た。
実施例1及び2で得られたシリコンウェハーをケーエルエー・テンコール株式会社製のウェハー検査システムSurfscan SP2XPで膜表面の欠陥を測定した。ウェハー内の欠陥分布を図1に、及び欠陥の個数を表1に示す。また、実施例1及び2で検出された欠陥の形状および元素分析を株式会社日立ハイテク製の欠陥レビューSEM RS6000で実施した結果を図2及び3に示す。
東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて12インチシリコンウェハーを205℃、60秒で焼成した。前記焼成済みのウェハーに調製例2で得られたレジスト下層膜形成組成物を東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて塗布した。塗布後の膜を大気下で205℃、60秒で焼成することで膜厚が200nmの塗布膜が形成された12インチシリコンウェハーを得た。
三益半導体工業製のスピンクリーナーMSC-5000NCを用いて12インチシリコンウェハーを回転させながらウェハー表面に23℃の超純水を1.5L/minで60秒吐出してウェハー表面の洗浄を行った。前記洗浄済みのウェハーに調製例2で得られたレジスト下層膜形成組成物を東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて塗布した。塗布後の膜を大気下で205℃、60秒で焼成することで膜厚が200nmの塗布膜が形成された12インチシリコンウェハーを得た。
東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて12インチシリコンウェハーを400℃、60秒で焼成した。前記焼成済みのウェハーに調製例1で得られたレジスト下層膜形成組成物を東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて塗布した。塗布後の膜を大気下で240℃、60秒で焼成した後さらに大気下で400℃、60秒で焼成することで膜厚が800nmの塗布膜塗布膜が形成された12インチシリコンウェハーを得た。
調製例2で得られたレジスト下層膜形成組成物を東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて12インチシリコンウェハー上に塗布した。塗布後の膜を大気下で205℃、60秒で焼成することで膜厚が200nmの塗布膜が形成された12インチシリコンウェハーを得た。
調製例1で得られたレジスト下層膜形成組成物を東京エレクトロン製の塗布装置CLEAN TRACK Lithius Pro APを用いて12インチシリコンウェハー上に塗布した。塗布後の膜を大気下で240℃、60秒で焼成した後さらに大気下で400℃、60秒で焼成することで膜厚が800nmの塗布膜が形成された12インチシリコンウェハーを得た。
実施例3~5で得られたシリコンウェハーをケーエルエー・テンコール株式会社製のウェハー検査システムSurfscan SP2XPで膜表面の欠陥を測定した。ウェハー内の欠陥分布を図4に、及び欠陥の個数を表2に示す。
Claims (7)
- 半導体製造用ウェハー表面の不純物検出方法であって、
該ウェハー表面に膜形成組成物を塗布し、焼成して、膜を形成する工程、次いでウェハー検査装置にて不純物を検出する工程を含む、半導体製造用ウェハー表面の不純物検出方法。 - 前記不純物が、フッ素原子を含む、請求項1に記載の不純物検出方法。
- 前記膜形成組成物が、樹脂を含む、請求項1又は2に記載の不純物検出方法。
- 前記膜形成組成物が、リソグラフィー用塗布膜形成組成物である、請求項1~3何れか1項に記載の不純物検出方法。
- 前記膜形成組成物が、レジスト下層膜形成組成物である、請求項1~4何れか1項に記載の不純物検出方法。
- ウェハー表面の不純物が除去された半導体製造用ウェハーの製造方法であって、
100℃~500℃に粗半導体製造用ウェハー(I)を加熱する工程及び/又は超純水で洗浄する工程(A)と、
前記工程(A)を経た半導体製造用ウェハー(II)を請求項1~5何れか1項に記載の不純物検出方法で検査する工程(B)と、
前記工程(B)を経た半導体製造用ウェハー(III)の中から、その表面上に存在する欠陥個数が、粗半導体製造用ウェハー(I)に比較し、80%以上低減された半導体製造用ウェハー(IV)を選択する工程(C)と
を含む、ウェハー表面の不純物が除去された半導体製造用ウェハーの製造方法。 - 半導体製造用ウェハーの選別方法であって、
100℃~500℃に粗半導体製造用ウェハー(I)を加熱する工程及び/又は超純水で洗浄する工程(A)と、
前記工程(A)を経た半導体製造用ウェハーを請求項1~5何れか1項に記載の不純物検出方法で検査する工程(B)と、
前記工程(B)を経た半導体製造用ウェハー(III)の中から、その表面上に存在する欠陥個数が、粗半導体製造用ウェハーに比較し、80%以上低減された半導体製造用ウェハー(IV)を選択する工程(C)と
を含み、
前記工程(C)が、前記工程(B)を経た半導体製造用ウェハー(III)を、その表面上に存在する欠陥個数が、粗半導体製造用ウェハー(I)に比較し、80%以上低減された半導体製造用ウェハー(IV)と、粗半導体製造用ウェハー(I)に比較し、80%未満低減された半導体製造用ウェハー(V)とに分け、半導体製造用ウェハー(IV)を選択することを含む、
半導体製造用ウェハーの選別方法。
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| KR20240119264A (ko) * | 2023-01-23 | 2024-08-06 | 닛산 가가쿠 가부시키가이샤 | 금속 산화물 레지스트 패턴 형성용 유기 수지 조성물 |
| KR102839122B1 (ko) | 2023-01-23 | 2025-07-28 | 닛산 가가쿠 가부시키가이샤 | 금속 산화물 레지스트 패턴 형성용 유기 수지 조성물 |
Also Published As
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| JPWO2022050405A1 (ja) | 2022-03-10 |
| CN115989571A (zh) | 2023-04-18 |
| US12598958B2 (en) | 2026-04-07 |
| JP2025133845A (ja) | 2025-09-11 |
| EP4207258A1 (en) | 2023-07-05 |
| KR20230062820A (ko) | 2023-05-09 |
| EP4207258A4 (en) | 2024-03-13 |
| US20230317527A1 (en) | 2023-10-05 |
| JP7715156B2 (ja) | 2025-07-30 |
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