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
  • G03F7/091—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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
  • G03F7/422—Stripping or agents therefor using liquids only
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/69—Etching of wafers, substrates or parts of devices using masks for semiconductor materials
  • H10P50/691—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials
  • H10P50/692—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials characterised by their composition, e.g. multilayer masks or materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
  • H10P50/286—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials
  • H10P50/287—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials by chemical means
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • 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
  • H10P76/2043—Photolithographic processes using an anti-reflective coating

Definitions

• the present invention uses a resist underlayer film forming composition, an uncured resist underlayer film obtained by removing a solvent from a coating film composed of the resist underlayer film forming composition, and the resist underlayer film forming composition.
• the present invention relates to a method for manufacturing a patterned substrate and a semiconductor device.
• a lithography process in which a resist underlayer film is provided between a substrate and a resist film formed on the substrate to form a resist pattern having a desired shape is widely known.
• the resist underlayer film is removed and the substrate is processed, and dry etching is mainly used as the process.
• dry etching is also used in the process of removing unnecessary resist patterns and underlying resist underlayers after substrate processing, but wet etching with a chemical solution is used for the purpose of simplifying the process process and reducing damage to the processed substrate. May be used.
• Patent Document 1 a. A dye-grafted hydroxyl-functional oligomer reaction product of a preselected phenol-or carboxylic acid-functional dye and a poly (epoxide) resin having an epoxy functional value greater than 2.0 and less than 10. The product has light-absorbing properties that are effective for ARC coating of the basal layer; b. Alkylated aminoplast crosslinkers derived from melamine, urea, benzoguanamine or glycoluril; c. Protonic acid curing catalyst; and d. Solvent system containing low to medium boiling alcohol; in the solvent system, the alcohol accounts for at least 20 (20)% by weight of the total solvent content and the molar ratio of alcohol is at least 4: 1 (4) per equivalent methylol unit of aminoplast.
• Consists of, and e An improved ARC composition with ether or ester bonds derived from poly (epoxide) molecules;
• the improved ARC eliminates the mutual mixing of resist / ARC components by the thermosetting action of ARCs, provides improved optical densities at target exposure and ARC layer thickness, and is a high molecular weight thermoplastic ARC showing high solubility differences.
• the improved ARC composition is disclosed, which eliminates the need for binders.
• This ARC composition is described in b. Alkylated aminoplast crosslinkers derived from melamine, urea, benzoguanamine or glycoluril, and c. Since it contains a proton acid curing catalyst, it provides a cured resist underlayer film. However, it is difficult to remove the cured resist underlayer film with a wet etching chemical solution.
• the resist underlayer film By applying a resist on the resist underlayer film and exposing and developing it with radiation (for example, ArF excimer laser light, KrF excimer laser light, i-ray), the resist underlayer film is coated with a desired resist pattern.
• Good resist solvent resistance is required so that peeling and damage are not caused by the resist solvent.
• a resist developer alkaline aqueous solution mainly used in the resist developing step is also required to have good resist developer resistance so as not to cause peeling or damage.
• the resist underlayer film has antireflection performance that suppresses reflection from the underlying substrate against radiation used in the lithography process and suppresses deterioration of the resist pattern due to standing waves. It has been demanded.
• the resist underlayer film is removed by wet etching with a chemical solution, it is required that the resist underlayer film exhibits sufficient solubility in the wet etching chemical solution and can be easily removed from the substrate.
• the wet etching chemical solution for removing the resist and the resist underlayer film an organic solvent is used in order to reduce damage to the processed substrate. Further, in order to improve the removability of the resist and the resist underlayer film, a basic organic solvent is used.
• the resist underlayer film exhibits good resistance to a resist solvent which is an organic solvent and a resist developer which is an alkaline aqueous solution, and exhibits removability, preferably solubility, only in a wet etching chemical solution. Then there was a limit.
• An object of the present invention is to solve the above problems.
• the present invention includes the following.
• a polymer (P) having a dicyanostyryl group or a compound (C) having a dicyanostyryl group is contained. Contains solvent, Free of alkylated aminoplast crosslinkers derived from melamine, urea, benzoguanamine, or glycoluril, Does not contain proton acid curing catalyst, Resist underlayer film forming composition.
• the polymer (P) having a dicyanostyryl group or the compound (C) having a dicyanostyryl group is an epoxy group-containing polymer precursor (PP) or an epoxy group-containing compound precursor (PC), respectively.
• the resist underlayer film forming composition according to [1] which is a reaction product of and an active proton compound.
• the dicyanostyryl group has the following formula (1): (In the formula (1), X represents an alkyl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a cyano group or a nitro group, R represents a hydrogen atom, an alkyl group or an arylene group, and n is 0 to 4.
• the m A's are alkylene groups having 1 to 10 carbon atoms which may be directly bonded, branched or substituted, respectively, and may contain an ether bond, a thioether bond or an ester bond in the alkylene group.
• Each of the m Bs independently represents a direct bond, an ether bond, a thioether bond or an ester bond.
• the m R 1 represents a hydrogen atom, a methyl group, an ethyl group or a propyl group, and may be bonded to Q to form a ring
• R 2 and R 3 are independently hydrogen atoms, methyl groups or propyl groups, respectively. Represents an ethyl group
• the m L's are independently represented by the following equation (3).
• Y represents an ether bond, a thioether bond or an ester bond, and represents R represents a hydrogen atom, an alkyl group or an arylene group.
• n represents an integer from 0 to 4
• Each of n Xs independently represents an alkyl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a cyano group or a nitro group
• a method of manufacturing a patterned substrate including. [13] A step of forming an uncured resist underlayer film composed of the resist underlayer film forming composition according to any one of [1] to [9] on a substrate containing copper on the surface. The step of forming a resist film on the uncured resist underlayer film and A step of forming a resist pattern by irradiating the resist film with light or an electron beam and subsequent development, and then a step of removing the resist underlayer film exposed between the resist patterns. A step of performing copper plating between the formed resist patterns, preferably between the resist patterns from which the resist underlayer film has been removed, The step of removing the resist pattern and the resist underlayer film existing under the resist pattern, and A method for manufacturing a semiconductor device, which comprises. [14] The production method according to [13], wherein at least one of the steps of removing the resist underlayer film is performed by a wet treatment.
• the resist underlayer film forming composition according to the present invention does not contain an alkylated aminoplast cross-linking agent derived from melamine, urea, benzoguanamine, or glycoluril and does not contain a proton acid curing catalyst, the resist underlayer film is uncured. It becomes a resist underlayer film.
• the uncured resist underlayer film exhibits resist solvent resistance and developer resistance, especially on a substrate containing copper on its surface.
• the resist underlayer film forming composition according to the present invention can be applied to a semiconductor manufacturing process. For example, since lithography is performed on a copper substrate in the rewiring step, an uncured resist underlayer film may be used. Further, since the resist underlayer film forming composition according to the present invention does not contain the above-mentioned cross-linking agent and the above-mentioned curing catalyst, there is an advantage that it can be removed with a wet etching chemical solution.
• the resist underlayer film-forming composition according to the present invention contains a polymer (P) having a dicyanostyryl group or a compound (C) having a dicyanostyryl group, and contains a solvent, but is derived from melamine, urea, benzoguanamine, or glycoluril. It does not contain the alkylated aminoplast cross-linking agent and does not contain a protonic acid curing catalyst.
• the dicyanostyryl group referred to in the present invention refers to a group represented by the following formula.
• X represents an alkyl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a cyano group or a nitro group
• R represents a hydrogen atom, an alkyl group or an arylene group
• n represents an integer of 0 to 4. Represented, * indicates a bonding portion with a part of the polymer (P) or the compound (C))
• the term "polymer” refers to a chemical substance having a repeating structural unit, and also includes an oligomer, and the term “compound” refers to a chemical substance other than a polymer.
• a "polymer having a dicyanostyryl group” is preferably a polymer having a dicyanostyryl group in the side chain of a repeating structural unit. In the present invention, any polymer and compound having a site capable of binding a dicyanostyryl group by a known chemical reaction can be used.
• the polymer (P) having a dicyanostyryl group or the compound (C) having a dicyanostyryl group referred to in the present invention is a polymer precursor (PP) containing an epoxy group or a compound precursor containing an epoxy group (C), respectively.
• the active proton compound referred to in the present invention means a compound included in the active proton compound, which is a term commonly used in organic chemistry, and is not particularly limited.
• the active proton compound include a compound having a hydroxyl group, a compound having a carboxy group, a compound having a thiol group, a compound having an amino group, and a compound having a compound having an imide group, and the compound having a hydroxyl group or a carboxy group. Is preferable.
• Examples of the carbonyl group in the active proton compound having a carbonyl group include a formyl group (aldehyde group) and a ketone group, but a formyl group is preferable.
• the dicyanostyryl group has the following formula (1-1):
• R 1 to R 3 represent a hydrogen atom, a methyl group or an ethyl group, and represent them.
• X represents an alkyl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group or a nitro group.
• Y represents an ether bond, a thioether bond or an ester bond, R represents a hydrogen atom, an alkyl group or an arylene group.
• n represents an integer of 0 to 4, and ** represents a bonding portion with a part of the polymer (P) or the compound (C)).
• the polymer (P) having a dicyanostyryl group or the compound (C) having a dicyanostyryl group contains an aromatic ring or an aliphatic ring.
• Aromatic compounds include benzene, thiophene, furan, pyridine, pyrimidine, pyrazine, pyrrole, oxazole, thiazole, imidazole, naphthalene, anthracene, quinoline, carbazole, quinazoline, purine, indolizine, benzothiophene, benzofuran, indole, phenylindole. , Acrydin and the like.
• the aromatic compound may have at least one or more hydroxyl groups.
• Such aromatic compounds having at least one or more hydroxyl groups are preferably phenolic hydroxy group-containing compounds.
• the phenolic hydroxy group-containing compound include phenol, dihydroxybenzene, trihydroxybenzene, hydroxynaphthalene, dihydroxynaphthalene, trihydroxynaphthalene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1 Examples thereof include 2,2-tetrakis (4-hydroxyphenyl) ethane and polynuclear phenol.
• polynuclear phenol examples include dihydroxybenzene, trihydroxybenzene, hydroxynaphthalene, dihydroxynaphthalene, trihydroxynaphthalene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 2,2'-biphenol, or 1 , 1,2,2-tetrakis (4-hydroxyphenyl) ethane and the like.
• the hydrogen atom of the aromatic compound is substituted with an alkyl group having 1 to 20 carbon atoms, a condensed ring group, a heterocyclic group, a hydroxy group, an amino group, a nitro group, an ether group, an alkoxy group, a cyano group, and a carboxyl group. It may have been done.
• the above aromatic compounds may be linked by a single bond or a spacer.
• the aromatic compound preferably contains one or more benzene ring, naphthalene ring, triazine ring or a combination thereof.
• the aliphatic ring in the present invention preferably has 4 or more, 6 or more, 10 or less, or 8 or less carbon atoms. Atoms other than carbon and hydrogen may be contained in the ring, for example, one or more atoms such as oxygen, nitrogen, sulfur, halogen, alkali metal, alkaline earth metal, transition metal and the like. Examples thereof include cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring, quinuclidine ring, hydantin ring, triazine ring, cyanuric acid and the like.
• R in the formula (1-1) is a hydrogen atom.
• X in the formula (1-1) is represented by an ether bond or an ester bond.
• the ester bond referred to in the present invention includes -COO- and -OCO-.
• the polymer (P) having a dicyanostyryl group or the compound (C) having a dicyanostyryl group is represented by the following formula (2).
• Q is a group obtained by removing m terminal atoms from a polymer or compound.
• m is 1 or more and less than or equal to the number of repeating units of the polymer.
• Q is a compound, m is an integer of 1 to 4.
• the m A's are alkylene groups having 1 to 10 carbon atoms which may be directly bonded, branched or substituted, respectively, and may contain an ether bond, a thioether bond or an ester bond in the alkylene group.
• Each of the m Bs independently represents a direct bond, an ether bond, a thioether bond or an ester bond.
• the m R 1 represents a hydrogen atom, a methyl group, an ethyl group or a propyl group, and may be bonded to Q to form a ring
• R 2 and R 3 are independently hydrogen atoms, methyl groups or propyl groups, respectively.
• the m L's are independently represented by the following equation (3). (In formula (3), Y represents an ether bond, a thioether bond or an ester bond, and represents R represents a hydrogen atom, an alkyl group or an arylene group.
• n represents an integer from 0 to 4
• n Xs independently represents an alkyl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a cyano group or a nitro group)].
• Q in the formula (2) includes an aromatic ring or an aliphatic ring.
• R in the formula (3) is a hydrogen atom.
• Y in the formula (3) is represented by an ether bond or an ester bond.
• alkyl group examples include a linear or branched alkyl group which may or may not have a substituent, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-.
• Nonadesyl group and Eikosyl group and the like An alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 12 carbon atoms is more preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is most preferable. Is.
• Examples of the alkoxy group include a group in which an oxygen atom is bonded to the alkyl group.
• Examples of the alkoxycarbonyl group include a group in which an oxygen atom and a carbonyl group are bonded to the alkyl group.
• Examples of the alkylene group include a divalent group obtained by further removing a hydrogen atom from the alkyl group.
• a methylene group For example, a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group and the like.
• the arylene group include a phenylene group, an o-methylphenylene group, an m-methylphenylene group, a p-methylphenylene group, an ⁇ -naphthylene group, a ⁇ -naphthylene group, an o-biphenylylene group, an m-biphenylylene group and a p-biphenylylene group.
• Examples thereof include a group, a 1-anthrylene group, a 2-anthrylene group, a 9-anthrylene group, a 1-phenanthrylene group, a 2-phenanthrylene group, a 3-phenanthrylene group, a 4-phenanthrylene group and a 9-phenanthrylene group. It is preferably an arylene group having 6 to 14 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms.
• Halogen atom usually means each atom of fluorine, chlorine, bromine, and iodine.
• polymer (P) having a dicyanostyryl group or the compound (C) having a dicyanostyryl group are as follows.
• L 1 is Or Means.
• the polymer (P) having a dicyanostyryl group or the compound (C) having a dicyanostyryl group may be obtained by the following two methods.
• the polymer (P) having a dicyanostyryl group or the compound (C) having a dicyanostyryl group includes a polymer precursor (PP) containing an epoxy group or a compound precursor (PC) containing an epoxy group, and a dicyanostyryl group. It can be obtained by reacting with an active proton compound having the above by any known method.
• the active proton compound having a dicyanostyryl group can also be obtained by cyanating the active proton compound having a carbonyl group.
• An example of the synthesis scheme is as follows.
• a step of reacting an active proton compound having a dicyanostyryl group with a compound precursor (PC) having an epoxy group is included.
• An example of the synthesis scheme when the compound (C) is a heterocyclic compound is as follows.
• Examples of the active proton compound having a carbonyl group of the present application can be exemplified by the following formulas (C-1) to (C-40), but the present invention is not limited thereto.
• Examples of the catalyst for activating the epoxy group used in the above reaction include quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and tetrabutylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. ..
• the amount used is usually 0.001 to 1 equivalent with respect to 1 equivalent of the epoxy group.
• the above reaction is carried out without a solvent, but is usually carried out with a solvent.
• a solvent any solvent that does not inhibit the reaction can be used.
• examples thereof include ethers such as 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran and dioxane.
• the reaction temperature is usually 40 ° C to 200 ° C.
• the reaction time is variously selected depending on the reaction temperature, but is usually about 30 minutes to 50 hours.
• the weight average molecular weight Mw of the compound obtained as described above is usually 200 to 3,000, or 500 to 2,000.
• the weight average molecular weight Mw of the similarly obtained polymer is usually 1,000 to 20,000, or 2,000 to 10,000.
• the solvent for the resist underlayer film forming composition according to the present invention is not particularly limited as long as it is a solvent capable of dissolving the polymer (P) having a dicyanostyryl group, the compound (C) having a dicyanostyryl group, and other components. can do.
• the resist underlayer film forming composition according to the present invention is used in a uniform solution state, it is recommended to use a solvent generally used in the lithography process in combination in consideration of its coating performance. ..
• Examples of such a solvent include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, and propylene glycol mono.
• Isobutyl lactate methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate.
• Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, etc. are preferable.
• propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable.
• the resist underlayer film forming composition according to the present invention does not contain an alkylated aminoplast cross-linking agent derived from melamine, urea, benzoguanamine, or glycoluril.
• cross-linking agent having at least two cross-linking substituents, that is, methoxymethylated glycol uryl, butoxymethylated glycol uryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethyl. It is a compound such as benzogwanamine, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea. It also does not contain condensates of these compounds.
• the resist underlayer film forming composition of the present invention does not also contain a cross-linking agent containing a cross-linking substituent having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule.
• a cross-linking agent containing a cross-linking substituent having an aromatic ring for example, a benzene ring or a naphthalene ring
• Examples of the cross-linking agent not contained in the resist underlayer film forming composition of the present invention include a compound having a partial structure of the following formula (4) and a polymer or oligomer having a repeating unit of the following formula (5). Be done.
• the R a , R b , R c , and R d are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms.
• na, nb, nc and nd each represent an integer of 0 to 3.
• the above-mentioned examples can be used for the above-mentioned alkyl group.
• the resist underlayer film forming composition of the present invention also does not contain the protonic acid curing catalyst commonly used with the above-mentioned cross-linking agent.
• Examples of the protonic acid curing catalyst not included in the resist underlayer film forming composition of the present invention include mineral acids and sulfonic acid compounds (for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, 4-phenol).
• mineral acids and sulfonic acid compounds for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, 4-phenol).
• the resist underlayer film forming composition of the present invention also does not contain an acid generator.
• the acid generator not included in the resist underlayer film forming composition of the present invention include a thermal acid generator and a photoacid generator.
• the thermoacid generator not included in the resist underlayer film forming composition of the present invention include 2,4,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, and other alkyl organic sulfonates. Esters and the like can be mentioned.
• Examples of the photoacid generator not contained in the resist underlayer film forming composition of the present invention include onium salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds and the like.
• the resist underlayer film forming composition of the present invention does not contain an onium salt compound.
• the onium salt compound not contained in the resist underlayer film forming composition of the present invention include diphenyliodonium hexafluorosulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butane sulfonate, diphenyliodonium perfluoronormal octane sulfonate, and diphenyliodonium camphor.
• Iodonium salt compounds such as sulfonate, bis (4-tert-butylphenyl) iodonium camphor sulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butane.
• Examples thereof include sulfonium salt compounds such as sulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.
• the resist underlayer film forming composition of the present invention does not contain a sulfonimide compound.
• the sulfoneimide compound not contained in the resist underlayer film forming composition of the present invention include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoronormalbutanesulfonyloxy) succinimide, and N- (camphasulfonyloxy) succinimide. And N- (trifluoromethanesulfonyloxy) naphthalimide and the like.
• the resist underlayer film forming composition of the present invention does not contain a disulfonyldiazomethane compound.
• the disulfonyldiazomethane compound not contained in the resist underlayer film forming composition of the present invention include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and bis (p-toluene).
• Examples thereof include sulfonyl) diazomethane, bis (2,4-dimethylbenzenesulfonyl) diazomethane, and methylsulfonyl-p-toluenesulfonyl diazomethane.
• the polymer (P) having a dicyanostyryl group or the compound (C) having a dicyanostyryl group contains a polymer precursor (PP) or an epoxy group containing an epoxy group, respectively.
• PP polymer precursor
• an active proton compound for example, a compound having a carboxylic acid. If there is a possibility that an unreacted active proton compound is present, it may be removed by a method known per se.
• the resist underlayer film forming composition of the present invention does not generate pinholes or stings, and a surfactant can be blended in order to further improve the coatability against surface unevenness.
• a surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol ether.
• Etc. Polyoxyethylene alkylallyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc.
• Polyoxyethylene sorbitan such as sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.
• Nonionic surfactants such as fatty acid esters, Ftop EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafuck F171, F173, R-30N, R-40, R-40N, R- 40LM (manufactured by DIC Co., Ltd., trade name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like can be mentioned.
• fatty acid esters Ftop EF301, EF303, EF352
• Megafuck F171, F173, R-30N, R-40, R-40N, R- 40LM
• the blending amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film material.
• These surfactants may be used alone or in combination of two or more.
• the ratio thereof is 0.0001 to 5 parts by mass, 0.001 to 1 part by mass, or 0.01 with respect to 100 parts by mass of the solid content of the resist underlayer film forming composition. To 0.5 parts by mass.
• a light absorber, a rheology adjuster, an adhesion aid, or the like can be added to the resist underlayer film forming composition of the present invention.
• Rheology modifiers are effective in improving the fluidity of the underlayer film forming composition.
• Adhesive aids are effective in improving the adhesion between the semiconductor substrate or resist and the underlayer film.
• Examples of the light-absorbing agent include commercially available light-absorbing agents described in "Technology and Market of Industrial Dyes” (CMC Publishing) and “Dye Handbook” (edited by Synthetic Organic Chemistry Association), for example, C.I. I. Disperse Yellow 1,3,4,5,7,8,13,23,31,49,50,51,54,60,64,66,68,79,82,88,90,93,102,114 and 124; C.I. I. Disperse Orange 1,5,13,25,29,30,31,44,57,72 and 73; C.I. I. Disperse Red 1,5,7,13,17,19,43,50,54,58,65,72,73,88,117,137,143,199 and 210; C.I.
• the above-mentioned absorbent is usually blended in a proportion of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the resist underlayer film forming composition.
• the rheology adjuster mainly improves the fluidity of the resist underlayer film forming composition, and particularly improves the film thickness uniformity of the resist underlayer film and the filling property of the resist underlayer film forming composition into the hole in the baking step. It is added for the purpose of enhancing.
• Specific examples include phthalate derivatives such as dimethylphthalate, diethylphthalate, diisobutylphthalate, dihexylphthalate and butylisodecylphthalate, adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate and octyldecyl adipate, and didi.
• Maleic acid derivatives such as normal butylmalate, diethylmalate, and dinonylmalate, oleic acid derivatives such as methyl olate, butyl oleate, and tetrahydrofurfuryl oleate, and stearic acid derivatives such as normal butyl stearate and glyceryl stearate can be mentioned. it can.
• These rheology adjusters are usually blended in a proportion of less than 30% by mass based on the total solid content of the resist underlayer film forming composition.
• Adhesive aids are added mainly for the purpose of improving the adhesion between the substrate or resist and the resist underlayer film forming composition, and particularly preventing the resist from peeling off during development.
• Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylmethylolchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylmethylolethoxysilane, diphenyldimethoxysilane, and phenyltriethoxy.
• Alkoxysilanes such as silane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, silazans such as trimethylsilylimidazole, methyloltrichlorosilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -aminopropyl Silanes such as triethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazol, thiouracil, Examples thereof include heterocyclic compounds such as mercaptoimidazole and mercaptopyrimidine, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea
• the solid content of the resist underlayer film forming composition according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass.
• the solid content is the content ratio of all the components excluding the solvent from the resist underlayer film forming composition.
• the total ratio of the polymer (P) and the compound (C) in the solid content is preferably 1 to 100% by mass, 50 to 100% by mass, and 80 to 100% by mass in that order.
• One of the scales for evaluating whether or not the resist underlayer film forming composition is in a uniform solution state is to observe the passability of a specific microfilter, but the resist underlayer film forming composition according to the present invention has. , Passes through a microfilter having a pore size of 0.1 ⁇ m and exhibits a uniform solution state.
• microfilter material examples include fluororesins such as PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultrahigh molecular weight polyethylene), and PP ( (Polypropylene), PSF (polysulphon), PES (polyethersulfone), nylon, but it is preferably made of PTFE (polytetrafluoroethylene).
• fluororesins such as PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer)
• PE polyethylene
• UPE ultrahigh molecular weight polyethylene
• PP polypropylene
• PSF polysulphon
• PES polyethersulfone
• nylon but it is preferably made of PTFE (polytetrafluoroethylene).
• the substrates used in the manufacture of semiconductor devices include, for example, silicon wafer substrates, silicon / silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low dielectric constant materials (low). -K material) Covered substrate and the like are included.
• the FOWLP process has begun to be applied for the purpose of high-speed response and power saving by shortening the wiring length between semiconductor chips.
• resist underlayer film forming composition In the RDL (rewiring) process for creating wiring between semiconductor chips, copper (Cu) is used as a wiring member, and an antireflection film (resist underlayer film forming composition) is applied as the copper wiring becomes finer. There is a need.
• the resist underlayer film forming composition according to the present invention can also be suitably applied to a substrate containing copper on its surface.
• the resist underlayer film forming composition of the present invention is applied onto a substrate used for manufacturing the above-mentioned semiconductor device (for example, a substrate containing copper on the surface) by an appropriate coating method such as a spinner or a coater, and then the resist underlayer film forming composition of the present invention is applied.
• a resist underlayer film is formed by removing the solvent.
• the conditions for removing the solvent are appropriately selected from a temperature of 80 ° C. to 400 ° C. and a time of 0.3 to 60 minutes.
• the temperature is 150 ° C to 350 ° C and the time is 0.5 to 2 minutes.
• the film thickness of the underlayer film formed is, for example, 10 to 1000 nm, 20 to 500 nm, or 30 to 400 nm, or 50 to 300 nm.
• the resist underlayer film forming composition according to the present invention does not contain an alkylated aminoplast cross-linking agent derived from melamine, urea, benzoguanamine, or glycoluril, and does not contain a protonic acid curing catalyst, so that the resist is formed.
• the lower layer film is an uncured resist lower layer film.
• an inorganic resist underlayer film (hard mask) on the organic resist underlayer film according to the present invention.
• a Si-based inorganic material film can be formed by a CVD method or the like.
• a resist film for example, a layer of photoresist is formed on the uncured resist underlayer film.
• the layer of the photoresist can be formed by a well-known method, that is, by applying the photoresist composition solution on the lower film and baking (baking).
• the film thickness of the photoresist is, for example, 50 to 10000 nm, or 100 to 2000 nm.
• the photoresist formed on the uncured resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure. Both negative photoresists and positive photoresists can be used. Positive photoresist consisting of novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester, chemically amplified photoresist consisting of a binder having a group that decomposes with an acid to increase the alkali dissolution rate and a photoacid generator, with an acid A chemically amplified photoresist composed of a low molecular weight compound that decomposes to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and a binder having a group that decomposes with an acid to increase the alkali dissolution rate.
• photoresists composed of low molecular weight compounds and photoacid generators that decompose with an acid to increase the alkali dissolution rate of the photoresist.
• the product name APEX-E manufactured by Chypre the product name PAR710 manufactured by Sumitomo Chemical Co., Ltd.
• the product name SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned.
• Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999,357-364 (2000), and Proc. SPIE, Vol. Fluorine-containing atomic polymer-based photoresists as described in 3999,365-374 (2000) can be mentioned.
• a resist pattern is formed by irradiation and development with light or an electron beam.
• Exposure is performed through a predetermined mask. Near ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (for example, EUV (wavelength 13.5 nm)) and the like are used for exposure. Specifically, i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), it is possible to use an ArF excimer laser (wavelength 193 nm) and F 2 excimer laser (wavelength 157 nm) or the like. Among these, i-line (wavelength 365 nm) is preferable.
• post-exposure heating post exposure break
• Post-exposure heating is carried out from a heating temperature of 70 ° C. to 150 ° C. and a heating time of 0.3 to 10 minutes under appropriately selected conditions.
• a resist for electron beam lithography can be used instead of a photoresist as a resist.
• the electron beam resist either a negative type or a positive type can be used.
• a chemically amplified resist consisting of an acid generator and a binder having a group that decomposes with an acid to change the alkali dissolution rate, and a low molecular weight compound that decomposes with an alkali-soluble binder, an acid generator and an acid to change the alkali dissolution rate of the resist.
• a chemically amplified resist composed of an acid generator, a binder having a group that decomposes with an acid to change the alkali dissolution rate, and a chemically amplified resist composed of a low molecular weight compound that decomposes with an acid to change the alkali dissolution rate of the resist are non-chemically amplified resists composed of binders having a group that is decomposed by an electron beam to change the alkali dissolution rate, and non-chemically amplified resists composed of a binder that is cut by an electron beam and has a site that changes the alkali dissolution rate. Even when these electron beam resists are used, a resist pattern can be formed in the same manner as when a photoresist is used with the irradiation source as an electron beam.
• the developing solution includes an aqueous solution of alkali metal hydroxide such as potassium hydroxide and sodium hydroxide, an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, ethanolamine and propylamine.
• An alkaline aqueous solution such as an amine aqueous solution such as ethylenediamine can be mentioned as an example.
• a surfactant or the like can be added to these developers.
• the development conditions are appropriately selected from a temperature of 5 to 50 ° C. and a time of 10 to 600 seconds.
• an organic lower layer film (lower layer) can be formed on a substrate, an inorganic lower layer film (intermediate layer) can be formed on the film, and a photoresist (upper layer) can be further coated on the film.
• the pattern width of the photoresist becomes narrower, and even when the photoresist is thinly coated to prevent the pattern from collapsing, the substrate can be processed by selecting an appropriate etching gas.
• a fluorine-based gas having a sufficiently fast etching rate for a photoresist can be used as an etching gas to process a resist underlayer film, and a fluorine-based gas having a sufficiently fast etching rate for an inorganic underlayer film can be etched.
• the substrate can be processed as a gas, and the substrate can be processed using an oxygen-based gas having a sufficiently high etching rate for the organic underlayer film as an etching gas.
• the inorganic underlayer film is removed using the photoresist pattern thus formed as a protective film, and then the organic underlayer film is removed using the film composed of the patterned photoresist and the inorganic underlayer film as a protective film. Is done. Finally, the semiconductor substrate is processed using the patterned inorganic underlayer film and organic underlayer film as protective films.
• the inorganic underlayer film in the portion from which the photoresist has been removed is removed by dry etching to expose the semiconductor substrate.
• dry etching of the inorganic underlayer film tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, 6 Gases such as sulfur fluorofluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used.
• a halogen-based gas is preferably used for dry etching of the inorganic underlayer film, and a fluorine-based gas is more preferable.
• the fluorine-based gas include tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, and difluoromethane (CH 2 F 2 ). Can be mentioned.
• the organic underlayer film is removed using a film composed of a patterned photoresist and an inorganic underlayer film as a protective film. Since the inorganic underlayer film containing a large amount of silicon atoms is difficult to be removed by dry etching with an oxygen-based gas, the organic underlayer film is often removed by dry etching with an oxygen-based gas.
• the processing of the semiconductor substrate is preferably performed by dry etching with a fluorine-based gas.
• fluorine-based gas examples include tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, and difluoromethane (CH 2 F 2 ). Can be mentioned.
• an organic antireflection film can be formed on the upper layer of the uncured resist lower layer film before the photoresist is formed.
• the antireflection film composition used there is not particularly limited, and can be arbitrarily selected and used from those conventionally used in the lithography process, and a commonly used method such as a spinner can be used.
• the antireflection film can be formed by coating and firing with a coater.
• the uncured resist underlayer film formed from the resist underlayer film forming composition may also have absorption to the light depending on the wavelength of the light used in the lithography process. Then, in such a case, it can function as an antireflection film having an effect of preventing the reflected light from the substrate. Further, the underlayer film formed of the resist underlayer film forming composition of the present invention can also function as a hard mask.
• the underlayer film of the present invention has a function of preventing an adverse effect on the substrate of a layer for preventing the interaction between the substrate and the photoresist, a material used for the photoresist, or a substance generated during exposure to the photoresist.
• It can also be used as a layer, a layer having a function of preventing diffusion of substances generated from the substrate during heating and firing into the upper photoresist, and a barrier layer for reducing the poisoning effect of the photoresist layer by the dielectric layer of the semiconductor substrate. It is possible.
• the resist underlayer film from the conventional resist underlayer film forming composition originally needs to be a cured film having solvent resistance in order to suppress mixing with the resist at the time of resist application. Further, at the time of resist patterning, it is necessary to use a developer for resolving the resist, and resistance to this developer is also indispensable. Therefore, it has been difficult to make the cured film insoluble in the resist solvent and the developing solution and soluble only in the wet etching solution by the conventional technique.
• the resist underlayer film forming composition according to the present invention it is possible to provide a resist underlayer film that is soluble in such a wet etching solution.
• the wet etching solution preferably contains, for example, an organic solvent, and may contain an acidic compound or a basic compound.
• organic solvent include dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, ethylene glycol, propylene glycol, diethylene glycol dimethyl ether and the like.
• the acidic compound include inorganic acids and organic acids, examples of the inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like, and examples of the organic acid include p-toluenesulfonic acid, trifluoromethanesulfonic acid and salicylic acid.
• 5-sulfosalicylic acid 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, acetic acid, propionic acid, trifluoroacetic acid, citric acid, benzoic acid, hydroxybenzoic acid, Examples thereof include naphthalene carboxylic acid.
• the basic compound include inorganic bases and organic bases, and examples of the inorganic bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline.
• the wet etching solution can use only one kind of organic solvent, or can use two or more kinds in combination. Moreover, only one kind of acidic compound or basic compound can be used, or two or more kinds can be used in combination.
• the blending amount of the acidic compound or the basic compound is 0.01 to 20% by weight, preferably 0.1 to 5% by weight, particularly preferably 0.2 to 1% by weight, based on the wet etching solution. Is.
• the wet etching solution is preferably an organic solvent containing a basic compound, and particularly preferably a mixed solution containing dimethyl sulfoxide and tetramethylammonium hydroxide.
• the FOWLP Fe-Out Wafer Level Package
• the resist underlayer film is applied in the RDL (rewiring) process for forming copper wiring.
• a typical RDL process is described below, but is not limited to this.
• a photosensitive insulating film is formed on the semiconductor chip, and then patterning is performed by light irradiation (exposure) and development to open the semiconductor chip electrode portion.
• a copper seed layer for forming a copper wiring to be a wiring member by a plating step is formed by sputtering.
• the resist underlayer film forming composition according to the present invention can remove the resist underlayer film by wet etching, the resist underlayer film in such an RDL step can be used as a resist underlayer film to simplify the process process and damage the processed substrate. From the viewpoint of reduction, it can be particularly preferably used.
• EPICLON HP-4710 manufactured by DIC Corporation, epoxy functional value: 5.81 eq./kg
• Example 2 12.23 g of propylene glycol monomethyl ether and 8.37 g of propylene glycol monomethyl ether acetate were added to 9.40 g of a solution of the reaction product corresponding to the above formula (A-3) (solid content was 22.3% by weight), and a resist was added. A solution of the underlayer film forming composition was prepared.
• Example 3 14.49 g of propylene glycol monomethyl ether and 8.37 g of propylene glycol monomethyl ether acetate are added to 7.14 g of a solution of the reaction product corresponding to the above formula (A-4) (solid content is 29.4% by weight), and a resist is added. A solution of the underlayer film forming composition was prepared.
• Example 4 12.66 g of propylene glycol monomethyl ether and 8.37 g of propylene glycol monomethyl ether acetate are added to 8.97 g of a solution of the reaction product corresponding to the above formula (A-5) (solid content is 23.4% by weight), and a resist is added. A solution of the underlayer film forming composition was prepared.
• Example 5 13.49 g of propylene glycol monomethyl ether and 8.37 g of propylene glycol monomethyl ether acetate are added to 8.14 g of a solution of the reaction product corresponding to the above formula (A-6) (solid content is 25.8% by weight), and a resist is added. A solution of the underlayer film forming composition was prepared.
• Example 6 12.86 g of propylene glycol monomethyl ether and 8.37 g of propylene glycol monomethyl ether acetate are added to 8.77 g of a solution of the reaction product corresponding to the above formula (A-7) (solid content is 23.9% by weight), and a resist is added. A solution of the underlayer film forming composition was prepared.
• the resist underlayer film forming composition for lithography prepared in Examples 1 to 6 is applied on a silicon wafer with a spin coater so as to have a film thickness of about 50 nm, and is placed on a hot plate. It was heated at 200 ° C. for 90 seconds.
• the obtained resist underlayer film has a wavelength of 193 nm (ArF excimer laser light wavelength), 248 nm (KrF excimer laser light wavelength) and 365 nm (i-line wavelength).
• the n value (refractive index) and the k value (attenuation coefficient) in the above were measured. The results are shown in Table 1.
• Examples 1 to 6 since Examples 1 to 6 have appropriate n and k values at 193 nm, 248 nm and 365 nm, they can be obtained from the resist underlayer film forming composition obtained in Examples 1 to 6.
• the coated film has an antireflection function that can suppress reflection (standing wave) from the underlying substrate, which causes an unfavorable resist pattern in the lithography process using radiation such as ArF excimer laser, KrF excimer laser, and i-ray. Therefore, it is useful as a resist underlayer film.
• the resist underlayer film forming composition prepared in Examples 1 to 6 was applied onto a copper substrate having a film thickness of 100 nm and heated at 200 ° C. for 90 seconds. A resist underlayer film was formed so as to have a film thickness of 170 nm.
• the copper substrate coated with the resist underlayer film composition is immersed in propylene glycol monomethyl ether (PGME) or propylene glycol monomethyl ether acetate (PGMEA), which is a general resist solvent, at room temperature for 1 minute, and after immersion.
• PGME propylene glycol monomethyl ether
• PMEA propylene glycol monomethyl ether acetate
• the coating film on the copper substrate was not removed (peeled) by PGME and PGMEA, and thus these organic solvents (resist solvents) were used.
• resist solvents organic solvents
• the coating film obtained from the resist underlayer film compositions of Examples 1 to 6 is useful as a resist underlayer film because an unfavorable peeling phenomenon does not occur due to the resist solvent.
• the resist underlayer film forming composition prepared in Examples 1 to 6 is applied onto a copper substrate having a thickness of 100 nm and heated at 200 ° C. for 90 seconds. As a result, a resist underlayer film was formed so as to have a film thickness of 170 nm.
• the copper substrate coated with the resist underlayer film composition is subjected to a 2.38 wt% tetramethylammonium hydroxide (tetramethylammonium hydroxide: TMAH) aqueous solution (product name: NMD-3, Tokyo Ohka Kogyo) which is an alkaline aqueous solution.
• TMAH tetramethylammonium hydroxide
• the coating film on the copper substrate was not removed (peeled) from the TMAH aqueous solution, and thus the resist developer (alkaline aqueous solution). It can be said that it has good chemical resistance to. That is, the coating film obtained from the resist underlayer film composition of Examples 1 to 6 can suppress an unfavorable peeling phenomenon by the resist developer, and therefore requires a development step with an alkaline aqueous solution. It is useful as an underlayer film.
• the resist underlayer film forming composition prepared in Examples 1 to 6 and Comparative Examples 1 and 3 was placed on a copper substrate having a thickness of 100 nm.
• the resist underlayer film was formed so as to have a film thickness of 170 nm by coating and heating at 200 ° C. for 90 seconds.
• the copper substrate coated with the resist underlayer film composition is immersed in a dimethyl sulfoxide solution of 0.5 wt% tetramethylammonium hydroxide ((TMAH)), which is a basic organic solvent, at 50 ° C. for 5 minutes.
• TMAH 0.5 wt% tetramethylammonium hydroxide
• the coating film on the copper substrate was a wet etching chemical solution (compared to the resist underlayer film compositions of Comparative Examples 1 and 3). Sufficient removability was obtained for (basic organic solvent). That is, since the coating film obtained from the resist underlayer film compositions of Examples 1 to 6 can exhibit good removability (peeling property) with respect to the wet etching chemical solution, the resist underlayer film is wet-etched. It is useful in the semiconductor manufacturing process of removing with a chemical solution.
• solubility test in wet etching chemical solution As an evaluation of solubility in a wet etching chemical solution (basic organic solvent), the resist underlayer film forming composition prepared in Examples 1 to 6 and Comparative Examples 1 and 3 was applied onto a silicon wafer substrate. By heating at 200 ° C. for 90 seconds, a resist underlayer film was formed so as to have a film thickness of 170 nm. Next, the film-formed resist underlayer film was peeled off from the substrate, and the obtained coating film was placed in a dimethyl sulfoxide solution of 0.5 wt% tetramethylammonium hydroxide (TMAH), which is a basic organic solvent, at 50 ° C.
• TMAH tt% tetramethylammonium hydroxide
• the resist underlayer film compositions of Examples 1 to 6 have a wet etching chemical solution (basic organic solvent) as compared with the resist underlayer film compositions of Comparative Examples 1 to 3. Sufficient solubility was obtained. That is, since the coating film obtained from the resist underlayer film compositions of Examples 1 to 6 exhibits good solubility in the wet etching chemical solution, in the semiconductor manufacturing step of removing the resist underlayer film with the wet etching chemical solution. It is useful. In particular, the coating film obtained from the resist underlayer film composition of Examples 1 to 6 is not only removable with a wet etching chemical solution, but also exhibits sufficient solubility, so that the removed film becomes a foreign substance (defect). It is more useful as a resist underlayer film because it is possible to prevent unfavorable contamination of the chemical solution caused by uneven dispersion of the (release film) in the chemical solution.
• a resist underlayer film that exhibits good resistance to a resist solvent that is mainly an organic solvent and a resist developer that is an alkaline aqueous solution, and exhibits removability, preferably solubility, only in a wet etching chemical solution. be able to.

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