Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • 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
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes

Definitions

• the present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a substrate for semiconductor processing, a method for manufacturing a semiconductor element, and a method for forming a pattern.
• microfabrication using lithography with a photoresist composition has traditionally been carried out.
• This microfabrication method involves forming a thin film of a photoresist composition on a silicon wafer, irradiating it with active energy rays such as ultraviolet light through a mask pattern on which a semiconductor device pattern is drawn, developing it, and then etching the silicon wafer using the resulting resist pattern as a protective film.
• BARC Bottom Anti-Reflective Coating
• the present applicant has proposed an anti-reflective film-forming composition that has a high anti-reflective light effect, does not cause intermixing with the resist layer, provides an excellent resist pattern and a wide focus depth margin, and produces an anti-reflective film for lithography that has a higher dry etching rate than resist (see Patent Document 1).
• the composition for forming a resist underlayer film is generally an organic solvent-based composition in which a polymer is dissolved in an organic solvent.
• organic solvent-based composition in which a polymer is dissolved in an organic solvent.
• the present invention aims to provide a composition for forming a resist underlayer film that uses water as a solvent, a resist underlayer film, a substrate for semiconductor processing, a method for manufacturing a semiconductor element, and a method for forming a pattern.
• the present invention includes the following.
• a composition comprising a first component and a solvent, the first component has an aromatic ring, at least one oxygen atom bonded directly to the aromatic ring by a single bond, and at least one hydroxy group other than a phenolic hydroxy group;
• the solvent contains 50% by mass or more of water relative to the solvent.
• a composition comprising a first component, a second component, and a solvent, the first component has an aromatic ring and at least one oxygen atom bonded directly to the aromatic ring by a single bond; the second component is a water-soluble polymer; a mass ratio of the first component to the second component (first component:second component) is 99:1 to 50:50; The solvent contains 50% by mass or more of water relative to the solvent.
• a composition for forming a resist underlayer film [3] The composition for forming a resist underlayer film according to [1], further comprising a second component which is a water-soluble polymer.
• first component:second component a mass ratio of the first component to the second component
• second component a mass ratio of the first component to the second component
• the first component ⁇ -glucosylrutin, troxerutin, and a reaction product of at least one of quercetin and quercetin glycoside with an epoxy group-containing compound
• the water-soluble polymer is at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polystyrene sulfonic acid, and water-soluble cellulose.
• a semiconductor substrate; [14] The resist underlayer film according to [14], A semiconductor processing substrate comprising: [16] A step of forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [13]; forming a resist film on the resist underlayer film;
• a method for manufacturing a semiconductor device comprising: [17] A step of forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [13]; forming a resist film on the resist underlayer film; a step of irradiating the resist film with light or an electron beam and then developing the resist film to obtain a resist pattern; Etching the resist underlayer film using the resist pattern as a mask;
• a pattern forming method comprising:
• the present invention provides a composition for forming a resist underlayer film, a resist underlayer film, a substrate for semiconductor processing, a method for manufacturing a semiconductor element, and a method for forming a pattern, all of which use water as a solvent. This reduces the amount of organic solvents that have been used in this field, thereby contributing to reducing the environmental impact.
• composition for forming resist underlayer film contains a first component and water.
• composition for forming a resist underlayer film of the present invention contains a first component, a second component, and water.
• the first component is an organic compound.
• the first component is, for example, a component that may be used in combination with the second component in a composition for forming a resist underlayer film.
• the first component is an organic compound that dissolves in a solvent in order to be used as a composition for forming a resist underlayer film.
• the molecular weight of the first component is not particularly limited, and the first component may be a low molecular weight compound or a high molecular weight compound.
• the organic compound that is the first component has, for example, an aromatic ring and at least one oxygen atom directly bonded to the aromatic ring via a single bond.
• the organic compound that is the first component has, for example, an aromatic ring and at least two oxygen atoms directly bonded to the aromatic ring by single bonds.
• the organic compound that is the first component has, for example, an aromatic ring, at least one oxygen atom directly bonded to the aromatic ring via a single bond, and at least one hydroxy group other than a phenolic hydroxy group.
• the organic compound that is the first component has, for example, an aromatic ring, at least two oxygen atoms directly bonded to the aromatic ring by single bonds, and at least one hydroxy group other than a phenolic hydroxy group.
• the organic compound that is the first component has, for example, an aromatic ring, at least two oxygen atoms directly bonded to the aromatic ring by single bonds, and at least two hydroxy groups other than phenolic hydroxy groups. Since the first component has an aromatic ring, excellent solvent resistance and excellent antireflection performance are imparted to the resist underlayer film obtained from the composition for forming a resist underlayer film.
• the organic compound that is the first component may or may not have a phenolic hydroxy group.
• hydroxy groups other than phenolic hydroxy groups include hydroxy groups bonded to carbon atoms not constituting an aromatic ring, such as hydroxy groups generated by a ring-opening reaction of an epoxy group and hydroxy groups contained in sugars.
• the organic compound which is the first component preferably has at least one of a flavone structure and a flavanone structure, more preferably a flavonol structure, and particularly preferably a quercetin structure, in terms of excellent light absorption properties for i-lines (365 nm).
• the flavone structure means flavone itself represented by the following formula (f-1) and a structure in which at least one hydrogen atom of flavone has been substituted.
• the flavanone structure means a flavanone itself represented by the following formula (f-2) and a structure in which at least one hydrogen atom of a flavanone has been substituted.
• the flavonol structure means the flavonol itself represented by the following formula (f-3), and a structure in which at least one hydrogen atom of the flavonol has been substituted.
• the quercetin structure means quercetin itself represented by the following formula (q) and a structure in which at least one hydrogen atom of quercetin has been substituted.
• the quercetin structure is an example of a flavonol structure.
• the flavonol structure is an example of a flavone structure. Therefore, when a compound has a quercetin structure, the compound also has a flavonol structure. Also, the compound also has a flavone structure.
• the aromatic ring may be a monocyclic ring or a condensed ring.
• the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
• the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an acenaphthylene ring, a phenanthrene ring, an anthracene ring, and a pyrene ring.
• aromatic heterocycle examples include a thiophene ring, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, an indole ring, an indazole ring, a benzotriazole ring, a quinazoline ring, an acridine ring, a chromanone ring, and a chromone ring.
• the benzene ring and chromone ring in the flavone structure, flavonol structure, and quercetin structure are each an aromatic ring in the present invention.
• the benzene ring and the chromanone ring in the flavanone structure are each an aromatic ring in the present invention.
• the oxygen atom of the -OH group in flavonol and quercetin is an oxygen atom directly bonded to the aromatic ring by a single bond.
• the oxygen atom is bonded to an atom other than the atoms constituting the aromatic ring by another single bond.
• the organic compound that is the first component is preferably a compound having at least one of a flavone structure and a flavanone structure.
• the organic compound that is the first component is preferably a reaction product between a compound having at least one of a flavone structure and a flavanone structure and an epoxy group-containing compound.
• Examples of compounds with a flavone structure include flavones and flavonols.
• flavonols which are compounds having a flavone structure
• quercetin and quercetin derivatives examples include quercetin and quercetin derivatives.
• An example of a quercetin derivative is quercetin glycoside.
• quercetin glycosides include, for example, quercitrin, isoquercitrin, hyperoside, rutin, troxerutin, ⁇ -glucosylrutin, and the like. These may be in the form of hydrates.
• quercetin hydrate, quercitrin, isoquercitrin, hyperoside, rutin hydrate, troxerutin, and ⁇ -glucosylrutin are shown below.
• Examples of compounds having a flavanone structure include hesperetin and hesperetin derivatives.
• An example of a hesperetin derivative is hesperetin glycoside.
• Such hesperetin glycosides include, for example, hesperetin and methylhesperetin. These may be in the form of hydrates.
• the structures of hesperetin, hesperesin, and methylhesperesin are shown below.
• naringenin and naringenin derivatives include naringenin and naringenin derivatives.
• Naringenin derivatives include, for example, naringenin glycosides.
• Such naringenin glycosides include, for example, naringin. These may be in the form of hydrates.
• the structures of naringenin and naringin hydrate are shown below.
• ⁇ Henaringenin ⁇ Naringin Hydrate Other examples include, for example, chrysin, baicalein, galangin, apigenin, wogonin, acacetin, luteolin, kaempferol, scutellarin, diosmetin, kaempferide, morin, isorhamnetin, myricetin, scutellarein tetramethyl ether, eupatilin, icaritin, tangeretin, nobiletin, etc. These may be hydrates. For reference, these structures are shown below.
• the epoxy group-containing compound used to obtain the reaction product is not particularly limited as long as it is a compound that has at least one epoxy group.
• the number of epoxy groups in the epoxy group-containing compound can be, for example, 1 to 4, with 1 or 2 being preferred.
• epoxy group-containing compounds examples include aliphatic epoxy compounds and aromatic epoxy compounds. Among these, aliphatic epoxy compounds are preferred in terms of their solubility in water.
• Examples of the aliphatic epoxy compound include glycidol, glycidyl ethers of aliphatic alcohols, and polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts.
• the aliphatic epoxy compound include glycidyl ethers of polyhydric alcohols such as glycidol, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12 to C13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and diglycidyl ether of neopentyl glycol; polyglycidy
• Further examples include compounds having a tricyclodecane structure and a glycidyl ether group, such as dimethyloltricyclodecane diglycidyl ether and tricyclodecane diglycidyl ether. Also included is a compound obtained by reacting an aliphatic glycidyl ether epoxy compound having two or more glycidyl ether groups with a main chain skeleton that contains a rubber component and includes a group capable of reacting with an epoxy group to form a covalent bond.
• aliphatic epoxy compound commercially available products can be used, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-252, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-422, Denacol EX-423, Denacol EX-424, Denacol EX-425, Denacol EX-426, Denacol EX-427, Denacol EX-428, Denacol EX-429, Denacol EX-430, Denacol EX-431, Denacol EX-432, Denacol EX-433, Denacol EX-434, Denacol EX-435, Denacol EX-436, Denacol EX-437, Denacol EX-438, Denacol EX-439, Denacol EX
• compounds having a cycloalkene oxide structure and an epoxy group that does not share a part of the ring structure with an aliphatic ring such as diglycidyl 4,5-epoxycyclohexane-1,2-dicarboxylate, are also included in the alicyclic epoxy compound.
• alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis( 3,4-epoxycyclohexylmethyl) adipate, methylene bis(
• alicyclic epoxy compound commercially available products can be used, such as UVR6105, UVR6110, and UVR6128 manufactured by Union Carbide Corporation; Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 2000, Celloxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolead GT-301, Epolead GT-302, Epolead GT-401, Epolead GT-403, ETHB, and Epolead HD300 manufactured by Daicel Chemical Industries, Ltd.; and THI-DE, DE-102, and DE-103 manufactured by JXTG Nippon Oil & Energy Corporation.
• UVR6105, UVR6110, and UVR6128 manufactured by Union Carbide Corporation
• Celloxide 2021P Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 2000, Celloxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolead
• aromatic epoxy compound examples include: Polyglycidyl ethers of polyhydric phenols having at least one aromatic ring, such as bisphenol A and bisphenol F, or alkylene oxide adducts thereof; Polyglycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups, such as resorcinol, hydroquinone, and catechol; Polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, such as phenyldimethanol, phenyldiethanol, and phenyldibutanol; Polyglycidyl esters of polybasic aromatic compounds having two or more carboxy groups, such as phthalic acid, terephthalic acid, trimellitic acid, etc.; Diepoxidized product of divinylbenzene; Glycidylamine compounds such as N,N-diglycidylaniline and its derivatives. Also included is a compound obtained by reacting an aromatic epoxy compound having two or more glycidyl
• aromatic epoxy compound commercially available products can be used, for example, Denacol EX-141, EX-142, EX-145, EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, EX-731, Oncoat EX-1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (manufactured by Nagase ChemteX Corporation); Oxol PG-100, Oxol EG-200, Oxol EG-210, Oxol EG-250 ( HP4032, HP4032D, HP4700 (manufactured by DIC Corporation); ESN-475V (manufactured by Tohto Kasei Co., Ltd.); YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-01
• the molecular weight of the epoxy group-containing compound is not particularly limited, but is preferably from 74 to 2,000, more preferably from 74 to 1,500, and particularly preferably from 74 to 1,000.
• the molecular weight of glycidol is 74.
• the mass ratio (F:E) of the compound (F) having at least one of a flavone structure and a flavanone structure to the epoxy group-containing compound (E) is preferably 10:1 to 1:5, and more preferably 5:1 to 1:3.
• the reaction to obtain the reaction product may be carried out, for example, in the presence of a catalyst.
• the catalyst is, for example, a quaternary phosphonium salt such as tetrabutylphosphonium bromide or ethyltriphenylphosphonium bromide, or a quaternary ammonium salt such as benzyltriethylammonium chloride.
• the amount of catalyst used may be selected appropriately from the range of 0.1 to 10% by mass based on the total mass of the polymer raw material used in the reaction.
• the optimum conditions for the temperature and time of the polymerization reaction may be selected, for example, from the ranges of 80 to 160°C and 2 to 50 hours.
• reaction product An example of the reaction product is shown below.
• An example below is the reaction product of quercetin and glycidol.
• An example below is the reaction product of rutin and glycidol.
• the molecular weight of the first component is not particularly limited. From the viewpoint of solubility in water, it is preferable that the weight average molecular weight of the first component is small.
• the weight average molecular weight of the first component is, for example, 300 to 100,000, preferably 300 to 50,000, more preferably 300 to 10,000, and particularly preferably 300 to 5,000.
• the content of the first component in the film-constituting components of the composition for forming a resist underlayer film is not particularly limited, but is preferably 25% by mass to 99% by mass, more preferably 50% by mass to 90% by mass, and particularly preferably 60% by mass to 80% by mass, based on the film-constituting components.
• the film constituent components are components other than the solvent in the composition for forming a resist underlayer film.
• the second component is used to improve the coatability of the composition for forming a resist underlayer film.
• the second component is a water-soluble polymer.
• the second component is a different compound than the first component.
• the water-soluble polymer is a polymeric compound that dissolves at least 1 g in 100 g of water at 25°C, preferably at least 5 g in 100 g of water at 25°C, and more preferably at least 10 g in 100 g of water at 25°C.
• Water-soluble polymers are not particularly limited, but examples include polyvinyl alcohol, water-soluble cellulose, polyethylene glycol (PEG), polyethylene oxide (PEO), polyvinylpyrrolidone, polyacrylic acid, polystyrene sulfonic acid, polyvinylacetamide, etc.
• Polyvinyl alcohol is a polymer obtained by hydrolyzing polyvinyl acetate and changing the acetyl groups in the polyvinyl acetate molecule to hydroxyl groups. The ratio of these hydroxyl groups expressed in mole percent is called the degree of saponification.
• Polyvinyl alcohols are known to have various properties depending on their degree of saponification. For example, polyvinyl acetate (0 mole percent saponification) is generally water-insoluble, while polyvinyl alcohol with a degree of saponification of 100 mole percent is known to be water-soluble.
• polyvinyl alcohols those with a degree of saponification of 60 mole percent or less have poor solubility in water, and those with a degree of saponification of 30 mole percent or less are practically insoluble. Conversely, if the degree of saponification is too high, the solubility is low, and those with a degree of saponification of 85 to 90 mole percent have the highest solubility. In the present invention, it is preferable to use polyvinyl alcohol with a degree of saponification of 70 mole percent or more. In general, the higher the degree of saponification, the better the developer resistance, so it is preferable to use polyvinyl alcohol with a degree of saponification of 75 mole percent or more.
• the degree of saponification of polyvinyl alcohol is preferably 99 mol% or less, and more preferably 98 mol% or less.
• the degree of polymerization of polyvinyl alcohol is usually expressed as the viscosity of a 4% by weight aqueous solution (20°C), and is generally about 1 to 80 cps (mPa ⁇ s).
• the polyvinyl alcohol used in the present invention is preferably one having a viscosity of 1 cps or more, and more preferably one having a viscosity of 2 cps or more.
• the upper limit of the viscosity is preferably 70 cps, and more preferably 65 cps, 50 cps, 40 cps, 30 cps, 20 cps, 10 cps, 8 cps, or 5 cps.
• the viscosity range is, for example, 1 to 20 cps, 2 to 10 cps, or 3 to 8 cps.
• Polyvinyl alcohol may be modified by replacing some of its hydroxyl groups with alkyl ether groups, alkyloxymethyl groups, acetyl acetate groups, or the like.
• the water-soluble cellulose is not particularly limited, but examples thereof include alkyl celluloses such as methyl cellulose and ethyl cellulose; hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose; and hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose. Among these, hydroxypropyl cellulose is more preferable.
• Hydroxypropyl cellulose is commercially available in various products with different viscosities from various companies, and any of them can be used in the present invention.
• the viscosity of 2% by weight aqueous solution (20°C) of hydroxypropyl cellulose is not particularly limited and can be appropriately selected according to the purpose, but is preferably 2.0 mPa ⁇ s (centipoise, cps) or more and 4,000 mPa ⁇ s (centipoise, cps) or less.
• the viscosity of hydroxypropyl cellulose is also believed to depend on the weight average molecular weight, degree of substitution, and molecular weight of hydroxypropyl cellulose.
• the weight-average molecular weight of hydroxypropyl cellulose is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 15,000 or more and 400,000 or less.
• the weight-average molecular weight can be measured, for example, using gel permeation chromatography (GPC).
• hydroxypropyl cellulose there are no particular limitations on the commercially available hydroxypropyl cellulose, and it can be appropriately selected depending on the purpose.
• the following commercially available products can be mentioned.
• - HPC-SSL or the like manufactured by Nippon Soda Co., Ltd.
• a molecular weight of 15,000 to 30,000 and a viscosity of 2.0 to 2.9 mPa ⁇ s - HPC-SL or the like manufactured by Nippon Soda Co., Ltd.
• a molecular weight of 30,000 to 50,000 and a viscosity of 3.0 to 5.9 mPa ⁇ s - HPC-L or the like manufactured by Nippon Soda Co., Ltd.
• a molecular weight of 55,000 to 70,000 and a viscosity of 6.0 to 10.0 mPa ⁇ s - HPC-M or the like manufactured by Nippon Soda Co., Ltd.
• polyvinylpyrrolidone examples include homopolymers of vinylpyrrolidone such as N-vinyl-2-pyrrolidone and N-vinyl-4-pyrrolidone, and copolymers of vinylpyrrolidone with vinyl acetate, ⁇ -olefin, styrene, etc.
• Polyvinylpyrrolidone may be three-dimensionally crosslinked. It is preferable to use polyvinylpyrrolidone having a K value of 60 or more in Fikentscher's formula, particularly a grade of K-60 to K-120, and a number average molecular weight of 30,000 to 280,000 is preferable.
• Polystyrene sulfonic acid includes, for example, compounds in which a sulfonic acid group is substituted on the benzene ring of polystyrene, such as poly(3-styrene sulfonic acid), poly(4-styrene sulfonic acid), and poly(3,5-styrene sulfonic acid).
• the number of sulfonic acid groups substituted on the benzene ring is preferably 1 to 5, and more preferably 1.
• the position of the sulfonic acid group may be any of the ortho position (1st or 5th position), meta position (2nd or 4th position), and para position (3rd position). Of these, meta position (2nd or 4th position) is preferred.
• the unit units constituting polystyrene sulfonic acid may be one type or two or more types. When there are two or more types of unit units constituting polystyrene sulfonic acid, it may be composed of a plurality of unit units with different numbers and positions of sulfonic acid group substitutions. Furthermore, it may be composed of unit units not substituted with sulfonic acid groups (i.e., units derived from styrene). However, in this case, polystyrene sulfonic acid is not composed only of units derived from styrene.
• the content of the second component (water-soluble polymer) in the composition for forming the resist underlayer film is not particularly limited.
• the mass ratio of the first component to the second component (first component:second component) in the composition for forming a resist underlayer film is preferably 99:1 to 50:50, more preferably 99:1 to 75:25, and particularly preferably 99:1 to 90:10.
• the composition for forming a resist underlayer film preferably contains a crosslinking agent.
• the crosslinking agent contained as an optional component in the composition for forming a resist underlayer film has, for example, a functional group that reacts by itself.
• crosslinking agents examples include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (tetramethoxymethylglycoluril) (POWDERLINK [registered trademark] 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.
• the crosslinking agent may also be a nitrogen-containing compound having 2 to 6 substituents bonded to nitrogen atoms and represented by the following formula (1d) per molecule, as described in WO 2017/187969.
• R1 represents a methyl group or an ethyl group. * represents a bond bonded to the nitrogen atom.
• the nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule may be a glycoluril derivative represented by the following formula (1E).
• R 1s each independently represent a methyl group or an ethyl group
• R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
• glycoluril derivative represented by formula (1E) examples include compounds represented by the following formulas (1E-1) to (1E-6).
• the nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2d) in one molecule that are bonded to nitrogen atoms with at least one compound represented by the following formula (3d).
• R1 represents a methyl group or an ethyl group
• R4 represents an alkyl group having 1 to 4 carbon atoms
• * represents a bond bonded to a nitrogen atom.
• the glycoluril derivative represented by the formula (1E) can be obtained by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the formula (3d).
• the nitrogen-containing compound having 2 to 6 substituents represented by the formula (2d) in one molecule is, for example, a glycoluril derivative represented by the following formula (2E).
• R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represent an alkyl group having 1 to 4 carbon atoms.
• glycoluril derivative represented by formula (2E) examples include compounds represented by the following formulas (2E-1) to (2E-4). Furthermore, examples of the compound represented by formula (3d) include compounds represented by the following formulas (3d-1) and (3d-2).
• the crosslinking agent may also be a crosslinkable compound represented by the following formula (G-1) or formula (G-2) described in WO 2014/208542.
• Q1 represents a single bond or an m1-valent organic group
• R1 and R4 each represent an alkyl group having 2 to 10 carbon atoms or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms
• R2 and R5 each represent a hydrogen atom or a methyl group
• R3 and R6 each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.
• n1 is an integer satisfying 1 ⁇ n1 ⁇ 3, n2 is an integer satisfying 2 ⁇ n2 ⁇ 5, n3 is an integer satisfying 0 ⁇ n3 ⁇ 3, n4 is an integer satisfying 0 ⁇ n4 ⁇ 3, and 3 ⁇ (n1+n2+n3+n4) ⁇ 6.
• n5 is an integer satisfying 1 ⁇ n5 ⁇ 3, n6 is an integer satisfying 1 ⁇ n6 ⁇ 4, n7 is an integer satisfying 0 ⁇ n7 ⁇ 3, n8 is an integer satisfying 0 ⁇ n8 ⁇ 3, and 2 ⁇ (n5+n6+n7+n8) ⁇ 5.
• m1 represents an integer from 2 to 10.
• the crosslinkable compound represented by the above formula (G-1) or (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms.
• Q2 represents a single bond or an m2-valent organic group.
• R8 , R9 , R11 , and R12 each represent a hydrogen atom or a methyl group
• R7 and R10 each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.
• n9 is an integer satisfying 1 ⁇ n9 ⁇ 3, n10 is an integer satisfying 2 ⁇ n10 ⁇ 5, n11 is an integer satisfying 0 ⁇ n11 ⁇ 3, n12 is an integer satisfying 0 ⁇ n12 ⁇ 3, and 3 ⁇ (n9+n10+n11+n12) ⁇ 6.
• n13 indicates an integer satisfying 1 ⁇ n13 ⁇ 3
• n14 indicates an integer satisfying 1 ⁇ n14 ⁇ 4
• n15 indicates an integer satisfying 0 ⁇ n15 ⁇ 3
• n16 indicates an integer satisfying 0 ⁇ n16 ⁇ 3
• m2 represents an integer from 2 to 10.
• Me represents a methyl group.
• the content of the crosslinking agent in the composition for forming a resist underlayer film is, for example, 1 mass % to 50 mass %, and preferably 5 mass % to 40 mass %, based on the total of the first component and the second component.
• the content ratio of the crosslinking agent in the composition for forming a resist underlayer film is, for example, 1 mass % to 50 mass %, and preferably 5 mass % to 40 mass %, relative to the total of the first component.
• the curing catalyst contained as an optional component in the composition for forming a resist underlayer film may be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator.
• thermal acid generators include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridinium trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.
• carboxylic acid compounds such as p-toluenesulfonic acid
• photoacid generators examples include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
• onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium triflu
• sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.
• disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
• the content of the curing catalyst relative to the crosslinking agent is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass.
• the composition for forming a resist underlayer film contains a solvent.
• the solvent includes water.
• the solvent may contain an organic solvent in addition to water.
• the solvent preferably contains 50% or more water by mass relative to the solvent, more preferably 70% or more water by mass relative to the solvent, even more preferably 80% or more water by mass relative to the solvent, and particularly preferably 90% or more water by mass relative to the solvent.
• organic solvents organic solvents generally used in chemical solutions for semiconductor lithography processes are preferred. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohex ...
• Examples of the solvent include heptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, ⁇ -butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.
• propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred.
• Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.
• a surfactant may be further added to the composition for forming a resist underlayer film in order to prevent pinholes, striations, and the like, and to further improve the coatability against surface unevenness.
• the surfactant examples include linear or branched alkylbenzenesulfonic acid (e.g., dodecylbenzenesulfonic acid, etc.), polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and polyoxyethylene sorbitan monolaurate.
• alkylbenzenesulfonic acid e.g., dodecylbenzenesulfonic
• nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as EFTOP EF301, EF303, and EF352 (manufactured by Tochem Products Co., Ltd., trade names), Megafac F171, F173, and R-30 (manufactured by DIC Corporation, trade names), Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited, trade names), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd., trade names); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co.,
• the amount of these surfactants to be added is not particularly limited, but is usually 2.0% by mass or less, and preferably 1.0% by mass or less, based on the total solid content of the composition for forming a resist underlayer film. These surfactants may be added alone or in combination of two or more kinds.
• the film constituent components contained in the composition for forming a resist underlayer film i.e., the components excluding the solvent, are, for example, 0.01% by mass to 10% by mass of the composition for forming a resist underlayer film.
• the composition for forming a resist underlayer film of the present invention is produced, for example, by a method of mixing the first component and a solvent by a known method.
• a method of mixing the first component and a solvent by a known method.
• the composition is in a homogeneous solution state.
• the composition is preferably filtered with a filter or the like to remove metal impurities, foreign matter, etc. present in the composition.
• One of the measures for evaluating whether a composition for forming a resist underlayer film is in a uniform solution state is to observe the passability through a specific microfilter.
• the composition for forming a resist underlayer film according to the present invention passes through microfilters having pore sizes of 0.1 ⁇ m, 0.05 ⁇ m, 0.03 ⁇ m, 0.02 ⁇ m, and 0.01 ⁇ m and exhibits a uniform solution state.
• the material of the microfilter may be fluororesin such as PTFE (polytetrafluoroethylene) or PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra-high molecular weight polyethylene), PP (polypropylene), PSF (polysulfone), PES (polyethersulfone), or nylon, but it is preferably made of PTFE (polytetrafluoroethylene). Since the resist underlayer film forming composition contains water as a solvent, it is preferable that the filter used to filter the resist underlayer film forming composition is a filter that has been subjected to a hydrophilization treatment.
• PTFE polytetrafluoroethylene
• PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
• PE polyethylene
• UPE ultra-high molecular weight polyethylene
• PP polypropylene
• PSF polysul
• the resist underlayer film of the present invention is a cured product of the above-mentioned composition for forming a resist underlayer film.
• the resist underlayer film can be produced, for example, by applying the above-mentioned composition for forming a resist underlayer film onto a semiconductor substrate and baking the applied composition.
• Semiconductor substrates onto which the resist underlayer film forming composition is applied include, for example, silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.
• the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin-coating (spin-on glass: SOG).
• ALD atomic layer deposition
• CVD chemical vapor deposition
• reactive sputtering ion plating
• vacuum deposition or spin-coating
• spin-on glass SOG
• the inorganic film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film.
• the inorganic film may be a single layer or a multilayer of two or more layers. In the case of a multilayer or more, each layer may be the same type of inorganic film or different types of inorganic film.
• the resist underlayer film forming composition of the present invention is applied onto such a semiconductor substrate by a suitable application method such as a spinner or coater.
• the resist underlayer film is then 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 350°C
• the baking time is 0.5 minutes to 30 minutes
• the baking temperature is 150°C to 300°C
• the baking time is 0.8 minutes to 10 minutes.
• the thickness of the resist underlayer film may be, for example, 0.001 ⁇ m (1 nm) to 10 ⁇ m, 0.002 ⁇ m (2 nm) to 1 ⁇ m, 0.005 ⁇ m (5 nm) to 0.5 ⁇ m (500 nm), 0.001 ⁇ m (1 nm) to 0.05 ⁇ m (50 nm), 0.002 ⁇ m (2 nm) to 0.05 ⁇ m (50 nm), 0.003 ⁇ m (3 nm) to 0.05 ⁇ m (50 nm), 0.004 ⁇ m (4 nm) to 0.05 ⁇ m (50 nm), 0.005 ⁇ m (5 nm) to 0.05 ⁇ m (5 0 nm), 0.003 ⁇ m (3 nm) to 0.03 ⁇ m (30 nm), 0.003 ⁇ m (3 nm) to 0.02 ⁇ m (20 nm), 0.005 ⁇ m (5 nm) to 0.02 ⁇ m (20 nm),
• the method for measuring the film thickness of the resist underlayer film is as follows.
• Measurement device name Optical interference film thickness meter (product name: Nanospec 6100, manufactured by Nanometrics Japan Co., Ltd.) Arithmetic average of four points (for example, four points are measured at 1 cm intervals in the X direction of the wafer)
• the semiconductor processing substrate of the present invention comprises a semiconductor substrate and the resist underlayer film of the present invention.
• the semiconductor substrate may be, for example, the semiconductor substrate described above.
• the resist underlayer film is disposed, for example, on a semiconductor substrate.
• the method for manufacturing a semiconductor device of the present invention includes at least the following steps. - forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention; and - forming a resist film on the resist underlayer film.
• the pattern forming method of the present invention includes at least the following steps.
• a step of etching the resist underlayer film using the resist pattern as a mask includes at least the following steps.
• a resist film is formed on the resist underlayer film.
• the thickness of the resist film is, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, or 1,000 nm or less.
• the lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, or 10 nm.
• the resist film formed on the resist underlayer film by a known method is not particularly limited as long as it responds to light or electron beam (EB) used for irradiation.
• EB light or electron beam
• the light or electron beam is not particularly limited, but examples thereof include i-line (365 nm), KrF excimer laser (248 nm), ArF excimer laser (193 nm), EUV (extreme ultraviolet; 13.5 nm), and EB (electron beam).
• a resist that responds to EB is also called a photoresist.
• photoresists include positive photoresists made of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists made of a binder having a group that decomposes with acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresists made of a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, chemically amplified photoresists made of a binder having a group that decomposes with acid to increase the alkaline dissolution rate of the photoresist, a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator, and resists containing metal elements.
• V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned.
• resist compositions include the following compositions:
• An actinic ray-sensitive or radiation-sensitive resin composition comprising: resin A having a repeating unit having an acid-decomposable group in which a polar group is protected with a protecting group that is cleaved by the action of an acid; and a compound represented by the following general formula (21).
• m represents an integer of 1 to 6.
• R 1 and R 2 each independently represent a fluorine atom or a perfluoroalkyl group.
• L 1 represents —O—, —S—, —COO—, —SO 2 — or —SO 3 —.
• L2 represents an alkylene group which may have a substituent or a single bond.
• W 1 represents a cyclic organic group which may have a substituent.
• M + represents a cation.
• a metal-containing film-forming composition for extreme ultraviolet or electron beam lithography comprising a compound having a metal-oxygen covalent bond and a solvent, the metal element constituting the compound belonging to Periods 3 to 7 of Groups 3 to 15 of the periodic table.
• a radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) containing an acid-dissociable group, and an acid generator.
• Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms.
• R 1 is a hydroxy group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms.
• n is an integer from 0 to 11. When n is 2 or more, multiple R 1s are the same or different.
• R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• R 3 is a monovalent group having 1 to 20 carbon atoms containing the above-mentioned acid dissociable group.
• Z is a single bond, an oxygen atom, or a sulfur atom.
• R 4 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• R 2 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom
• X 1 represents a single bond, -CO-O-* or -CO-NR 4 -*
• * represents a bond to -Ar
• R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more groups selected from the group consisting of a hydroxyl group and a carboxyl group.
• resist films examples include:
• a resist film comprising a base resin containing a repeating unit represented by the following formula (a1) and/or a repeating unit represented by the following formula (a2) and a repeating unit that generates an acid bonded to the polymer main chain upon exposure.
• R A is each independently a hydrogen atom or a methyl group.
• R 1 and R 2 are each independently a tertiary alkyl group having 4 to 6 carbon atoms.
• R 3 is each independently a fluorine atom or a methyl group.
• m is an integer of 0 to 4.
• X 1 is a single bond, a phenylene group or a naphthylene group, or a linking group having 1 to 12 carbon atoms containing at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group.
• X 2 is a single bond, an ester bond, or an amide bond.
• resist materials examples include:
• R A is a hydrogen atom or a methyl group.
• X 1 is a single bond or an ester group.
• X 2 is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, a part of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group or a lactone ring-containing group, and at least one hydrogen atom contained in X 2 is substituted with a bromine atom.
• X 3 is a single bond, an ether group, an ester group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, a part of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group.
• Rf 1 to Rf 4 are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, and at least one of them is a fluorine atom or a trifluoromethyl group. 2 may combine to form a carbonyl group.
• R 1 to R 5 are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, some or all of the hydrogen atoms of these groups may be substituted with a hydroxy group, a carboxy group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group
• a resist material comprising a base resin containing a polymer containing a repeating unit represented by the following formula (a):
• R A is a hydrogen atom or a methyl group.
• R 1 is a hydrogen atom or an acid labile group.
• R 2 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine.
• X 1 is a single bond, a phenylene group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which may contain an ester group or a lactone ring.
• X 2 is -O-, -O-CH 2 - or -NH-.
• m is an integer of 1 to 4.
• u is an integer of 0 to 3, with the proviso that m+u is an integer of 1 to 4.
• a resist composition which generates an acid upon exposure and changes its solubility in a developer by the action of the acid
• the composition contains a base component (A) whose solubility in a developer changes under the action of an acid, and a fluorine additive component (F) that is decomposable in an alkaline developer
• the fluorine additive component (F) is a resist composition containing a fluorine resin component (F1) having a structural unit (f1) containing a base dissociable group, and a structural unit (f2) containing a group represented by the following general formula (f2-r-1):
• Rf 21 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group.
• n′′ is an integer of 0 to 2. * represents a bond.
• the structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).
• R is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
• X is a divalent linking group having no acid dissociable site.
• a aryl is a divalent aromatic cyclic group which may have a substituent.
• X 01 is a single bond or a divalent linking group.
• R 2 is each independently an organic group having a fluorine atom.
• coatings examples include the following:
• a coating comprising a metal oxo-hydroxo network with organic ligands via metal carbon bonds and/or metal carboxylate bonds.
• RzSnO (2-(z/2)-(x/2)) (OH) x , where 0 ⁇ z ⁇ 2 and 0 ⁇ (
• a coating solution comprising an organic solvent and a first organometallic compound having the formula RSnO (3/2-x/2) (OH) x , where 0 ⁇ x ⁇ 3, wherein the solution contains from about 0.0025M to about 1.5M tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, the alkyl or cycloalkyl group being bonded to the tin at a secondary or tertiary carbon atom.
• An aqueous inorganic pattern forming precursor solution comprising water, a mixture of metal suboxide cations, polyatomic inorganic anions, and a radiation sensitive ligand comprising a peroxide group.
• the irradiation with light or electron beams is performed, for example, through a mask (reticle) for forming a predetermined pattern.
• the exposure dose and the irradiation energy of the electron beam are not particularly limited.
• baking Post Exposure Bake
• the baking temperature is not particularly limited, but is preferably from 60°C to 150°C, more preferably from 70°C to 120°C, and particularly preferably from 75°C to 110°C.
• the baking time is not particularly limited, but is preferably from 1 second to 10 minutes, more preferably from 10 seconds to 5 minutes, and particularly preferably from 30 seconds to 3 minutes.
• an alkaline developer is used.
• the development temperature is, for example, from 5°C to 50°C.
• the development time may be, for example, from 10 seconds to 300 seconds.
• alkaline developer for example, aqueous solutions of alkalis such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and cyclic amines such as pyrrole and piperidine can be used.
• alkalis
• the resist underlayer film is etched using the formed resist pattern as a mask.
• the etching may be dry etching or wet etching, but is preferably dry etching.
• the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and when the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed.
• the semiconductor substrate is then processed by a known method (e.g., dry etching) to manufacture a semiconductor device.
• the weight average molecular weights of the polymers shown in the following Synthesis Examples 1 to 7 are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC).
• GPC column Shodex GF-710HQ, Shodex GF-510HQ, Shodex GF-310HQ (registered trademark) (Showa Denko K.K.)
• Eluent N,N-dimethylformamide (DMF)
• Standard sample Polystyrene (Tosoh Corporation)
• the weight average molecular weight Mw measured in terms of polystyrene was 2600.
• the obtained reaction product was dissolved in ultrapure water to a concentration of 10% by mass to obtain an aqueous solution of the reaction product.
• Example 1 0.12 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-phenolsulfonate, 0.02 g of polyvinyl alcohol (Poval PXP-05, Nippon Vinyl Acetate & Poval Corporation), and 24.89 g of ultrapure water were added to 4.93 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 1 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• aqueous solution solid content: 10% by mass
• Example 2 0.12 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-phenolsulfonate, 0.02 g of polyvinyl alcohol (Poval PXP-05, Nippon Vinyl Acetate & Poval Corporation), and 24.89 g of ultrapure water were added to 4.93 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 2 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• aqueous solution solid content: 10% by mass
• Example 3 0.12 g of tetramethoxymethylglycoluril, 0.02 g of pyridinium p-phenolsulfonate, 0.02 g of polyvinyl alcohol (Poval PXP-05, Nippon Vinyl Acetate & Poval Corporation), and 24.89 g of ultrapure water were added to 4.93 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 3 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• aqueous solution solid content: 10% by mass
• Example 4 To 4.93 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 4, 0.12 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-phenolsulfonate, 0.02 g of polyvinyl alcohol (Poval PXP-05, Nippon Vinyl Acetate & Poval Corporation), and 24.89 g of ultrapure water were added to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m
• Example 5 0.12 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-phenolsulfonate, 0.02 g of polyvinyl alcohol (Poval PXP-05, Nippon Vinyl Acetate & Poval Corporation), and 24.89 g of ultrapure water were added to 4.93 g of the aqueous solution of the reaction product obtained in Synthesis Example 5 (solid content: 10% by mass) to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m
• Example 6 To 4.93 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 6, 0.12 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-phenolsulfonate, 0.02 g of polyvinyl alcohol (Poval PXP-05, Nippon Vinyl Acetate & Poval Corporation), and 24.89 g of ultrapure water were added to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m
• Example 7 To 4.93 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 7, 0.12 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-phenolsulfonate, 0.02 g of polyvinyl alcohol (Poval PXP-05, Nippon Vinyl Acetate & Poval Corporation), and 24.89 g of ultrapure water were added to obtain a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m
• Example 8 To 0.49 g of troxerutin, 0.12 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-phenolsulfonate, 0.02 g of polyvinyl alcohol (Poval PXP-05, Nippon Vinyl Acetate & Poval Corporation), and 29.34 g of ultrapure water were added to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m
• Example 9 0.12 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-phenolsulfonate, 0.02 g of polyvinyl alcohol (Poval PXP-05, Nippon Vinyl Acetate & Poval Co., Ltd.), and 29.34 g of ultrapure water were added to 0.49 g of ⁇ -glycosylrutin to prepare a solution.
• the solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• each of the resist underlayer film forming compositions prepared in Examples 1 to 9 was applied (spin-coated) onto a silicon wafer using a spin coater.
• the silicon wafer after application was heated on a hot plate at 205°C for 1 minute to form a coating (underlayer film) with a thickness of 25 nm.
• the silicon wafer after the underlayer film formation was immersed in a mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate in a mass ratio of 7:3 for 1 minute, spin-dried, and baked at 100°C for 30 seconds.
• the thickness of the protective film before and after immersion in the mixed solvent was measured using an optical interference film thickness meter (product name: Nanospec 6100, manufactured by Nanometrics Japan Co., Ltd.).
• Film thickness reduction rate (%) ((A-B) ⁇ A) x 100
• B Film thickness after immersion in solvent
• Table 1 It should be noted that if the film thickness reduction rate is about 1% or less, it can be said that the film has sufficient solvent resistance.
• the films formed from the compositions for forming resist underlayer films of Examples 1 to 9 showed very little change in film thickness even after immersion in a solvent. Therefore, the films formed from the compositions for forming resist underlayer films of Examples 1 to 9 have sufficient solvent resistance to function as underlayer films. In Examples 2, 4, 7 and 8, the film thickness reduction rate is negative, but this does not pose any particular problem.
• the films formed from the resist underlayer film forming compositions of Examples 1 to 9 have absorption at 365 nm and can be used as resist underlayer films.

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