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WO2018123626A1 - Composition de résine négative pour électrode en saillie et procédé de fabrication d'une électrode en saillie - Google Patents

Composition de résine négative pour électrode en saillie et procédé de fabrication d'une électrode en saillie Download PDF

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Publication number
WO2018123626A1
WO2018123626A1 PCT/JP2017/044987 JP2017044987W WO2018123626A1 WO 2018123626 A1 WO2018123626 A1 WO 2018123626A1 JP 2017044987 W JP2017044987 W JP 2017044987W WO 2018123626 A1 WO2018123626 A1 WO 2018123626A1
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Prior art keywords
resist film
resist composition
negative resist
protruding electrode
negative
Prior art date
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PCT/JP2017/044987
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English (en)
Japanese (ja)
Inventor
信寛 佐藤
信紀 阿部
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Zeon Corp
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Zeon Corp
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Publication of WO2018123626A1 publication Critical patent/WO2018123626A1/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering

Definitions

  • the present invention relates to a negative resist composition for bump electrodes and a method for producing the bump electrodes.
  • Flip chip connection is often used in applications such as LEDs (Light Emitting Diodes) and laser devices.
  • LEDs Light Emitting Diodes
  • laser devices In such flip chip connection, it can be referred to as a protruding electrode or a bump (hereinafter simply referred to as “protruding electrode”).
  • a substrate having an electrode is used.
  • the protruding electrode is also used for a probe used for inspecting a flexible printed circuit (FPC) substrate or a liquid crystal display panel. The needs for such probes are also expanding in recent years.
  • FPC flexible printed circuit
  • a method for manufacturing a bump electrode a method including a baking process in which a temperature in the thickness direction of the resist film has a temperature gradient when the resist film subjected to the exposure process is baked has been proposed.
  • a baking process a temperature gradient in the thickness direction of the resist film is formed by heating one side of the resist film and cooling the other side.
  • the resist film has different resistances in the thickness direction with respect to the developer, and it is possible to satisfactorily form the tapered shape of the protruding electrode when developed with the developer.
  • Patent Document 1 is an apparatus that is used to cool or heat a resist film because the resist film is cooled or heated to vary the resistance to a developing solution at various points in the resist film. Depending on the performance and the like, it was difficult to stably form a good reverse tapered shape from the resist film. Further, the tapered shape of the protruding electrode obtained by the manufacturing method described in Patent Document 1 has room for improvement.
  • the present inventors have intensively studied for the purpose of solving the above problems. Then, the present inventors obtained a protruding electrode using a resist composition having a predetermined wavelength or less of ultraviolet light transmittance when a resist film having a specific thickness is formed. The inventors have found that the taper shape of the protruding electrode can be made particularly favorable, and have completed the present invention.
  • the present invention aims to advantageously solve the above-mentioned problems, and the negative resist composition for bump electrodes of the present invention has a wavelength when a resist film having a thickness of 3.5 ⁇ m is formed.
  • the light transmittance of the resist film at 365 nm is 30% or less.
  • the “light transmittance at a wavelength of 365 nm” is determined by the method described in Examples for a resist film having a thickness of 3.5 ⁇ m formed using the negative resist composition for protruding electrodes of the present invention. It is the measured light transmittance.
  • the “thickness” of the resist film can be measured by the method described in Examples.
  • the negative resist composition for bump electrodes of the present invention preferably contains a light absorber containing at least one of a compound satisfying the following formula (I) and a bisazide compound.
  • p and q are each 0 or 1
  • R 11 and R 21 are hydrogen atoms
  • R 12 and R 22 each have 1 to 1 carbon atoms which may have a substituent.
  • R 3 is an organic group containing a hydrocarbon group or a phenylene group
  • R 13 and R 23 are each a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent
  • R 12 and R 13 , R 22 and R 23 , and / or R 13 and R 23 may be bonded to each other to form a ring.
  • the negative resist composition for protruding electrodes of the present invention preferably further contains a resin, and preferably contains 0.1 parts by mass or more of the light absorber with respect to 100 parts by mass of the resin. This is because if the negative resist composition for protruding electrodes of the present invention contains the light absorber in a proportion of the lower limit value or more, a protruding electrode having a better taper shape can be formed.
  • the negative resist composition for bump electrodes of the present invention preferably contains a halogen-containing triazine photoacid generator. This is because if the negative resist composition for protruding electrodes of the present invention contains a halogen-containing triazine photoacid generator, a protruding electrode having a better taper shape can be formed.
  • the method for manufacturing a protruding electrode according to the present invention is a method for forming a resist film having a thickness of 3.5 ⁇ m at a wavelength of 365 nm.
  • a resist film forming step of forming a negative resist film by applying a negative resist composition for protruding electrodes on the substrate, the resist film having a light transmittance of 30% or less, and exposing the negative resist film An exposure process; a baking process for baking the negative resist film that has undergone the exposure process; a developing process for developing the negative resist film that has undergone the baking process to obtain an opening through which the substrate is exposed; and plating.
  • the present invention it is possible to provide a negative resist composition for a protruding electrode capable of stably forming a protruding electrode having a good taper shape. Moreover, according to this invention, the manufacturing method of the protruding electrode which has a favorable taper shape can be provided.
  • the negative resist composition for protruding electrodes of the present invention is not particularly limited, and can be used when forming protruding electrodes applicable to various applications.
  • the negative resist composition for protruding electrodes of the present invention can be used particularly suitably when manufacturing a protruding electrode finer than a protruding electrode of the order of 100 ⁇ m as conventionally manufactured.
  • the protruding electrode manufacturing method of the present invention is characterized by using the negative electrode resist composition for protruding electrodes of the present invention.
  • the negative resist composition for protruding electrodes of the present invention is characterized in that when a resist film having a thickness of 3.5 ⁇ m is formed, the light transmittance of the resist film at a wavelength of 365 nm is 30% or less. According to the negative electrode resist composition for bump electrodes satisfying such a condition, a negative taper shape for bump electrodes can be stably formed, so that a bump electrode having a good taper shape can be stably formed. Can be formed.
  • the light transmittance at a wavelength of 365 nm is preferably 20% or less, and more than 10%. It is preferable that it is more than 13%. If the light transmittance of the resist film at a wavelength of 365 nm is 30% or less, it is possible to optimize the distribution of the amount of light reaching the resist film in the thickness direction in the exposure process, thereby having a favorable reverse taper shape.
  • a negative resist film can be formed.
  • the negative resist composition for bump electrodes of the present invention is a step of forming a temperature gradient in the thickness direction of the resist film by setting the formed resist film to have the above-mentioned specific light transmittance. Since a reverse taper shape can be formed in the resist film without performing the step, a good reverse taper shape can be stably formed.
  • the light transmittance of the resist film naturally varies depending on the thickness of the formed resist film even when the resist film is formed using the same resist composition.
  • a resist film having various thicknesses according to the application is formed to form the protruding electrode. Even when manufactured, it has been found that a protruding electrode having a good taper shape can be stably manufactured.
  • the negative resist composition for protruding electrodes of the present invention is not particularly limited, and is, for example, a photosensitive resist composition containing a resin (a), a crosslinking component that crosslinks the resin (a), and a light absorber. It is possible. Furthermore, the crosslinking component may be a combination of a compound that generates an acid upon irradiation with light and a compound that crosslinks the resin (a) using the acid generated by the light as a catalyst.
  • the resin (a) is not particularly limited, and an alkali-soluble resin that can be generally used for forming a resist can be used.
  • alkali-soluble means that the insoluble fraction is less than 0.1% by mass when dissolved in a solution having a pH of 8 or higher.
  • examples of the alkali-soluble resin include novolak resin, polyvinyl phenol resin, polyvinyl alcohol resin, resol resin, acrylic resin, styrene-acrylic acid copolymer resin, hydroxystyrene polymer resin, polyvinyl hydroxybenzoate, and mixed resins thereof. Etc. Among these, it is preferable to use the novolac resin alone or in combination with other resins.
  • novolak resin a commercially available novolak resin or a novolak resin prepared by reacting phenols with aldehydes or ketones in the presence of an acidic catalyst (for example, oxalic acid) can be used.
  • an acidic catalyst for example, oxalic acid
  • a novolak resin by using metacresol and paracresol together and subjecting these to formaldehyde, formalin or paraformaldehyde for condensation reaction.
  • the charging ratio of metacresol to paracresol is usually 80:20 to 20:80, preferably 70:30 to 40:60, based on mass.
  • the average molecular weight of the novolak resin is a weight average molecular weight in terms of monodisperse polystyrene measured by gel permeation chromatography (GPC) and is preferably 1000 or more and 10,000 or less.
  • polyvinylphenol resin examples include a homopolymer of vinyl phenol and a copolymer of vinyl phenol and a monomer copolymerizable therewith.
  • the monomer copolymerizable with the vinylphenol resin examples include isopropenylphenol, acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic imide, and vinyl acetate.
  • the polyvinylphenol resin a homopolymer of vinylphenol is preferable, and a homopolymer of p-vinylphenol is more preferable.
  • the average molecular weight of polyvinyl phenol resin is 1000 or more and 20000 or less by the weight average molecular weight (Mw) of monodispersed polystyrene measured by GPC.
  • a crosslinking component is a component which bridge
  • the crosslinking component includes a compound that generates an acid upon irradiation with light (hereinafter also referred to as a “photoacid generator”) and a compound that crosslinks the resin (a) using an acid generated by light as a catalyst (acid-sensitive substance: And also referred to as “acid crosslinking agent”). Both of these compounds are preferable in that they are excellent in compatibility with the resin (a) and can provide a cross-linked chemically amplified resist having good sensitivity when combined with the resin (a).
  • the compound that generates an acid by light is not particularly limited as long as it is a substance that generates a Bronsted acid or a Lewis acid when exposed to light, and includes an onium salt, a halogenated organic compound, a quinonediazide compound, a sulfone compound, and an organic compound.
  • An acid ester compound, an organic acid amide compound, an organic acid imide compound, a compound represented by the following formula (X), or the like can be used.
  • a resist composition contains a halogenated organic compound or a compound represented by the following formula (X) as a photoacid generator.
  • the following formula (X) It is more preferable to include a halogen-containing triazine compound that is a compound represented by Y) or an organic compound having a halogen group and a triazine ring structure, and more preferable to include a halogen-containing triazine compound.
  • R 4 represents a monovalent to trivalent organic group
  • R 5 represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group
  • n is 1 Indicates a natural number of ⁇ 3.
  • the aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, a furyl group, a thienyl group.
  • heterocyclic groups such as These may have one or more suitable substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like.
  • R 5 is particularly preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • R 4 is an aromatic compound group and R 5 is a lower alkyl group.
  • the acid generator represented by the above formula (X) is specifically 2,2 ′-(1,3-phenylene) bis [2- (butylsulfonyloxy) represented by the following formula (Y): Imino) acetonitrile].
  • the halogenated organic compounds include halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, and halogen-containing thiazoles.
  • Compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2-pyrone compounds, other halogen-containing heterocyclic compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, sulfenyl halides Compound etc. are mentioned.
  • halogen-containing triazine compound examples include 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [ 2- (4-Methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [1- (4-methoxy) naphthyl] -4,6-bis (trichloromethyl) ) -1,3,5-triazine and the like.
  • 2- [1- (4-methoxy) naphthyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (4-methoxyphenyl) is used.
  • the acid crosslinking agent is a compound (acid-sensitive substance) that can crosslink the resin in the presence of an acid generated by light irradiation (exposure).
  • acid cross-linking agents include known acid cross-linking compounds such as alkoxymethylated urea resins, alkoxymethylated melamine resins, alkoxymethylated uron resins, alkoxymethylated glycoluril resins, and alkoxymethylated amino resins. Can be mentioned.
  • acid crosslinking agents include alkyl etherified melamine resins, benzoguanamine resins, alkyl etherified benzoguanamine resins, urea resins, alkyl etherified urea resins, urethane-formaldehyde resins, resol type phenol formaldehyde resins, alkyl etherified resole type phenol formaldehydes. Examples thereof include resins and epoxy resins.
  • the acid crosslinking agent is preferably a resin having a weight average molecular weight (Mw) in terms of monodisperse polystyrene measured by GPC and having a weight average molecular weight of 300 or more and less than 10,000.
  • alkoxymethylated melamine resins are preferable, and specific examples thereof include methoxymethylated melamine resins, ethoxymethylated melamine resins, n-propoxymethylated melamine resins, and n-butoxymethylated melamine resins. it can.
  • a methoxymethylated melamine resin such as hexamethoxymethylmelamine is particularly preferable in terms of good resolution.
  • alkoxymethylated melamine resins include, for example, PL-1170, PL-1174, UFR65, CYMEL (registered trademark) 300, CYMEL (registered trademark) 303 (above, manufactured by Mitsui Cytec), BX-4000, Nicarak MW-30 and MX290 (manufactured by Sanwa Chemical Co., Ltd.).
  • the acid crosslinking agent can be used alone or in combination of two or more.
  • the acid crosslinking agent is blended in an amount of usually 0.5 to 60 parts by mass, preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass with respect to 100 parts by mass of the resin. If the blending amount of the acid crosslinking agent is not less than the above lower limit value, the crosslinking reaction is sufficiently advanced to reduce the residual film ratio of the resist pattern after development using an alkali developer, It is possible to avoid the occurrence of deformation such as meandering. If the compounding amount of the acid crosslinking agent is not more than the above upper limit, the resulting resist pattern can have high resolution.
  • the light absorber absorbs light irradiated to the resist film.
  • a reverse taper-shaped resist pattern can be formed.
  • a resist composition using a combination of a photoacid generator and an acid crosslinking agent as a crosslinking component is a crosslinked chemical amplification resist, and the acid generated by light irradiation diffuses in the resist film, and light is Since the cross-linking reaction is caused to a non-contact region, the reverse taper shape of the resist pattern can be well controlled by the presence of the light absorber.
  • the light absorber is not particularly limited, and examples thereof include bisazide compounds; natural compounds such as azo dyes, methine dyes, azomethine dyes, curcumin, and xanthones; 4,4′-bis (dimethylamino) benzophenone (so-called “ Dialkylamino compounds such as Michler's ketone]); cyanovinylstyrene compounds; 1-cyano-2- (4-dialkylaminophenyl) ethylenes; p- (halogen-substituted phenylazo) -dialkylaminobenzenes; 1-alkoxy-4- (4'-N, N-dialkylaminophenylazo) benzenes; 1,2-dicyanoethylene; 9-cyanoanthracene; 9-anthrylmethylenemalononitrile; N-ethyl-3-carbazolylmethylenemalononitrile; -(3,3-dicyano-2-propeny
  • a bisazide compound having an azide group at both ends or a compound satisfying the following formula (I) is preferable.
  • p and q are each 0 or 1
  • R 11 and R 21 are hydrogen atoms
  • R 12 and R 22 each have 1 to 1 carbon atoms which may have a substituent.
  • 3 is an organic group containing a hydrocarbon group or a phenylene group
  • R 13 and R 23 are each a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent
  • R 12 and R 13 , R 22 and R 23 , and / or R 13 and R 23 may be connected to each other to form a ring.
  • Examples of the substituent that R 12 and R 22 may have, and the substituent that R 13 and R 23 may have when they are hydrocarbon groups having 1 to 3 carbon atoms include, for example, an amino group, an azide group, Examples thereof include a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, and a dialkyl (1 to 3 carbon atoms) amino group.
  • R 12 and R 22 may be the same or different from each other.
  • R 13 and R 23 may be the same or different from each other.
  • the bisazide compound is not particularly limited.
  • bisazide compounds satisfying the above formula (I) can be suitably used as the light absorber.
  • Examples of bisazide compounds satisfying the above formula (I) include 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, and 2,6-bis (4′-azidobenzal) -4- Examples include methylcyclohexanone, 2,6-bis (4′-azidobenzal) -4-ethylcyclohexanone, and 4,4′-diazidobenzophenone. These can be used singly or in combination.
  • examples of the light absorber other than the bisazide compound that can be represented by the above (I) include natural compounds such as curcumin, 4,4′-bis (dimethylamino) benzophenone, and the like. These can be used singly or in combination.
  • the “conjugated structure” means a structure in which sp 2 carbon atoms are continuously bonded.
  • the light absorber may have one or a plurality of conjugated structures in its structure, but the total number of sp 2 carbon atoms constituting all the conjugated structures contained in the light absorber may be 6 or more. Preferably, it is 12 or more, more preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
  • the light absorber preferably contains two or more conjugated structures, and preferably has 2 or more and 20 or less sp 2 carbon atoms constituting each conjugated structure.
  • the light absorber preferably contains two or more conjugated structures having a benzene ring structure.
  • a bisazide compound such as 2,6-bis (4′-azidobenzal) -4-methylcyclohexanone represented by the following formula (II), represented by the following formula (III): Curcumin or 4,4′-bis (dimethylamino) benzophenone represented by the following formula (IV) is preferably used, and 2,6-bis (4′-azidobenzal) -4-methylcyclohexanone is preferably used. Is more preferable.
  • “Et” represents an ethyl group.
  • the resist composition preferably contains a light absorber with respect to 100 parts by mass of the resin (a), preferably more than 1.0 part by mass, more preferably more than 1.5 parts by mass, and still more preferably 1.8 parts by mass. More than 10 parts by mass, usually 8 parts by mass or less, more preferably 5 parts by mass or less. If the compounding amount of the light absorber in the resist composition is more than 1.0 part by mass with respect to 100 parts by mass of the resin (a), a protruding electrode having a more favorable tapered shape can be formed.
  • the storage stability of a resist composition can be improved. Furthermore, generally, when the resist film thickness is thick, the light beam hardly penetrates the resist film, so the amount of the light absorber may be relatively small. When the resist film thickness is thin, a relatively large amount is used. It is preferable.
  • a salt can be formed by acid-base interaction with an acid that is undesirably generated from a photoacid generator or the like during storage of the resist composition, and the storage stability of the resist composition It is because it can improve.
  • the basic compound include inorganic basic compounds and organic basic compounds.
  • an organic basic compound is more preferable because of its high solubility in an organic solvent. This is because the uniformity of the coating film formed by applying the resist composition solution on the substrate can be improved.
  • organic basic compound examples include nitrogen-containing basic compounds, organic halides, alkoxides, phosphazene derivatives, and Verkade bases.
  • the basic compound it is preferable to use a nitrogen-containing basic compound. This is because the storage stability of the resist composition can be further improved.
  • nitrogen-containing basic compounds include aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, amino alcohols, aromatic amines, quaternary ammonium hydroxides, and alicyclic amines. Is mentioned.
  • an aliphatic primary amine, an aliphatic secondary amine, and an aliphatic tertiary amine are blended as the nitrogen-containing basic compound.
  • nitrogen-containing basic compound examples include butylamine, hexylamine, ethanolamine, triethanolamine, 2-ethylhexylamine, 2-ethylhexyloxypropylamine, methoxypropylamine, diethylaminopropylamine, N-methylaniline, N- Ethylaniline, N-propylaniline, dimethyl-N-methylaniline, diethyl-N-methylaniline, diisopropyl-N-dimethylaniline, N-methylaminophenol, N-ethylaminophenol, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethylaminophenol, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5 Diazabicyclo [4.3.0] non-5-ene, and the like. Of these, tri
  • the ratio is, for example, 0.001 to 10 parts by mass, preferably 0.005 to 8 parts by mass with respect to 100 parts by mass of the resin (a). Preferably, it may be 0.01 to 5 parts by mass.
  • the content of the basic compound is within the above range, the storage stability of the resist composition can be improved.
  • a surfactant can be optionally added to the resist composition.
  • the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenol ether, and other polyoxyethylene alkyl ethers.
  • Oxyethylene aryl ethers such as polyethylene glycol dilaurate and ethylene glycol distearate; EFTOP EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), Megafax F171, F172, F173, F177 (Dainippon) Ink), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-382, S Fluorosurfactants such as C-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Asahi Glass Co., Ltd.); Organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.); Acrylic acid type Or methacrylic acid (co) polymer polyflow No.
  • the amount of these surfactants is usually 2 parts by mass or less, preferably 1 part by mass or less, per 100 parts by mass of the solid content of the resist composition.
  • solvent An organic solvent is preferably used as a solvent for dissolving the above-described components.
  • the organic solvent is used in an amount sufficient to uniformly dissolve or disperse each component as described above.
  • the solid content concentration in the resist composition solution is usually about 5 to 50% by mass, preferably about 10 to 45% by mass.
  • organic solvent examples include alcohols such as n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, and cyclohexyl alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; propyl formate, Esters such as butyl formate, ethyl acetate, propyl acetate, butyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate, ethyl ethoxypropionate, ethyl pyruvate; tetrahydrofuran, Cyclic ethers such as dioxane; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl
  • a resist composition can be produced by mixing the above-described components by a known method.
  • the resist composition is used as a resist composition solution obtained by, for example, dissolving each component in an organic solvent and filtering.
  • known mixers such as a stirrer, ball mill, sand mill, bead mill, pigment disperser, crushed grinder, ultrasonic disperser, homogenizer, planetary mixer, and fill mix can be used.
  • the general filtration method using filter media, such as a filter can be employ
  • the method for producing a protruding electrode of the present invention is characterized by using a negative resist film formed using the negative resist composition for a protruding electrode of the present invention described above. More specifically, the method for producing a protruding electrode of the present invention includes a resist film forming step of applying a negative resist composition for a protruding electrode of the present invention on a substrate to form a negative resist film, an exposure step, , A baking step, a developing step, a bump electrode forming step, and a resist film removing step. According to the method for manufacturing a protruding electrode of the present invention, it is possible to stably form a protruding electrode having a good taper shape.
  • the manufacturing method of the protruding electrode of the present invention may include a preparation step of preparing the negative electrode resist composition for the protruding electrode described above prior to the resist film forming step.
  • the resist composition of the present invention is dissolved in an organic solvent to prepare a negative resist composition solution for bump electrodes.
  • a negative resist composition solution for bump electrodes For example, each component contained in the negative resist composition for bump electrodes of the present invention or the negative resist composition for bump electrodes of the present invention is added to the organic solvent as described above.
  • a negative resist composition solution for bump electrodes can be prepared by mixing and dissolving with a known mixer or the like, and optionally performing a filtration treatment or the like.
  • the resist composition solution obtained in the preparation step is applied onto a substrate to form a coating film.
  • the substrate is not particularly limited as long as it is a general substrate that can be used as a semiconductor substrate, and may be, for example, a silicon substrate, a glass substrate, an ITO film formation substrate, a chromium film formation substrate, or a resin substrate.
  • a general coating method such as spin coating, spraying, brush coating, or dip coating can be employed.
  • the organic solvent is removed from the applied resist composition solution by a known method to form a negative resist film.
  • the method for removing the organic solvent is not particularly limited, and examples thereof include a method for heating the coating film and a method for placing the coating film at room temperature, under heating, and / or under a reduced pressure atmosphere.
  • the bump electrode manufacturing method of the present invention may include a pre-bake step of heating the resist film prior to the exposure step.
  • the heating temperature may be 80 ° C. or more and 120 ° C. or less, and the heating time may be 10 seconds or more and 200 seconds or less, without particular limitation.
  • the pre-baking step is not particularly limited, and can be performed by placing a substrate on which a coating film is formed on a heating mechanism such as a hot plate provided in a general baking apparatus.
  • the pre-bake temperature can be controlled by changing the set temperature of the hot plate or the like.
  • the film thickness of the resist film obtained through the prebaking process is 0.1 micrometer or more and 15 micrometers or less normally.
  • the resist film that has undergone the pre-baking process is irradiated with light.
  • the light beam is, for example, actinic radiation having a wavelength of 13.5 nm or more and 450 nm or less.
  • the light beam includes ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, extreme ultraviolet light (Extreme Ultra Violet), and the like. It can be.
  • the exposure light source is not particularly limited.
  • a semiconductor laser irradiation device for example, a semiconductor laser irradiation device, a metal halide lamp, a high-pressure mercury lamp, an excimer laser (KrF, ArF, F 2 ) irradiation device, an X-ray exposure device, an electron beam exposure device, And an EUV exposure apparatus.
  • the exposure amount is usually 10 mJ / cm 2 or more and 2000 mJ / cm 2 or less
  • the exposure time is usually 1 second or more and 180 seconds or less.
  • the bump electrode manufacturing method of the present invention may further include a post-bake step of holding the resist film under a post-exposure bake temperature condition after the start of the exposure step.
  • the post-bake process may be started before the exposure process is completed, or may be started after the exposure process is completed, as long as the exposure process is started.
  • the post-exposure bake process can be performed using the same apparatus as the pre-bake process. However, when the post-bake process is started before the exposure process is completed, the sample stage of the exposure apparatus has a hot plate-like function. It is preferable.
  • the time for the post-bake process is usually 10 seconds or more and 200 seconds or less, and the post-bake temperature is usually 100 ° C.
  • the post-exposure baking process does not “heat” the resist film at about room temperature ( For example, you may hold
  • a resist pattern having an opening through which the substrate is exposed is developed using an alkali developer by a general development method such as paddle development, spray development, and dip development.
  • the alkaline developer used in the development process may be an alkaline aqueous solution having a pH of 8 or higher.
  • alkali examples include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate and ammonia; primary amines such as ethylamine and propylamine; secondary amines such as diethylamine and dipropylamine; trimethylamine and triethylamine Tertiary amines such as; alcohol amines such as diethylethanolamine and triethanolamine; quaternary such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide Ammonium hydroxides; and the like.
  • inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate and ammonia
  • primary amines such as ethylamine and propylamine
  • secondary amines such as diethylamine and dipropylamine
  • a water-soluble organic solvent such as methyl alcohol, ethyl alcohol, propyl alcohol, and ethylene glycol, a surfactant, a resin dissolution inhibitor, and the like can be added to the alkaline aqueous solution.
  • ⁇ Projection electrode formation process> metal is deposited in the opening of the negative resist film by plating.
  • the plating method is not particularly limited, and a general plating method such as electrolytic plating can be employed (see, for example, JP-A-2007-73919).
  • the negative resist film is removed from the substrate.
  • the removal method is not particularly limited, and includes a general method such as cleaning using a known solvent capable of dissolving the negative resist film.
  • ⁇ Thickness of resist film> About the resist film obtained by the Example and the comparative example, the film thickness was measured about five points in the resist film surface using a film thickness measuring device (manufactured by SCREEN Holdings, “VM-1210”), and the number average value Was calculated.
  • VM-1210 film thickness measuring device
  • ⁇ Light transmittance> Using a resist film having a thickness of 3.5 ⁇ m obtained in Examples and Comparative Examples as an object to be measured, a light beam at a wavelength of 365 nm using an ultraviolet spectrophotometer (“V-560” manufactured by JASCO Corporation) according to JIS K0115. The transmittance (%) was measured. The measured light transmittance was evaluated according to the following criteria.
  • a substrate with a resist film having a resist pattern obtained in Examples and Comparative Examples was used as a measurement target.
  • SEM scanning electron microscope
  • the line width (top line width) on the resist surface side and the line width (bottom line width) on the substrate side were measured for a line portion which is an opening of the resist pattern.
  • the measurement of the line width was performed at arbitrary three measurement points. Then, the bottom line width was divided by the top line width for each measurement point, and the “bottom line width / top line width ratio” was calculated.
  • the average value of the ratios calculated for all measurement points was defined as the “bottom line width / top line width ratio” of the substrate with the resist film as the measurement target, and evaluation was performed according to the following criteria. If the resist pattern of the resist film has a good reverse taper shape, the taper shape of the protruding electrode formed using such a resist film becomes good.
  • Bottom line width / top line width ratio is 0.8 or more
  • Example 1 Preparation of resist composition solution (preparation process)> A novolak resin having a weight average molecular weight (weight average molecular weight in terms of monodisperse polystyrene measured by GPC) of 3000 obtained by dehydrating and condensing 70 parts of m-cresol and 30 parts of p-cresol as resin (a) Using.
  • a weight average molecular weight weight average molecular weight in terms of monodisperse polystyrene measured by GPC
  • a halogen-containing triazine-based photoacid generator 1 (trade name “TAZ110”, 2- [2- (4- Methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine) 2.0 parts, alkoxymethylated melamine resin as an acid crosslinking agent (Mitsui Cytec, trade name “Cymel”) Trademark) 303 ") 8.0 parts, bisazide compound as a light absorber (trade name” BAC-M ", 2,6-bis (4'-azidobenzal) -4-methylcyclohexanone, manufactured by Toyo Gosei Co., Ltd.) 0 part and 0.5 part of triethanolamine (boiling point: 335 ° C.) as a basic compound are mixed with propylene glycol monomethyl ether acetate (P MEA) was dissolved in 176 parts. The obtained dispersion of the resist composition was diluted in 176 parts. The obtained disper
  • the resist film was exposed with a parallel light mask aligner (manufactured by Canon, trade name “PLA501F”, ultraviolet light source, irradiation wavelength 365 nm to 436 nm) using a 20 ⁇ m line & space (L & S) pattern mask.
  • the exposure amount was 300 mJ / cm 2, and exposure was performed so that the width of the line portion and the width of the space portion were 1: 1 (exposure process).
  • the temperature was set to 100 ° C., a silicon wafer with a resist film was placed on the hot plate, and the post-baking process was performed by holding for 100 seconds.
  • Example 2 In preparing the resist composition solution, the same procedure as in Example 1 was performed except that no basic compound was blended. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 In preparing the resist composition solution, the light absorber was changed to 1.5 parts in the same manner as in Example 1 except that the basic compound was not added. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 In preparing the resist composition solution, a novolak having a weight average molecular weight of 3000 obtained by dehydrating and condensing 70 parts of m-cresol and 30 parts of p-cresol as resin (a) with 19 parts of formaldehyde. A mixture of 97 parts of resin and 3 parts of a poly p-vinylphenol resin having a weight average molecular weight of 5000 (manufactured by Maruzenka Chemical Co., Ltd., “Marcalinker (registered trademark) S-2P”) was used. Example 1 was used except that 100 parts of such resin (a) was used, no basic compound was blended, and the blending amount of the light absorber was changed to 1.5 parts. . Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 6 In preparing the resist composition solution, 2.0 parts of curcumin (San-Eigen FFI Co., Ltd.) was used as a light absorber instead of 2.0 parts of “Bac-M” in Example 1 (Example 5). ), 2.0 parts of Michler's ketone (Example 6) were used, respectively, and no basic compound was blended in each Example. Except for these points, the procedure was the same as in Example 1. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 7 In preparing the resist composition solution, the halogen-containing triazine photoacid generator 2 (2- [1- (4-methoxy) naphthyl] -4,6-bis (trichloromethyl) -1,3 is used as the photoacid generator. , 5-triazine) was used in the same manner as in Example 1 except that no basic compound was added. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 8 In preparing the resist composition solution, the halogen-containing triazine photoacid generator 2 (2- [1- (4-methoxy) naphthyl] -4,6-bis (trichloromethyl) -1,3 is used as the photoacid generator. , 5-triazine) 2.0 parts, and as a light absorber, 2.0 parts of Michler's ketone was used, and the same procedure as in Example 1 was performed except that no basic compound was added. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 9 In preparing the resist composition solution, as the photoacid generator, a photoacid generator 3 (2,2 ′-(1,3-phenylene) bis [2- (butylsulfonyloxyimino) represented by the following formula (Y) is used. ) Acetonitrile]) 2.0 parts, and a bisazide compound as a light absorber (trade name “BAC-M”, 2,6-bis (4′-azidobenzal) -4-methylcyclohexanone, manufactured by Toyo Gosei Kogyo) The procedure was the same as in Example 1 except that 2.0 parts was used and no basic compound was blended. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 In preparing the resist composition solution, as a light absorber, in place of 2 parts of “Bac-M” in Example 1, other light absorbers that are not represented by the formula (I) and are not bisazide compounds ( The same procedure as in Example 1 was conducted except that 2.0 parts of “SOT-Z” (formula (Z)) manufactured by Hodogaya Chemical Co., Ltd. were blended, and no basic compound was blended. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • NNK novolak
  • PVP polyvinylphenol
  • photoacid generator 1 (2- [2- (4-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl).
  • photoacid generator 2 is 2- [1- (4-methoxy) naphthyl] -4,6-bis (trichloromethyl) -1,3,5- Triazine
  • photoacid generator 3 is (2,2 ′-(1,3-phenylene) bis [2- (butylsulfonyloxyimino) acetonitrile])
  • Bac-M is 2,6- Bis (4′-azidobenzal) -4-methylcyclohexanone
  • PMEA represents propylene glycol monomethyl ether acetate.
  • the light transmittance of the resist film at a wavelength of 365 nm is 30% or less (that is, the evaluation result of the light transmittance is A or B evaluation).
  • the evaluation result of the light transmittance is A or B evaluation.
  • a resist film having a good reverse taper shape can be formed, and as a result, a projecting electrode having a good taper shape can be formed.
  • the protruding electrode having a good taper shape could be formed without intentionally carrying out an operation for forming a temperature gradient in the thickness direction of the resist film.
  • the present invention it is possible to provide a negative resist composition for a protruding electrode capable of stably forming a protruding electrode having a good taper shape. Moreover, according to this invention, the manufacturing method of the protruding electrode which has a favorable taper shape can be provided.

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Manufacturing Of Printed Wiring (AREA)
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Abstract

La présente invention concerne une composition de résine négative pour une électrode en saillie présentant un film de résine ayant une transmittance égale ou inférieure à 30 % à une longueur d'onde de 365 nm lors de la production d'un film de résine d'une épaisseur de 3,5 µm.
PCT/JP2017/044987 2016-12-26 2017-12-14 Composition de résine négative pour électrode en saillie et procédé de fabrication d'une électrode en saillie Ceased WO2018123626A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04217324A (ja) * 1990-12-19 1992-08-07 Matsushita Electron Corp 半導体装置の製造方法
JP2005316412A (ja) * 2004-03-31 2005-11-10 Nippon Zeon Co Ltd 感放射線性樹脂組成物
JP2010224308A (ja) * 2009-03-24 2010-10-07 Fujifilm Corp カラーフィルタ及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04217324A (ja) * 1990-12-19 1992-08-07 Matsushita Electron Corp 半導体装置の製造方法
JP2005316412A (ja) * 2004-03-31 2005-11-10 Nippon Zeon Co Ltd 感放射線性樹脂組成物
JP2010224308A (ja) * 2009-03-24 2010-10-07 Fujifilm Corp カラーフィルタ及びその製造方法

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