JP2005159225A - Forming method of insulating film, and manufacturing method of electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a forming method of a film having opening portions on metals, without requiring any process for providing the openings on the metals after forming the film, by forming no film on desired metals, in an electronic device wherein such one or more kinds of metals as electrodes and insulators are formed on a single substrate. <P>SOLUTION: The forming method of a film includes first and second methods. In a first method, by coating the whole of a substrate 5 with a coating liquid whereto any metal is non-wettable, the film of the coating liquid is so formed on the surface of the substrate 5 other than metal electrodes 1, 3 as to form insulating films 6 selectively by solidifying the film of the coating liquid. In a second method for forming insulating films selectively in an electronic device wherein metals comprising two or more kinds of different ones from each other and insulators are formed in a single substrate, by coating the whole of the substrate with a coating liquid whereto only the desired metals of the two or more kinds of different metals from each other are non-wettable, the film of the coating liquid is so formed on the whole of the substrate other than the non-wettable desired metals to the coating liquid as to form insulating films selectively on the substrate other than the desired metals by solidifying the film of the coating liquid. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for selectively forming an insulating film in an electronic device in which a metal such as an electrode and an insulator are formed on the same substrate, an electronic device having an insulating film formed by this method, and the same The present invention relates to a method for manufacturing an electronic device.

  Conventionally, in an electronic device in which a metal such as an electrode and an insulator are formed on the same substrate, there are various coating methods (spin coat, roll coat, curtain coat, spray coat, doctor coat, rod, etc.) Coating, etc.) and dip coating methods are used. However, in these methods, since a film is formed on the entire surface of the substrate, when the metal on the substrate is an electrode, the opening formed on the metal (a specific metal) is removed by removing the film formed on the metal. For this purpose, it is necessary to perform pattern processing such as photolithography and etching.

  However, in order to provide an opening on the metal, for example, when etching using a photoresist is performed, various complicated processes such as mask alignment, exposure, development, and washing are necessary. There was also a problem of the treatment of the waste liquid resulting from this.

On the other hand, in order not to form an insulating film on a specific electrode on an electronic device, a method of forming a resin film so as to expose the top of the protruding electrode has also been proposed (see Patent Document 1). However, this method has a drawback in that since the resin film is formed according to the height of the protruding electrode, the insulating film cannot be formed more than the height of the protruding electrode. Furthermore, it is not possible to identify any dissimilar metal formed on the electronic device and selectively form an opening only on at least one metal.
JP-A-9-167784

  Accordingly, in an electronic device in which one or more kinds of metals such as electrodes and an insulator are formed on the same substrate, a method for selectively forming an insulating film, which selectively insulates on a substrate other than a desired metal. By forming the film, there is no need to provide an opening on the metal after the formation of the insulating film. An insulating film forming method for forming an opening on a desired metal and an electronic device using the same There was a need for a manufacturing method.

  As a result of earnest research to solve the above problems, the inventors of the present application have found that in electronic devices in which one or more kinds of metals such as electrodes and an insulator are formed on the same substrate, the difference in wetting between different materials. By applying a solution that does not show wettability only to a specific metal and applying it to the substrate, the coating solution is selectively repelled on the surface of the specific metal and a film is not formed. In addition, it was discovered that a film can be selectively formed on other insulators and other metals formed on the substrate, and the present invention has been completed.

  The present invention is a method for selectively forming an insulating film in an electronic device in which a metal and an insulator are formed on the same substrate, and the coating is performed by applying a coating solution that does not show wetness to the metal to the entire substrate. Forming a coating liquid film on the entire substrate other than the metal not wetted by the liquid, and solidifying the coating liquid film, thereby selectively forming an insulating film on the substrate other than the metal; and A method of selectively forming an insulating film in an electronic device in which two or more kinds of different metals and an insulator are formed on the same substrate, and showing wetness only to a desired metal among the two or more kinds of different metals. By applying a coating solution that is not applied to the entire substrate, a coating solution film is formed on the entire substrate other than the desired metal that does not get wet with the coating solution, and the coating solution film is solidified to select on the substrate other than the desired metal. Insulating film can be formed It relates to a method which is characterized in. The present invention also relates to an electronic device having an insulating film formed by this method.

  The present invention also relates to a method for manufacturing an electronic device having an insulating film, wherein the insulating film is formed by the above-described method of selectively forming an insulating film.

  According to the present invention, in an electronic device in which one or more kinds of metals such as electrodes and an insulator are formed on the same substrate, an insulating film is not selectively formed on a desired metal, thereby forming an insulating film on the metal after forming the insulating film. An insulating film having a film opening can be formed on a desired metal without requiring a step of providing the film opening. Also, using this method, various semiconductors can be manufactured without the step of forming the film opening.

  The present invention is a method for selectively forming an insulating film in an electronic device in which a metal and an insulator are formed on the same substrate, and the coating is performed by applying a coating solution that does not show wetness to the metal to the entire substrate. A method of selectively forming an insulating film on a substrate other than the metal by forming a coating liquid film on the entire substrate other than the metal that is not wetted by the liquid and solidifying the coating liquid film; and A method of selectively forming an insulating film in an electronic device in which two or more kinds of different metals and an insulator are formed on the same substrate, wherein only a desired metal is not wetted out of two or more kinds of different metals. By applying the coating liquid to the entire substrate, a coating liquid film is formed on the entire substrate other than the desired metal that is not wetted by the coating liquid, and the coating liquid film is solidified, so that the coating liquid film is solidified. Forming an insulating film on It relates to a method for the feature.

  In the method of the present invention, “not wet” and “not wet” mean that the coating liquid does not wet the metal surface, that is, the contact angle between the coating liquid that does not wet the metal and the metal that does not wet the coating liquid. The contact angle θ2 of the portion wetted by the coating solution and the coating solution is θ1 / θ2> 1, and the coating solution is repelled by a desired metal surface after coating, while the substrate is more stable and has a small contact angle. Or gather on the insulator surface. The contact angle is measured using a minimum contact angle measuring device (MCA-1) manufactured by Kyowa Interface Co., Ltd. θ1 / θ2 is> 1, but preferably θ1 / θ2> 1.1, particularly preferably θ1 / θ2> 2.

  In the method of the present invention, an electronic device in which a metal and an insulator are formed on the same substrate means that an insulating film having an opening must be formed on the metal, a metal such as an electrode and a metal wiring, and a semiconductor. Insulating material refers to any electronic device formed on the same substrate. In the method of the present invention, an electronic device in which two or more kinds of different metals and an insulator are formed on the same substrate is an insulating film having an opening on a specific metal of two or more kinds of different metals. It refers to an arbitrary electronic device in which two or more kinds of different metals such as electrodes and metal wirings that need to be formed and an insulator including a semiconductor are formed over the same substrate. Such electronic devices include various electronic devices. Here, the substrate that constitutes the electronic device; the metal such as the electrode and the metal wiring; and the insulator including the semiconductor include arbitrary ones.

  In the method of the present invention, the coating solution that does not show wetness to the metal does not show wetness to a specific metal surface, that is, the contact angle when contacting a specific metal surface is θ1, and the contact to other parts When the angle is θ2, the coating solution satisfies the relational expression of θ1 / θ2> 1. By selecting a coating solution that does not show wetness against the desired metal and applying it to the entire substrate surface, the coating solution is repelled on the non-wetting metal surface and a coating solution film is not formed, and a film opening is formed. The On the other hand, a coating liquid film is formed on the surface of other metals, insulators, and substrates that are wetted by the coating liquid. By solidifying the coating liquid film, other metals other than the desired metal, insulator, and substrate surface can be selected. Thus, an insulating film is formed.

Regarding the coating liquid, the coating liquid that can be used in the method of the present invention is a liquid composition that forms an insulating film by solidification, and any liquid that does not wet a metal surface that does not form an insulating film. Can do.
In this coating solution, an organic component and an inorganic component which are usually used for forming an insulating film can be appropriately blended. Among these, as an organic component, in addition to various epoxy compounds and siloxane compounds, prepolymers such as curable monomers and oligomers that form an insulating resin by curing can be used. It can also be melted or dissolved in a solvent for use. Of these, thermoplastic resins include prepolymers and polymers composed of vinyl acetate, vinyl alcohol, vinyl butyral, vinyl chloride, methacrylate, acrylic acid, methacrylic acid, styrene, ethylene, amide, cellulose, isobutylene, vinyl ether, and the like. be able to. Examples of the thermosetting resin include prepolymers and polymers made of urea, melamine, phenol, resorcinol, epoxy, episulfide, isocyanate, imide and the like. These compounds can be used alone or in combination of two or more. Among these, oxirane compound-modified silane coupling agents represented by epoxy or oxetane can be specifically mentioned.

When such a curable prepolymer is blended in the coating solution, a curing agent and a polymerization initiator for curing the prepolymer can be blended as necessary. The kind of these hardening | curing agents and a polymerization initiator can be suitably selected according to the kind of prepolymer to mix | blend.

  In addition, as an inorganic component usually used for forming an insulating film, various metal alkoxides, various metal chlorides, water glass, colloidal silica, various silicon oxides, silicon nitrides, silicon fluorides, metal oxides, A metal nitride, a metal silicide, a metal phosphate, etc. can be mentioned. Among these, organosilicate, TMOS and the like can be specifically mentioned.

  A coating liquid containing such an inorganic component can be formed into an inorganic insulating film by using a sol-gel reaction, high-temperature baking, or the like. In this case, a sol-gel reaction catalyst can also be blended in the coating liquid.

  As a catalyst for the sol-gel reaction, an inorganic component is hydrolyzed and polycondensed; an acid such as hydrochloric acid; an alkali such as sodium hydroxide; an amine; or dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, Organotin compounds such as dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetraalkyl titanate Organic titanate compounds such as: tetrabutyl zirconate, tetrakis (acetylacetonate) zirconium, tetraisobutyl zirconate, butoxytris ( Cetylacetonato) Zirconium, zirconium naphthenate, and other organic zirconium compounds; Tris (ethyl acetoacetate) aluminum, tris (acetylacetonato) aluminum, and other organic aluminum compounds; Zinc naphthenate, cobalt naphthenate, cobalt octylate, etc. A metal catalyst etc. can be mentioned. Among these, a dibutyltin compound (SCAT-24 manufactured by Sansha Machinery Chemical Co., Ltd.) can be specifically mentioned as a commercial product. These compounds can be used alone or in combination of two or more.

  These organic components and inorganic components can be used as needed alone or in combination of organic and inorganic as appropriate.

  In the coating liquid that can be used in the present invention, a stabilizer, a coupling agent and the like can be appropriately selected and blended as necessary. Specific examples of such stabilizers include 2,6-di-tert-butyl-phenol, 2,4-di-tert-butyl-phenol, 2,6-di-tert-butyl-4-ethyl- Phenol-based antioxidants exemplified by phenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butyl-anilino) -1,3,5-triazine and the like Agent, alkyldiphenylamine, N, N'-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-N'-isopropyl-p-phenylenediamine, etc. Aromatic amine antioxidants, dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, bis [2-methyl Sulfide hydroperoxide decomposer exemplified by -4- {3-n-alkylthiopropionyloxy} -5-tert-butyl-phenyl] sulfide, 2-mercapto-5-methyl-benzimidazole, and the like, tris (isodecyl) phos Phyto, phenyl diisooctyl phosphite, diphenyl isooctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzyl phosphate diethyl ester, sodium bis (4 -Tert-butylphenyl) phosphate, etc., a phosphorus hydroperoxide decomposing agent, phenyl salicylate, a salicylate light stabilizer exemplified by 4-tert-octylphenyl salicylate, etc., 2,4-dihydroxy Benzophenone light stabilizers exemplified by cibenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2′-methylenebis Benzotriazole light stabilizers exemplified by [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, phenyl-4-piperidinyl Hindered amine light stabilizers exemplified by carbonates, bis- [2,2,6,6-tetramethyl-4-piperidinyl sebacate] and the like, [2,2′-thio-bis (4-t-octylphenol) Lat)]-2-ethylhexylamine-nickel- (II) Over preparative based light stabilizers, and the like oxalic acid anilide-based light stabilizer. Further, as such a coupling agent, specifically, ((tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, epoxy-modified silane coupling agent as a fluorine-based silane coupling agent) (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), as an oxetane-modified silane coupling agent (TESOX manufactured by Toagosei Co., Ltd.), or vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane Β-glycidoxypropylmethyldimethyl Silane coupling agents such as xysilane, γ-methacryloxyxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, triethanolamine titanate, titanium acetylacetonate, titanium ethylacetate Acetate, titanium lactate, titanium lactate ammonium salt, tetrastearyl titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, dicumylphenyloxyacetate titanate, isopropyl trioctainol titanate, isopropyl dimethacryliso Stearoyl titanate, titanium lactate ethyl ester, octylene glycol thiol Titanate, isopropyl triisostearoyl titanate, triisostearyl isopropyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, tetra (2-ethylhexyl) titanate, butyl titanate dimer, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tris (Dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite Titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis ( Octyl pyrophosphate) ethylene titanate, tetra -i- propyl titanate, tetra -n- butyl titanate, and titanium-based coupling agents such as diisostearoyl ethylene titanate. These compounds can be used alone or in combination of two or more.

  Moreover, in order to confirm easily the condition of the coating liquid after application | coating, various pigment | dyes and pigments can also be mix | blended with a coating liquid as needed. Examples of such dyes include anthraquinone dyes, aminium dyes, polymethine dyes, diimonium dyes, cyanine dyes, phthalocyanine dyes, pyrazolone dyes, nigrosine dyes, anthraquinone dyes, azo dyes, and chromium complex dyes. However, it is not limited to these. Examples of such pigments include colorless or colored pigments, specifically, titanium dioxide, barium sulfate, calcium carbonate, magnetic iron oxide, ultramarine, ultramarine, ultramarine, zinc yellow, red rose, yellow lead, Inorganic pigments such as lead white, titanium white, carbon black, transparent iron oxide, aluminum powder, and organics such as azo, triphenylmethane, quinoline, anthraquinone, phthalocyanine, lake pigment, isoindoline pigment, quinacridone pigment A pigment, carbon black, a metal colloid, etc. are mentioned, However, It is not limited to these. The pigment preferably has a particle size of 100 nm or less, and more preferably 1 to 50 nm, so that the surface of the formed film is smooth. These dyes and pigments can be used alone or in combination of two or more.

  In the coating solution that can be used in the present invention, various fillers can be blended as necessary in order to improve the mechanical strength, thermal characteristics, and electrical characteristics of the insulating film to be formed. As such a filler, an insulating filler can be preferably used. On the other hand, when a conductor filler is used, it is necessary to add it within a range not imparting conductivity to the film itself so as not to short-circuit between electrodes and wiring. There is. Insulating fillers include powders of metal oxides such as alumina, silica, zirconia and titania, sols such as colloidal silica, titania sol and alumina sol, clay minerals such as talc, kaolinite and smectite, and carbides such as silicon carbide and titanium carbide. And nitrides such as silicon nitride, aluminum nitride and titanium nitride, borides such as boron nitride, titanium boride and boron oxide, complex oxides such as mullite, hydroxides such as aluminum hydroxide and magnesium hydroxide, etc. It is done. As the conductive filler, metals such as Ag, Cu, Au, Al, Mg, Rh, W, Mo, Co, Ni, Pt, Pd, Cr, Ta, Pb, V, Zr, Ti, In, Fe, and Zn Powders, flakes, or colloids can be used. Sn—Pb, Sn—In, Sn—Bi, Sn—Ag, Sn—Zn alloy powders and flakes, acetylene black, furnace black, channel black Conductive carbon-based materials such as carbon black, graphite, graphite fiber, graphite fibril, carbon fiber, activated carbon, charcoal, carbon nanotube, fullerene, and metal oxide-based conductive filler include zinc oxide, tin oxide, indium oxide , Titanium oxide (titanium dioxide, titanium monoxide, etc.) Ri surplus electrons include filler indicating the generated conductive. The particle size of the filler is preferably 100 nm or less, and more preferably 1 to 50 nm so that the surface of the formed film is smooth. Such fillers can be used alone or in combination of two or more, and fillers whose surfaces are treated with a coupling agent or the like can also be preferably used.

  In addition, various surfactants can be added to the coating solution that can be used in the present invention in order to adjust the interfacial tension and wetting of the coating solution. Examples of such surfactants include soaps, lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl benzene sulfonate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate. Acid, N-acyl amino acid salt, α-olefin sulfonate, alkyl sulfate ester salt, alkyl phenyl ether sulfate ester salt, methyl taurate, and the like. Examples of amphoteric surfactants include alkyl diaminoethyl glycine hydrochloride, 2 -Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, fatty acid alkyl betaine, sulfobetaine, amidoxide, etc. Nonionic (nonionic) surfactants include polyethylene glycol alkyl ester compounds, alkyl ether compounds such as triethylene glycol monobutyl ether, ester compounds such as polyoxysorbitan esters, alkylphenol compounds, fluorine Type compounds, silicone type compounds and the like. These compounds can be used alone or in combination of two or more.

  The blending ratio of the various blending components as described above constituting the coating liquid can be appropriately determined according to the blending component.

Regarding Metals The method of the present invention can be applied to any metal that can be formed on a substrate of an electronic device. That is, by appropriately selecting a coating solution that does not wet only the selected metal, an insulating film can be selectively formed on the other metal other than the selected metal, the insulator, and the substrate surface. Examples of such metals include Ag, Cu, Au, Al, Mg, Rh, W, Mo, Co, Ni, Pt, Pd, Cr, Ta, Pb, V, Zr, Ti, In, Fe, and Zn. Examples thereof include metals and Sn—Pb, Sn—In, Sn—Bi, Sn—Ag, and Sn—Zn alloys.

Regarding the combination of the coating liquid and the metal, the method of the present application can be performed by appropriately selecting an arbitrary coating liquid that does not show wetness with respect to the desired metal as described above.

Regarding an insulator, in an electronic device in which an insulating film is formed by the method of the present invention, any insulator that is normally used can be used as an insulator that can be formed on a substrate. Such insulators include Si ₃ N ₄ , AlN, SiO ₂ , La ₂ O ₃ , Nb ₂ O ₃ , Y ₂ O ₃ , ZrO ₂ , BaTiO ₃ , PbTiO ₃ , SrTiO ₃ , MgF ₂ , CeF _2. , Ce ₂ O ₃ , ZnS, Ta ₂ O ₅ , TiO ₂ , HfO ₂ , BN, BeO, and other inorganic insulators, and organic substances such as polycarbonate, polyimide, epoxy resin, acrylic resin, and silicone. Examples of such an insulator include semiconductors such as Si, GaN, SiC, GaAs, InP, and SiGa.

Regarding the substrate, in the electronic device in which the insulating film is formed by the method of the present invention, as the substrate on which the metal or insulator is formed, any substrate that is normally used as a substrate for an electronic device can be used. Examples of such a substrate material include semiconductors such as Si, GaN, SiC, GaAs, InP, and SiGa, SiO ₂ , Al ₂ O ₃ , AlN, BeO, mullite, cordierite, steatite, forsterite, and sapphire. Inorganic insulators, resins such as phenol resin, polyimide, and epoxy resin, and composite materials such as glass-epoxy, paper-epoxy, and glass-polyimide can be given.
When a semiconductor such as silicon is used as the substrate, a substrate whose surface is covered with an insulating oxide film or a substrate passivated with an insulator such as Si ₃ N ₄ or polyimide can be preferably used.

Implementation of the method of the present invention
Preparation of coating solution The implementation of the method of the present invention will be described below. One or more kinds of metals such as electrodes and insulators as described above are formed on a substrate, and then a coating solution that does not show wetness with respect to a specific metal that does not form an insulating film is prepared.
The coating liquid that can be used in the present invention can be adjusted in viscosity and wettability by dissolving appropriately selected blending components as described above in an appropriate amount of solvent. A solvent can be suitably selected according to a compounding component. Specific examples of such solvents include hydrocarbons (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene, toluene, xylene, ethylbenzene, amylbenzene, turpentine oil, pinene, and the like). , Halogenated hydrocarbons (methyl chloride, chloroform, carbon tetrachloride, ethylene chloride, methyl bromide, ethyl bromide, chlorobenzene, chlorobromomethane, bromobenzene, fluorodichloromethane, dichlorodifluoromethane, difluorochloroethane, etc.), alcohol (methanol , Ethanol, n-propanol, isopropanol, n-amyl alcohol, isoamyl alcohol, n-hexanol, n-heptanol, 2-octanol, n-dodecanol, nonanol, cyclohexa Ether, acetal (ethyl ether, dichloroethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, ethylbenzyl ether, furan, furfural, 2-methylfuran, cineol, methylal) , Ketones (acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-amyl ketone, diisobutyl ketone, phorone, isophorone, cyclohexanone, acetophenone, etc.), esters (methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, Propyl acetate, acetic acid-n-amyl, methyl cyclohexyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl stearate), polyhydric alcohols and their derivatives Glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether), fatty acids and phenols ( Formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, isovaleric acid, phenol, cresol, o-cresol, xylenol, etc., nitrogen compounds (nitromethane, nitroethane, 1-nitropropane, nitrobenzene, monomethylamine, dimethyl) Amine, trimethylamine, monoethylamine, diamylamine, aniline, monomethyl Aniline, o-toluidine, o-chloroaniline, dichloroamine, dicyclohexylamine, monoethanolamine, formamide, N, N-dimethylformamide, acetamide, acetonitrile, pyridine, α-picoline, 2,4-lutidine, quinoline, morpholine Etc.), sulfur, phosphorus, other compounds (carbon disulfide, dimethyl sulfoxide, 4,4-diethyl-1,2-dithiolane, dimethyl sulfide, dimethyl disulfide, methanethiol, propane sultone, triethyl phosphate, triphenyl phosphate, (Diethyl carbonate, ethylene carbonate, amyl borate, etc.), inorganic solvents (liquid ammonia, silicone oil, etc.), water and the like.

  The above ingredients are combined with a solvent and stirred to form a solution or suspension. Stirring can be performed by appropriately selecting various stirring devices such as a propeller mixer, a planetary mixer, a hybrid mixer, a kneader, a homogenizer for emulsification, and an ultrasonic homogenizer. Moreover, it can also stir, heating or cooling as needed.

Preparation of Wetting of Coating Solution The coating solution used in the present invention does not form an insulating film, that is, a contact angle θ1 with respect to a specific metal surface forming an insulating film opening, and a contact angle with respect to other parts wetted by the coating solution It is necessary to adjust the wetting so that θ2 has a relationship of θ1 / θ2> 1. Wetting is adjusted by blending various wettability coating liquid materials, and surfactants, silane coupling agents, etc. are added to the coating liquid as additives as appropriate, or diluted with a solvent, or the solvent is evaporated. Can be further adjusted by concentration. As such a surfactant, the above-described surfactants can be used.

Application of coating solution As long as the coating solution prepared as described above is a method that does not hinder the repelling of the coating solution because the desired specific metal does not get wet, film formation in an electronic device in this technical field It can apply | coat by the arbitrary apply | coating methods normally used for (1). As such a method, a coating method using various coaters (spin coating, roll coating, curtain coating, spray coating, doctor coating, rod coating, etc.), a coating method by immersing in a coating solution, and coating by inkjet. Examples thereof include a method, a method of laminating a film and then heating to dissolve the film into a film, and a method of condensing the vaporized coating solution on a substrate to form a film. Moreover, it can also apply | coat combining these methods.

The frequency | count of application | coating can be suitably selected as needed. Further, the same coating solution can be applied a plurality of times, or different types of coating solutions having different wettability can be freely combined and applied a plurality of times.

For example, there is a method of selectively forming an insulating film in an electronic device in which a metal and an insulator are formed on the same substrate, wherein (a) the desired metal is wet but the substrate other than the desired metal is wet A step of forming a first coating liquid film only on the desired metal surface by applying a first coating liquid that does not show the above to the entire substrate, (b) insoluble in the first coating liquid and the desired The desired metal on which the first coating liquid film is formed by applying a second coating liquid on the entire substrate, which shows wetness on the substrate other than the metal of the above, but does not show wetness on the first coating liquid film A step of selectively forming a second coating liquid film on a substrate other than the substrate, and (c) the first coating liquid film on the desired metal is solidified before the second coating liquid film is solidified. At the same time or after solidification, it can be removed by washing or transpiration, and the second coating liquid film can be solidified. Forming method comprising the step of selectively forming a dielectric film on a substrate other than metal (A method).
The present invention also relates to a method of selectively forming an insulating film in an electronic device in which a metal and an insulator are formed on the same substrate, wherein (a ′) wetting is shown on a substrate other than the desired metal, A step of forming a first coating liquid film on the entire substrate other than the desired metal by applying a first coating liquid not showing wetting; (b ′) insoluble in the first coating liquid; And applying a second coating solution that shows wetness to the desired metal but does not wet the first coating solution film to the entire surface of the desired metal other than the first coating solution film. A step of forming a second coating liquid film; and (c ′) after the second coating liquid film is removed or simultaneously, the first coating liquid film is solidified or the first coating liquid film is solidified. Thereafter, by removing the second coating liquid film, an insulating film is selectively formed on the substrate other than the desired metal. Forming method characterized in that to (B method) can also be exemplified.

  Regarding the method A, preferably, a first coating solution that shows wetness on a desired metal but does not show wetness on a substrate other than the desired metal, and a first coating solution that is insoluble in the first coating solution. A second coating liquid having a smaller specific gravity and showing wetness to the substrate other than the desired metal but not showing wetness to the first coating liquid film is placed in the same immersion container and left to stand. A liquid in which the coating liquid is separated into an upper layer and the first coating liquid is separated into a lower layer is prepared. An electronic device in which a metal and an insulator are formed on the same substrate is immersed in a lower layer of two layers of liquid, then the interface between the lower layer and the upper layer, the interface between the lower layer and the upper layer, and the interface between the upper layer and the air. By sequentially passing through the electronic device, the second coating liquid film is not formed on the desired metal surface, but only the first coating liquid film is formed, and the desired metal surface is formed on the first coating liquid. The film is protected by the liquid film, and a film made of the first coating liquid and a film made of the second coating liquid are formed on the insulator and the substrate on the substrate. Thereafter, the first coating liquid is removed, for example, by washing or transpiration, whereby a film opening can be formed on the metal. The film of the first coating solution can be removed before the coating film is solidified, can be removed simultaneously with the solidification of the coating film, or can be removed after the coating film is solidified.

  As described above, the insulating film is formed by protecting the desired metal for forming the opening with the second coating liquid before, after, or simultaneously with the application of the first coating liquid for forming the insulating film. It is possible to prevent contamination by the first coating liquid.

  As described above, the coating solution for protecting a metal has a wettability specifically for Au and Ag in order to protect components that show wettability specifically for the metal to be protected, such as Au and Ag. Good thiol, disulfide, dithiolane and the like can be preferably blended.

  The coating can be performed in normal air, but can be performed in a molten metal in various known solvents such as a gas atmosphere, a vacuum, and water in addition to an air atmosphere. Moreover, the temperature of application | coating can be performed at arbitrary temperature suitable for preparation of the wettability and viscosity of a coating liquid.

  Moreover, in order to evaporate the solvent contained in a coating liquid after application | coating as needed, the process of combining heating, pressure reduction, or these can also be implemented.

Solidification of the coating solution Next, the coating solution formed by coating is solidified or cured. Solidification can be performed by appropriately selecting a known solidification method according to the composition of the coating solution. For example, it can be appropriately carried out by using a method such as a polymerization reaction or sol-gel reaction by high energy, heat, anaerobic, moisture, high frequency, solvent evaporation, solidification from a molten state, thermal fusion, or the like.

Metal Pretreatment In the method of the present invention, a coating solution film is formed on a substrate other than a specific metal by selecting a coating solution that does not exhibit wettability to a specific metal. However, even different types of metals may exhibit almost the same wettability with respect to the same coating solution, and it may be difficult to selectively form a coating film on either of them. In such a case, the wettability of a specific metal among different metals can be modified by subjecting the metal surface to pretreatment before applying the coating solution. Specifically, an electronic device in which two or more kinds of different metals and insulators having different reactivity with respect to oxidation, reduction, hydroxylation, nitridation, sulfurization, carbonization, or phosphation are formed on the same substrate, A step of selectively modifying only a metal surface having reactivity to one or two or more reactions selected from oxidation, reduction, hydroxylation, nitridation, sulfurization, carbonization, or phosphation. Can be performed before the step of applying the coating liquid. By performing such pretreatment, the wettability of the metal surface can be improved and the coating liquid can be easily wetted.

For example, in an electronic device in which Au and Al are formed on the same substrate with little difference in wettability with the same coating solution but with different reactivity to oxidation / hydration, the Al surface is selective in the air. Oxidized / hydroxylated to Al ₂ O ₃ and Al (OH) ₃ . Al is oxidized / hydroxylated in this manner, so that it exhibits higher wettability to the coating solution than Au that is not oxidized, while the wettability of the Au surface that is not oxidized / hydroxylated remains unchanged. .

  In addition, for example, for a substrate on which two or more kinds of metals that are easily oxidized but have a difference in ease of reduction are formed, all the metals are oxidized and then subjected to a reduction step, whereby only the metals that are easily reduced are obtained. By selectively reducing, the wettability of the non-reduced metal surface can be improved, and the same effect as that of Au and Al can be obtained.

As described above, the reactivity of various metals to oxidation, reduction, hydroxylation, nitridation, sulfidation, carbonization, and phosphation can be easily known by those skilled in the art, so two or more types of metals were formed. In the substrate, by selecting a difference in reactivity with respect to metal oxidation or the like as necessary, a wettability is selectively changed for a specific metal among two or more kinds of metals on the same substrate to form a film. The metal and the metal forming the film opening can be selected as appropriate.
A person skilled in the art can appropriately select a method for subjecting various metals to oxidation, reduction, hydroxylation, nitridation, sulfurization, carbonization, or phosphation. For example, in order to oxidize a metal, it is possible to adopt means such as leaving it in the air, leaving it in an oxygen atmosphere, heating it in the presence of oxygen, reacting it with an oxidant solution, or subjecting it to sputtering. In order to reduce the metal, means such as heating in a reducing atmosphere, for example, heating in a hydrogen atmosphere, hydrogen plasma irradiation, or reaction with a reducing agent solution can be employed. In order to hydroxylate a metal, it is possible to take means such as immersing it in water, leaving it under high temperature and high humidity, or spraying water vapor. In order to nitride a metal, means such as heating in a nitrogen, NH ₃ , NO, or NO ₂ atmosphere, reacting with a solution, or subjecting to sputtering can be employed. In order to sulfidize a metal, it is possible to adopt means such as leaving it in a hydrogen sulfide atmosphere, reacting with a solution, or subjecting it to sputtering. In order to carbonize the metal, means such as sputtering can be employed. In order to phosphide the metal, means such as reacting with a phosphoric acid solution or subjecting to sputtering can be employed. The practitioner can carry out these steps alone or in combination of two or more.

Treatment with a coupling agent In addition, an electronic device in which two or more kinds of different metals and an insulator are formed on the same substrate, and selectively reforms only a metal surface that is reactive to oxidation or the like. By further treating the electronic device with a coupling agent, only the surface-modified metal surface can be further modified. The coupling agent is strongly bonded to the surface of the metal that has been surface-modified by oxidation, hydroxylation, etc., while it does not bind strongly to the surface of the metal that has not been surface-modified. Finally, the coupling agent can be selectively chemically bonded to a metal surface that has been surface-treated by oxidation, hydroxylation, or the like to further modify only the metal surface.

By appropriately selecting the coupling agent, desired properties can be imparted to the metal surface. By selecting a coupling agent, it is possible to make the pretreated metal surface more easily wetted or less wettable.
For example, when a fluorine-based silane coupling agent (such as (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane) is used, the silane coupling agent is selectively bonded and modified by pretreatment. The finished metal surface has water repellency. For this reason, when an aqueous coating solution is applied thereafter, the coating solution is repelled on the modified metal, so that a film is not selectively formed, and an opening is formed.
As described above, for example, when a fluorine-based coupling agent having a highly hydrophobic molecular structure is used, the metal surface becomes hydrophobic, and for example, a coupling agent having a strongly hydrophilic molecular structure such as a hydroxyl group. When the is used, the metal surface becomes hydrophilic, and when a coupling agent having a strongly lipophilic structure such as a phenyl group in the molecule is used, the metal surface is modified to be lipophilic.

  An example of modification of a metal surface by a coupling agent is an electronic device in which Au and Al having a difference in reactivity to oxidation / hydration are formed on the same substrate, and only Al is obtained by pretreatment of the metal. In an oxidized / hydroxylated electronic device, when the substrate is treated with a silane coupling agent, the silane coupling agent binds by a strong chemical reaction with hydroxyl groups on the hydroxylated Al surface, while oxidation is also water. Since it does not bind firmly to Au that has not been oxidized, the coupling agent bonded to Au can be easily removed by washing after the treatment. In this way, only Al is further surface-modified according to the type of coupling agent used.

  The treatment with the coupling agent is performed by immersing the electronic device after subjecting the metal to oxidation or the like in a solution of the coupling agent or by diluting the coupling agent solution diluted with an alcohol solvent such as methanol or ethanol into the electronic device. It is preferable to use 10% to 0.1% water and 10% to 0.1% organic acid such as acetic acid, or both as the hydrolysis catalyst. Can be used. The solvent and concentration of the coupling agent solution can be appropriately selected depending on the type of coupling agent selected.

  As described above, a coating solution that does not wet the metal on the substrate is selected, and in the case of a substrate on which two or more kinds of different metals are formed, the metal pretreatment is appropriately performed according to the difference in the reactivity of the metal with respect to oxidation or the like. By selecting the method, the wettability of only a specific metal is modified, and the wettability of a metal subjected to treatment such as oxidation can be further changed by appropriately selecting a coupling agent. By appropriately selecting these conditions, it is possible to form a film opening without forming an insulating film on a desired metal.

  The modified layer by the coupling agent on the metal surface of the film opening formed in this way can be removed by acid or alkali cleaning, plasma cleaning, or the like so as not to hinder electrical bonding, for example.

  Thus, the electronic device in which the insulating film is selectively formed by the method of the present invention can be used for manufacturing an electronic device through various processes as necessary. For example, the metal electrode having the insulating film opening formed as described above can be subjected to various known electrical bonding such as bonding using solder, ultrasonic bonding, and pressure bonding.

  In addition, the method of the present invention can smooth the unevenness caused by electronic devices such as circuits, resistors, and capacitors on the substrate, and can improve the yield and reliability in the multilayering process of wiring and substrate performed to improve the mounting density. Improve and solve the problem of depth of focus of stepper in photolithography.

  The method for forming an insulating film of the present invention can be used for forming an insulating film in the manufacture of an electronic device having the insulating film. Furthermore, for example, in the manufacture of an electronic device having an insulating film, in the step of selectively forming an insulating film on a substrate other than the desired metal, before the coating liquid film is solidified, it is simultaneously solidified or solidified. Later, at least two or more desired metals of the electronic device can be electrically connected. In addition, metal wirings can be formed between at least two desired metals of an electronic device obtained by selectively forming an insulating film on a substrate other than the desired metal. In addition, metal protrusions of the same type or different types from the desired metal can be formed on the desired metal of the electronic device obtained by selectively forming an insulating film on a substrate other than the desired metal. As such a metal protrusion, a low melting point metal bump can be formed. And, as this low melting point metal bump, by using a low melting point metal such as Sn—Pb alloy, Sn—In alloy, Sn—Bi alloy, Sn—Ag alloy, Sn—Zn alloy, etc., between metal electrodes The electrical connection can also be made. Furthermore, the first opening is formed on the first metal electrode by applying the first coating liquid to the electronic device having the first metal electrode using the method of the present invention in the manufacture of the electronic device. A first insulating film may be formed, and then a second metal wiring may be formed on the first insulating film and in the first opening.

  In the method of the present invention, the coating liquid layer is solidified after the coating liquid is applied. However, it is also possible to perform electrical bonding by pressing the metal electrodes together using the shrinkage during solidification. .

  In addition, for example, when a film is formed by blending a thermoplastic resin as a film component in the coating solution, the electrodes may be cooled after thermocompression bonding, and electrical bonding may be performed by pressure welding by cooling and solidifying the thermoplastic resin. it can. As such a thermoplastic resin, a resin of a type that undergoes a polymerization reaction after electrical joining and changes to a thermosetting resin by increasing the cross-linking density can be preferably used.

  Hereinafter, the method of the present invention will be described with reference to examples. In the description of the embodiments, parts and materials related to the implementation of the method of the present invention have been described for each electronic device, but a part of normal metal electrodes, insulators, substrates, etc. included in normal electronic devices are described. Was omitted.

In Example 1, an electronic device having an insulating film opening in a metal electrode on a substrate was produced by the method of the present invention. An example of the manufacturing method is shown in FIGS. Here, (a) is an electronic device in which an electronic device 2 having a metal electrode 1 and an electronic device 4 having a metal electrode 3 are embedded in a resin substrate 5 and integrated. (B) shows the step between the surface of the electronic device 2 and the metal electrode 1 by selectively forming the insulating film 6, the step between the surface of the electronic device 4 and the metal electrode 3, the electronic devices 2 and 4 and the resin. This is an electronic device in which a step with the substrate 5 is smoothed and a film opening is formed on the electrode. (C) is an electronic device in which the metal electrodes 1 and 3 are electrically joined by the metal wiring 7 on the surface smoothed by the insulating film 6 in the electronic device of (b).
Creation of (a) The electronic device of (a) was created. Metal electrodes 1 and 3 in (a) are bumps (metal protrusions) in which nickel is plated with gold, and the size thereof is any one of ψ (diameter) 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, Each height is 5 μm. Furthermore, Si ₃ N ₄ was formed on the surfaces of 2 and 4 other than the metal electrodes 1 and ₃ as a passivation film. An epoxy resin substrate is used as the substrate 5, and there is a step of 5 μm between the chip surface and the substrate surface. (A) has a difference in height depending on the level difference between the surface of the electronic device 2 and the metal electrode 1, the level difference between the surface of the electronic device 4 and the metal electrode 3, and the level difference between the electronic devices 2 and 3 and the resin substrate 5. It wasn't. FIG. 2 shows an electron micrograph of a bump having a diameter of 20 μm and a height of 5 μm.
Preparation of (b) Next, the metal electrodes 1 and 3 are not wetted, but other insulators and the substrate are selected on the metal electrodes 1 and 3 by applying a coating solution that wets the entire substrate and curing. Insulating film 6 having a film opening was formed to obtain (b). Details are described below.
Preparation of coating liquid Epoxy-modified silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) 100 parts, photocation initiator (Adeka Optomer SP-170, Asahi Denka Kogyo Co., Ltd.) 4 parts, ethanol 20 parts, acetone 50 parts were put into a planetary mixer with a cooling jacket and stirred until a uniform solution was obtained to obtain a coating solution. At this time, the coating liquid was stirred while cooling in a range where the liquid temperature did not exceed 25 ° C. so that the coating liquid did not react with the heat generated during stirring to obtain a coating liquid. The contact angle of this coating solution with respect to the Au bump was 30 °. The contact angle with respect to the Si ₃ N ₄ passivation film was 17 °, and the contact angle with respect to the epoxy substrate was 18 °. All contact angles are values at 25 ° C.
Application The application liquid prepared above was applied on the electronic device (a) so as to have a liquid thickness of 8 to 11 μm from the surface of the epoxy substrate 5 using spin coating. When this coating solution was applied, the metal electrodes 1 and 3 selectively repelled the coating solution, and an opening of the solution was formed on the metal electrode, exposing the metal portion.
Next, after curing the coating solution, the coating solution was allowed to stand at room temperature for 5 minutes to evaporate the solvent, and then UV of wavelength 365 nm was irradiated at 6000 mJ / cm ² using a metal halide lamp (EYE GRANDAGE ECS-301) manufactured by Eye Graphic. Then, the coating film was cured to obtain (b) as an insulating film.
Preparation of (c) Next, using the smoothed surface of (b), an Ag wiring 7 was formed between the metal electrodes 1 and 3 to be electrically connected to obtain (c).
Confirmation of Insulating Film Formation State Electron micrographs showing the state before and after the above film formation were taken (before formation: FIG. 2A; after formation: FIG. 2B). It was confirmed that an opening was formed on the metal electrode and the metal surface was exposed.
Further, in the schematic diagram on the right side of FIG. 2B, the portion indicated by the dotted line is perpendicular to the substrate, and the FIB (focused ions) is formed so that the formed insulating film, the metal electrode, and the edge portion of the opening are accommodated. The section was observed with a transmission electron microscope (TEM). At that time, in order to prevent the resin from being damaged due to the influence of cutting, carbon was sputtered twice on the surface of the electronic device observation portion, and then tungsten was further deposited.
The transmission electron microscope image is shown in FIG. As shown in FIG. 3, it was confirmed that an opening was formed on the metal electrode and the metal surface was exposed. Moreover, it was confirmed that there was no insulating film on the metal electrode of any size, and an opening was formed.
When metal wiring is formed on the surface of an electronic device having a step on the substrate surface as shown in FIG. 1A, the thickness of the wiring is reduced at the edge portion of the step, and the possibility of disconnection is increased. According to the method of the present invention, the surface can be smoothed by forming a film on the surface of the electronic device. On the other hand, since the film opening can be formed on the metal electrode, the exposed metal surface and the smoothed electronic device can be formed. By using the surface, electrical connection can be performed by a simple process (inkjet printing, screen printing, drawing with a nozzle, sputtering, plating, etc.).

In Example 2, an electronic device having an insulating film opening in a metal electrode on a substrate was produced by the method of the present invention. An example of the manufacturing method is shown in FIG. Here, (a) is an electronic device in which the metal electrode 8 is formed. (B) is an electronic device in which an insulating film is formed on the back, front, side, and all surfaces of the electronic device other than on the metal electrode 8 by selectively forming the insulating film 11. (C) is an electronic device in which a metal wiring 12 is formed through an insulating film 11 in order to electrically connect the electrode 8 and the back surface of the electronic device. (D) is an electronic device in which an electrode 13 is formed on the wiring 12 for use in subsequent electrical connection. (E) is an electronic device in which film openings are formed on the electrodes 8 and 13 by selectively forming the coating liquid film 14. (F) uses two electronic devices (e) to electrically bond the electrodes 8 and 13 having the film openings to form the insulating film 14 as an insulating film of the electronic device (f). .
Creation of (a) The electronic device of (a) was created. The metal electrode 8 in (a) is a bump obtained by plating gold on nickel, and has a size of ψ10 μm and a height of 5 μm, and is formed on the substrate 10. As a passivation film 9, Si ₃ N ₄ was formed in a portion other than the metal electrode 8. Since silicon is used for the substrate 10 and the wafer is broken after the passivation film 9 is formed, the silicon 10 is exposed at the end face.
Preparation of (b) Next, the metal electrode 8 does not show wetness, but a coating solution which wets other insulators and the substrate is applied to the entire substrate and cured to selectively open the film on the metal electrode 8. An insulating film 11 having a portion was formed to obtain (b). Details are described below.
Preparation of coating liquid 20 parts of organosilane (M silicate 51, manufactured by Tama Chemical Industry Co., Ltd.), 50 parts of organosilica sol (Snowtex MA-ST-M, manufactured by Nissan Chemical Industries, Ltd.), oxetane-modified silane coupling agent (Tojo) A planetary with a cooling jacket containing 30 parts of TESOX manufactured by Synthetic Co., Ltd., 0.1 part of dibutyltin-based hydrolysis catalyst (SCAT-24 manufactured by Sankyo Co., Ltd.), thermal cation initiator (SI-100), and 50 parts of acetone. The mixture was put into a Lee mixer and stirred until a uniform solution was obtained to obtain a coating solution. At this time, the coating liquid was stirred while cooling in a range where the liquid temperature did not exceed 25 ° C. so that the coating liquid did not react with the heat generated during stirring to obtain a coating liquid. The contact angle of this coating solution with respect to the metal electrode 8 was 23 °. The contact angle with respect to the passivation film 9 was 15 °. The contact angle with respect to the substrate 10 was 17 °. All contact angles are values at 25 ° C.
The coating solution is put in 0.8 liter in a 1 liter beaker, the electronic device (a) is immersed therein, and this is pulled out from the solution perpendicularly to the substrate surface at a speed of 50 mm / min. Formed. As a result, the metal electrode 8 was repelled without being wetted by the coating solution, so that the coating solution film was not formed on the metal electrode 8 and a film opening was formed.
Curing of the coating solution Next, the electronic device on which the coating solution film was formed was allowed to stand at room temperature for 5 minutes to evaporate the solvent, and then heated at 150 ° C. for 3 hours to cure the coating solution film, thereby insulating film 11. As a result, (b) was obtained.
Create (c) Next, via the first insulating film 11 surface formed was obtained by forming an Al wiring 12 between the metal electrodes 8 and the rear surface of the substrate and (c).
(D) creating then a gold electrode 13 is formed on the back surface of the metal wiring, and electric and the electrode 8 connected. Next, the Al wiring was left in the air for 48 hours to oxidize / hydroxide the surface.
(E) Next, the metal electrodes 8 and 13 do not show wetness, but the metal of the metal wiring and the first insulating film are coated with a second coating solution showing wetness on the entire substrate. A second coating liquid film 14 having a film opening was selectively formed on the electrodes 8 and 13 to obtain (e). This coating film 14 was made into a semi-cured film by heating at 80 ° C. for 1 hour.
The coating solution used here is the one used in (b) above. The contact angle of this coating solution with respect to the first insulating film 11 was 8 °. Further, the contact angle with respect to the metal wiring 13 was 10 °. All contact angles are values at 25 ° C. Application was also performed in the same manner as in the preparation of (b) above.
Preparation of (f) Next, two electronic devices (d) obtained were crimped and the metal electrodes were electrically joined together, and then the previously formed second semi-cured coating liquid film 14 was formed. It hardened | cured by heating at 150 degreeC for 3 hours, and was set as the insulating film of the electronic device (f).
As described above, an electronic device having a high mounting density can be manufactured with a build-up structure more easily than a conventional build-up structure using a through electrode of a silicon substrate. Thereby, the drilling process at the time of forming a penetration electrode and the cleaning process accompanying it become unnecessary. In the present embodiment in which the substrate is Si, even when the metal wiring is turned to the back via the chip end surface, the entire surface of the chip is protected by the insulating film formed by the method of the present invention, thereby preventing a short circuit. I was able to. Thereby, formation of metal wiring can be performed by a simple process such as ink jet printing, screen printing, drawing with a nozzle, sputtering, plating, or the like. As such a wiring material, Al, Cu, Ag, Au, Pd, etc. can be used. A conductive paste in which metal powder is bound with a resin is used, or metal nanoparticles are sintered at low temperature to form a wiring. Can be used. In addition, this method can be used in the same way for interlayer connection of multilayer PWB, and can eliminate complicated processes such as a drilling process and a cleaning process accompanying the formation of through vias, and a plating process of the inner wall of the hole, It is possible to eliminate the environmental burden caused by the waste liquid associated with the cleaning process.

In Example 3, an electronic device having a film opening in a metal electrode on a substrate was produced by the method of the present invention. An example of the manufacturing method is shown in cross-sectional views in FIGS. 5A and 5B. Here, (a) is an electronic device in which an electrode 15 made of a metal that is not easily oxidized / hydroxylated and an electrode 16 made of a metal that is easily oxidized / hydroxylated are formed on the same substrate. (B) is an electronic device in which a film opening is formed on the metal electrode by selectively forming the insulating film 19. (C) is an electronic device in which the metal wiring 20 made of a metal that is easily oxidized / hydroxylated is turned to the back surface of the substrate on which the electrodes 15 and 16 are formed. (D) is an electronic device in which an electrode is formed on the back surface of the substrate through the metal wiring 20, and is similarly oxidized / hydroxylated on the wiring electrically connected to the electrode 16 made of metal that is easily oxidized / hydroxylated. An electrode 22 made of an easy metal is formed on the back surface, while an electrode 21 made of a metal that is less susceptible to oxidation / hydration is formed on the wiring electrically connected to the electrode 15 made of a metal that is not easily oxidized / hydroxide. It is an electronic device. In (d), wettability was further improved by oxidizing / hydrating the surfaces of the electrodes 16 and 22 made of a metal that is easily oxidized / hydroxylated and the surfaces of the metal wiring 20 made of a metal that is easily oxidized / hydroxylated. (E) forms the film | membrane 23 which has an opening part only in the metal electrodes 15 and 21 by apply | coating a 2nd coating liquid further. (F) shows solder bumps 24 formed by reflowing solder balls on metal electrodes 15 and 21 having film openings. (G) forms the coating liquid film 25 which has an opening only in the solder bump 24 by further applying a third coating liquid. (H) joins the electronic devices (g) by electrically joining the solder bumps 24, and the film 25 is used as an insulating film of the electronic device (h).
Creation of (a) The electronic device of (a) was created. The metal electrode 15 in (a) is a bump made of nickel plated with gold (not easily subjected to oxidation / hydration), and has a size of ψ10 μm and a height of 5 μm. The metal electrode 16 is an aluminum bump (easily oxidized / hydroxylated), and has a size of ψ10 μm and a height of 5 μm. As the passivation film 17, Si ₃ N ₄ was formed on portions other than the metal electrodes 15 and 16. Silicon was used for the substrate 18.
(B) Preparation The metal electrodes 15 and 16 do not show wetness, but other insulators and substrates wet the coating solution over the entire substrate, and are cured to selectively adhere to the metal electrodes 15 and 16. An insulating film 19 having a film opening was formed to obtain (b). The same coating solution as that described in Example 2 (b) was used, and the coating solution was applied by the same coating method, and the coating solution film was cured under the same conditions. The contact angle of the coating solution with respect to the metal electrode 15 was 23 °. The contact angle of this coating solution with respect to the metal electrode 16 was 19 °. The contact angle with respect to the substrate 18 was 17 °. The contact angle with respect to the passivation film 17 was 15 °. All contact angles are values at 25 ° C.
(C) Next, by forming the metal wiring 20 made of Al as a metal that is easily oxidized / hydroxylated through the surface of the formed first insulating film 19, it is electrically connected to the metal electrodes 15 and 16. The connected wiring 20 was turned to the back surface of the substrate to obtain (c). The wiring 20 does not electrically connect the metal electrodes 15 and 16.
(D) creation Subsequently, the formed metal wiring 20 to form a metal electrode. At this time, for the wiring electrically connected to the electrode 16 made of a metal that is easily oxidized / hydroxylated, an electrode 22 made of Al is formed as a metal that is also easily oxidized / hydroxylated. For the wiring electrically connected to the electrode 15 made of a difficult metal, the Ni electrode 20 plated with the metal Au which is also difficult to be oxidized / hydroxylated was formed.
Next, by leaving (d) in a high-temperature and high-humidity atmosphere at 85 ° C./85% for 1 hour, only the surfaces of the electrodes 16 and 22 made of a metal that is easily oxidized / hydroxylated and the surface of the metal wiring 20 are oxidized / hydroxylated. Modified.
(E) Preparation The metal electrodes 15 and 21 are not wetted, but the metal electrodes 16 and 22 surface-modified by oxidation / hydration, the metal of the metal wiring 20, and the first insulating film 19 are wet. By applying the liquid over the entire substrate, a second coating liquid film 23 having a film opening was selectively formed on the metal electrodes 15 and 21 and cured to obtain (e).
The coating solution used here has the composition of (b) above, and was prepared by the same method as in the preparation of (b) above. The contact angle of the coating solution with respect to the metal electrodes 15 and 21 was 23 °. Moreover, the contact angle with respect to the metal electrodes 16 and 22 surface-modified by oxidation / hydration was 10 °. Moreover, the contact angle with respect to the metal of the metal wiring 20 surface-modified by oxidation / hydration was 10 °. The contact angle with respect to the first insulating film 19 was 8 °. All contact angles are values at 25 ° C. Application and curing were also performed in the same manner as in the preparation of (b) above.
(F) the creation Then, on the metal electrodes 15 and 21 having a film opening portion, by reflowing the Sn- based solder balls to form solder bumps 24.
(G) Next, a third coating solution that does not show wetness to the solder but shows wetness to the second insulating film is applied to the entire substrate, thereby selectively opening the film opening on the solder. A third coating liquid film 25 having the following was formed. This coating film 25 was made into a semi-cured film by heating at 80 ° C. for 1 hour.
The coating solution used here is a coating solution having the same composition as in (b) above, and was prepared by the same method. The contact angle of this coating solution with respect to the solder 24 was 28 °, and the contact angle with respect to the second insulating film was 8 °. All contact angles are values at 25 ° C. Moreover, application | coating was performed by the method similar to preparation of previous (b).
Preparation of (h) Next, two electronic devices (g) obtained were thermocompression bonded to electrically bond the solder bumps 24, and at the same time, the third coating liquid film 25 previously formed was removed. It hardened | cured by heating at 200 degreeC for 1 hour, and was set as the insulating film of the electronic device (h).
This example is an example in which the second embodiment is developed in that a film is selectively formed on electrodes of different kinds of metals that show different wetness with respect to the same coating solution by modifying the metal. . By utilizing this, only an arbitrary metal can be selectively and easily connected electrically. In addition to the method of providing electrical connection by providing solder bumps on the metal surface having openings and thermally bonding as shown in the above embodiments, metal bumps (Au, Cu, Ag, Al, etc.) are ultrasonically applied. It is also possible to use a method of electrical connection by heating or heating.

Example 4 shows a method of manufacturing various electronic devices by using a film formed by the method of the present invention, and is shown in FIG.
Production of (a) and (b) The electronic devices of (a) and (b) were produced. The metal electrodes 28 and 29 in (a) and (b) are bumps in which nickel is plated with gold, the size is ψ10 μm, and the height is 5 μm. As the passivation film 27, Si ₃ N ₄ was formed on portions other than the metal electrodes 28 and 29. Silicon was used for the substrate 26.
Preparation of (c) and (d) Next, the metal electrodes 28 and 29 are not wetted, but the substrate is selected on the metal electrodes 28 and 29 by applying a coating liquid that wets the entire substrate and curing. An insulating film 30 having a film opening was formed to obtain (c) and (d). Details are described below.
Preparation of coating solution 70 parts of oxetane-modified silane coupling agent (TESOX manufactured by Toagosei Co., Ltd.), 30 parts of oxetane-modified silsesquioxane (OX-SQ manufactured by Toagosei Co., Ltd.), thermal cation initiator (Sanshin Chemical Co., Ltd.) 2 parts by company Sun Aid SI-100), 20 parts of ethanol and 50 parts of acetone were put into a planetary mixer with a cooling jacket and stirred until a uniform solution was obtained to obtain a coating solution. At this time, the coating liquid was stirred while cooling in a range where the liquid temperature did not exceed 25 ° C. so that the coating liquid did not react with the heat generated during stirring to obtain a coating liquid. The contact angle of this coating solution with respect to metals 28 and 29 was 29 °. Further, the contact angle with respect to the passivation film 26 was 16 °. All contact angles are values at 25 ° C.
Application The application liquid prepared above was applied on the electronic devices (a) and (b) so as to have a liquid thickness of 6 to 8 μm using spin coating. By applying this coating solution, the metals 28 and 29 selectively repel the coating solution, and an opening of the coating solution was formed on the metal, exposing the metal portion.
(E) Next, the electrodes 28 of the electronic device (c) and (d) on which the coating liquid film is formed are joined together, ultrasonically bonded, and the coating liquid film 30 is further cured at 120 ° C. for 30 minutes. An insulating film was obtained. A film opening was formed on the electrode 29 by bonding the electronic devices (c) and (d) having different lengths. The insulating film thus obtained functioned as an interlayer insulating film between (c) and (d) and a protective film for the electronic device (e).
When the method of the present invention is applied to bonding an electronic device, it is possible to prevent the coating liquid from adhering to the metal electrode, so that a film can be formed on the substrate before bonding. For this reason, as shown in (f), when the electronic devices having different lengths are joined with an adhesive, there is an excess adhesive on the electrode 31 at a location near the end of the shorter part. The problem of adhering and preventing the conductive connection was solved.

In Example 5, contrary to the above example, the surface-modified metal electrode was further treated with a coupling agent imparting water repellency to make the metal electrode difficult to wet, and then film formation was performed on the substrate. An electronic device having a film opening in a metal electrode was prepared. An example of the manufacturing method is shown in FIG. Here, (a) shows a case where the metal wiring 33 and the metal electrode 32 are formed on the substrate 34. (B) is an electronic device in which a film opening is formed on a metal electrode by selectively forming an insulating film 35 with respect to (a).
The metal wiring 33 and the metal electrode 32 were formed on the production substrate 34 of (a), and (a) was produced. The metal wiring 33 is an Ag wiring, 32 is an Al electrode, the size of the electrode is ψ10 μm, and the height is 5 μm. A polyimide film (thickness: 50 μm) was used for the substrate 34.
Preparation of (b) The Al surface was oxidized by heating (a) prepared above at 150 ° C. for 30 minutes. Subsequently, the electronic device (a) is immersed in a coupling agent [(tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane (manufactured by Chisso Corporation) in 1% methanol]. The Al surface was further modified by heating at 150 ° C. for 30 minutes. Next, this was immersed and washed with acetone, thereby removing the coupling agent on the Ag wiring 33 and the polyimide film 34 and drying it.
The surface-modified Al does not show wetness, but the first coating liquid that shows wetness on the metal wiring is applied to a thickness of 5 to 10 μm by spin coating on the electronic device after drying. As a result, a coating liquid film 35 having an opening was formed on the metal electrode 32.
The coating solution used here is 60 parts of water-soluble oxetane resin (EOXA manufactured by Toagosei Co., Ltd.), 2 parts of thermal cation initiator (Sun Aid SI-100 manufactured by Sanshin Chemical Industry Co., Ltd.), 20 parts of ethanol, 50 parts of water. Was added to a planetary mixer with a cooling jacket and stirred until a homogeneous solution was obtained. At this time, the coating liquid was stirred while cooling in a range where the liquid temperature did not exceed 25 ° C. so that the coating liquid did not react with the heat generated during stirring to obtain a coating liquid. The contact angle of the coating solution with respect to the metal electrode 32 after the surface modification was 60 °. Moreover, the contact angle with respect to the metal of the metal wiring 33 was 23 degrees. The contact angle with respect to the substrate 34 was 29 °. All contact angles are values at 25 ° C.
Next, the surface of the metal electrode was exposed by performing plasma treatment on the electronic device and removing the coupling agent remaining on the metal electrode 33.

  Since the insulating film is formed using the coating liquid that does not wet only the specific metal formed on the film substrate by using the method of the present invention, the insulating film opening can be formed on any metal surface. Thereby, it can be used for TAB (Tape Automated Bonding) wiring protection.

2 shows a method of creating an electronic device according to the method of the present invention. The scanning electron micrograph which shows the surface of the electronic device before and behind forming a film | membrane by the method of this invention is shown. The transmission electron micrograph of the film | membrane of the electronic device formed into a film by the method of this invention and the slice of a metal electrode is shown. A method for producing an electronic device according to the method of the present invention will be described. 2 shows a method of creating an electronic device according to the method of the present invention. 2 shows a method of creating an electronic device according to the method of the present invention. 2 shows a method of creating an electronic device according to the method of the present invention. 2 shows a method of creating an electronic device according to the method of the present invention.

Explanation of symbols

Metal substrate; 1 Electronic device; 2 Metal electrode; 3 Electronic device; 4 Substrate; 5 Insulating film; 6 Metal wiring; 7 Metal electrode; 8 Passivation film; 9 Substrate; 10 Insulating film; 11 Metal wiring; Insulating film; 14 Metal electrode that is not easily oxidized / hydroxylated; 15 Metal electrode that is easily oxidized / hydroxylated; 16 Passivation film; 17 Substrate; 18 Insulating film; 19 Metal wiring that is easily oxidized / hydroxylated; 21 metal electrode that is easily oxidized / hydroxylated; 22 insulating film; 23 solder bump; 24 insulating film; 25 substrate; 26 passivation film; 27 metal electrode; 28 metal electrode; 29 insulating film; 30 metal electrode; Metal electrode; 32 Metal wiring; 33 Substrate; 34 Insulating film; 35

Claims (15)

  A method of selectively forming an insulating film in an electronic device in which a metal and an insulator are formed on the same substrate, and a coating solution that does not wet the metal is applied to the entire substrate so that the coating solution does not get wet. A method of forming an insulating film, wherein an insulating film is selectively formed on a substrate other than the metal by forming a coating liquid film on the entire substrate other than the metal and solidifying the coating liquid film.   A method of selectively forming an insulating film in an electronic device in which two or more kinds of different metals and an insulator are formed on the same substrate, and showing wetness only to a desired metal among the two or more kinds of different metals. By applying a coating solution that is not applied to the entire substrate, a coating solution film is formed on the entire substrate other than the desired metal that does not get wet with the coating solution, and the coating solution film is solidified to select on the substrate other than the desired metal. A method of forming an insulating film, characterized by forming an insulating film selectively.   The contact angle θ1 between the coating liquid that does not wet the metal and the metal that does not wet the coating liquid and the contact angle θ2 of the portion wetted by the coating liquid and the coating liquid have a relationship of θ1 / θ2> 1. 3. A method for forming an insulating film as described in 2.   An electronic device in which two or more kinds of different metals and insulators having different responsiveness to oxidation, reduction, hydroxylation, nitridation, sulfurization, carbonization, or phosphation are formed on the same substrate is oxidized, reduced, water A step of selectively modifying only a metal surface having reactivity to one or two or more reactions selected from oxidation, nitridation, sulfurization, carbonization, or phosphation, The method for forming an insulating film according to claim 2, which is performed before the coating step.   Surface modified metal surface by subjecting it to a combination of one or more reactions selected from oxidation, reduction, hydroxylation, nitridation, sulfidation, carbonization, or phosphation followed by further treatment with a coupling agent The method for forming an insulating film according to claim 4, wherein only the material is further modified.   6. The method of forming an insulating film according to claim 5, wherein the surface of the metal and the coating liquid are easily wetted by surface modification by treatment with a coupling agent.   6. The method of forming an insulating film according to claim 5, wherein the surface of the metal and the coating liquid are made difficult to wet by surface modification by treatment with a coupling agent.   A first coating liquid film is formed only on the surface of the desired metal by applying a first coating liquid that shows wetting to the desired metal but does not wet the substrate other than the desired metal to the entire substrate. Then, by applying a second coating solution that is insoluble in the first coating solution and shows wetness to the substrate other than the desired metal, but does not show wetness in the first coating solution film, over the entire substrate, A second coating liquid film is selectively formed on a substrate other than the desired metal on which the first coating liquid film is formed, and then the first coating liquid film on the desired metal is The insulating film is selectively formed on a substrate other than the desired metal by solidifying the second coating liquid film before solidifying the coating liquid film, simultaneously with solidification or after solidification, and solidifying the second coating liquid film. The method for forming an insulating film according to any one of 1 to 7.   An electronic device having an insulating film formed by the method according to claim 1.   A method for manufacturing an electronic device having an insulating film, wherein the insulating film is formed by the method according to claim 1.   A method of manufacturing an electronic device having an insulating film, wherein in the step of selectively forming an insulating film on a substrate other than a desired metal by the method according to any one of claims 1 to 8, A method of manufacturing an electronic device, comprising: electrically connecting at least two or more desired metals of the electronic device before solidification, simultaneously with solidification, or after solidification.   A method of manufacturing an electronic device having an insulating film, the electronic device obtained by selectively forming an insulating film on a substrate other than a desired metal by the method according to any one of claims 1 to 8. A method of manufacturing an electronic device, comprising forming a metal wiring between at least two desired metals.   A method of manufacturing an electronic device having an insulating film, the electronic device obtained by selectively forming an insulating film on a substrate other than a desired metal by the method according to any one of claims 1 to 8. A method of manufacturing an electronic device, comprising forming a metal protrusion of the same kind or different kind from the desired metal on the desired metal.   The method for manufacturing an electronic device according to claim 13, wherein the metal protrusion is made of a low melting point metal.   A method for manufacturing an electronic device having an insulating film, wherein a first coating liquid is applied to an electronic device having a first metal electrode by the method according to any one of claims 1 to 8. Forming a first insulating film having a first opening on the metal electrode, and then forming a second metal wiring on the first insulating film and in the first opening. A method for manufacturing an electronic device.