WO2022249500A1 - アンダーバリアメタルとソルダー層とを含む構造体及び構造体の製造方法 - Google Patents
アンダーバリアメタルとソルダー層とを含む構造体及び構造体の製造方法 Download PDFInfo
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- WO2022249500A1 WO2022249500A1 PCT/JP2021/022601 JP2021022601W WO2022249500A1 WO 2022249500 A1 WO2022249500 A1 WO 2022249500A1 JP 2021022601 W JP2021022601 W JP 2021022601W WO 2022249500 A1 WO2022249500 A1 WO 2022249500A1
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- acid
- plating
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- current density
- cathode current
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Images
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Definitions
- the present invention relates to a structure containing an underbarrier metal and a solder layer, and more particularly to a structure containing a solder layer provided as a conductive component such as an electrode or wiring of an electronic component, or a bonding component.
- solder materials such as tin (Sn) and Sn alloys, indium (In) and In alloys, which have a low melting point and excellent ductility, have been used as bonding materials for electronic parts and the like.
- the solder material is mainly applied to the substrate by a ball mount method, a paste method, a plating method, an inkjet method, or the like.
- a copper (Cu) or Cu alloy base material, a nickel (Ni) alloy base material, or the like is used as the base material. is generally provided with a Cu layer or a Ni layer.
- UBM under-barrier metal
- Patent Document 2 by using Fe alloy plating with a specific composition as UBM, it is possible to reduce intermetallic compounds in the joints as described above. Heading.
- the base material may be destroyed, the under-barrier metal may be separated from the base material, or cracks may occur in the under-barrier metal itself, resulting in failure to function as the under-barrier metal. It was found that problems such as being unable to
- the present invention has been made in view of the above problems, and an object of the present invention is to obtain a highly reliable underbarrier metal that can further suppress the formation of intermetallic compounds between a substrate containing a metal and a solder layer. That's what it is.
- the inventors of the present invention have made intensive studies and found that, in a structure including an underbarrier metal and a solder layer, the internal stress of the underbarrier metal is set to 260 MPa or less, resulting in high reliability.
- the inventors have completed the present invention by discovering that an under-barrier metal can be obtained.
- a structure according to one embodiment of the present invention includes a base material, a solder layer formed on the base material, and Fe and Co formed between the base material and the solder layer. and an under-barrier metal that is an alloy layer containing: and an internal stress of the under-barrier metal is 260 Mpa or less.
- the underbarrier metal which is an alloy layer containing Fe and Co, is formed between the base material and the solder layer. Therefore, the under-barrier metal can prevent the metal in the base material from reacting with an element such as Sn contained in the solder layer due to the metal diffusion of the metal in the base material to form an intermetallic compound. Furthermore, in the structure according to the present invention, the internal stress of the underbarrier metal is 260 Mpa or less. Generation of cracks and the like can be suppressed. As a result, the structure has good electrical characteristics, connection reliability, etc., is highly reliable, and is suitable for use in electronic parts and the like.
- the under-barrier metal preferably contains Fe at a mass ratio of 10% or more.
- the underbarrier metal preferably contains Fe at a mass ratio of 10% or more.
- an Sn layer or Sn alloy layer, or an In layer or In alloy layer can be applied as the solder layer.
- a method for manufacturing a structure according to an embodiment of the present invention is a method for manufacturing a structure including an under-barrier metal and a solder layer by sequentially forming an under-barrier metal and a solder layer on a substrate by plating.
- water at least one source of iron ions, at least one source of cobalt ions, at least one acid selected from the group consisting of inorganic acids, alkanesulfonic acids and salts of said acids; forming an under-barrier metal having an internal stress of 260 Mpa using a plating solution comprising at least one stress-relieving agent, wherein the plating solution contains 0.5 g/L to 100 g/L of the stress-relieving agent. It is characterized by containing at a concentration of
- the metal in the base material reacts with an element such as Sn contained in the solder layer due to the metal diffusion of the metal in the base material as described above, and the intermetallic An under-barrier metal for suppressing the generation of compounds is obtained. Furthermore, since the internal stress of the under-barrier metal can be set to 260 Mpa or less, the breakage of the base material, the peeling of the under-barrier metal from the base material, and the occurrence of cracks in the under-barrier metal due to the internal stress are prevented. can be suppressed. Therefore, according to the manufacturing method of the present invention, it is possible to obtain a structure having good electrical characteristics, connection reliability, etc., high reliability, and suitable for use in electronic parts and the like.
- the structure according to the present disclosure it is possible to obtain a highly reliable under-barrier metal that can further suppress the formation of intermetallic compounds between the metal-containing substrate and the solder layer.
- the structure has good electrical characteristics, connection reliability, etc., is highly reliable, and is suitable for use in electronic parts and the like.
- FIG. 1 is a diagram showing a structure according to one embodiment of the present invention.
- an under-barrier metal (UBM) 11 is formed on a base material 10, and a solder layer 12 is formed on the UBM 11.
- the substrate 10 is not particularly limited, it is possible to use, for example, a metal substrate made of Cu or Ni, a glass substrate, a silicon substrate or a sapphire substrate, an organic material substrate, or the like.
- a metal thin film made of Cu, Ni, an alloy containing them, or the like is formed on the upper surface by plating or sputtering. May form structures.
- the base material 10 includes the metal thin film and the structure formed on the upper surface of the base material.
- the base material 10 is not limited to a flat substrate, and may be, for example, a rod-shaped or linear strip.
- the solder layer 12 is made of Sn or an Sn alloy containing Sn as a single metal, or In or an In alloy containing In as a single metal.
- Sn alloys and In alloys include, but are not limited to, Sn--Ag, Sn--Ag--Cu, Sn--Cu, Sn--Bi, Sn--In, and In--Bi.
- the solder layer 12 is formed by, for example, a ball mount method, a paste method, a plating method, an inkjet method, or the like, although not limited to the following methods.
- the Sn plating solution used is basically composed of a soluble stannous salt, an acid or its salt as a solution base, and, if necessary, an antioxidant. agents, stabilizers, complexing agents, surfactants, brighteners, smoothing agents, pH adjusters, conductive salts, preservatives and other additives.
- the soluble stannous salts include stannous salts of organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, 2-propanolsulfonic acid, sulfosuccinic acid, and p-phenolsulfonic acid, and borofluoride.
- stannous, stannous sulfate, stannous oxide, stannous chloride, sodium stannate, potassium stannate and the like can be used.
- a Sn alloy film may be formed using a plating solution containing Sn salt and other metal salts such as Ag and Cu, or a Sn plating film and Ag may be used.
- an alloy film may be formed by stacking a film of another metal such as Cu or Cu and then heat-treating and melting the film.
- the In plating solution used basically includes a soluble indium salt, an acid or its salt as a solution base, and, if necessary, an antioxidant, a stabilizing agent, and an antioxidant. agents, complexing agents, surfactants, brighteners, smoothing agents, pH adjusters, conductive salts, preservatives and other additives.
- the soluble indium salts include indium sulfamate, indium sulfate, indium borofluoride, indium oxide, indium methanesulfonate, and indium 2-hydroxypropanesulfonate.
- an In alloy film may be formed using a plating solution containing In salt and another metal salt such as Sn or bismuth (Bi), or In plating may be used.
- An alloy film may be formed by laminating a film and another metal film such as Sn or Bi, followed by heat treatment and melting.
- the antioxidant prevents oxidation of Sn ions and In ions in the bath.
- salts thereof, phenolsulfonic acid or salts thereof, catecholsulfonic acid or salts thereof, hydroquinonesulfonic acid or salts thereof, hydrazine and the like can be used.
- the above-mentioned stabilizer is for stabilizing or preventing decomposition of the plating bath.
- Known stabilizers such as acids can be used.
- the complexing agent is contained to stabilize Sn ions and In ions in the neutral region to prevent white precipitates and decomposition of the bath.
- Acids, monocarboxylic acids and the like can be used, and specific examples include gluconic acid, citric acid, glucoheptonic acid, gluconolactone, glucoheptolactone, formic acid, acetic acid, propionic acid, butyric acid, ascorbic acid, oxalic acid, Malonic acid, succinic acid, glycolic acid, malic acid, tartaric acid, diglycolic acid, or salts thereof can be used.
- Gluconic acid citric acid, glucoheptonic acid, gluconolactone, glucoheptolactone, or salts thereof are particularly preferred.
- the surfactant contributes to improving the appearance, denseness, smoothness, adhesion, etc. of the plating film, and various usual nonionic, anionic, amphoteric, or cationic surfactants can be used.
- anionic surfactant alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and the like can be used.
- Cationic surfactants include mono- to trialkylamine salts, dimethyldialkylammonium salts, trimethylalkylammonium salts and the like.
- Nonionic surfactants include C 1 -C 20 alkanols, phenols, naphthols, bisphenols, C 1 -C 25 alkylphenols, arylalkylphenols, C 1 -C 25 alkylnaphthols, C 1 -C 25 alkoxyl phosphates (salts ), sorbitan ester, polyalkylene glycol, C 1 -C 22 aliphatic amide, etc., and 2 to 300 mol of ethylene oxide (EO) and/or propylene oxide (PO) are added and condensed.
- Examples of amphoteric surfactants that can be used include carboxybetaine, sulfobetaine, imidazolinebetaine, aminocarboxylic acid, and the like.
- Examples of the brightening agent or semi-brightening agent include benzaldehyde, o-chlorobenzaldehyde, 2,4,6-trichlorobenzaldehyde, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde, furfural, 1-naphthaldehyde, 2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 3-acenaphthaldehyde, benzylideneacetone, pyridideneacetone, furfurylideneacetone, cinnamaldehyde, anisaldehyde, salicylaldehyde, crotonaldehyde, acrolein, glutaraldehyde, para Aldehyde, various aldehydes such as vanillin, triazine, imidazole, indole, quinoline, 2-vinylpyridine, ani
- Examples of the above-mentioned smoothing agent which overlaps with the above-mentioned brightener etc., include ⁇ -naphthol, ⁇ -naphthol-6-sulfonic acid, ⁇ -naphthalenesulfonic acid, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde, ( o-, p-) methoxybenzaldehyde, vanillin, (2,4-, 2,6-) dichlorobenzaldehyde, (o-, p-) chlorobenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, 2(4)- hydroxy-1-naphthaldehyde, 2(4)-chloro-1-naphthaldehyde, 2(3)-thiophenecarboxaldehyde, 2(3)-furaldehyde, 3-indolecarboxaldehyde, salicy
- gelatin gelatin, polypeptone, N-(3-hydroxybutylidene)-p-sulfanilic acid, N-butylidenesulfanilic acid, N-cinnamoylidenesulfanilic acid, 2,4-diamino-6-(2'-methylimidazolyl (1′))ethyl-1,3,5-triazine, 2,4-diamino-6-(2′-ethyl-4-methylimidazolyl(1′))ethyl-1,3,5-triazine, 2, 4-Diamino-6-(2'-undecylimidazolyl(1'))ethyl-1,3,5-triazine, phenyl salicylate, or benzothiazoles are also effective as leveling agents.
- benzothiazoles examples include benzothiazole, 2-methylbenzothiazole, 2-mercaptobenzothiazole, 2-(methylmercapto)benzothiazole, 2-aminobenzothiazole, 2-amino-6-methoxybenzothiazole, 2-methyl -5-chlorobenzothiazole, 2-hydroxybenzothiazole, 2-amino-6-methylbenzothiazole, 2-chlorobenzothiazole, 2,5-dimethylbenzothiazole, 6-nitro-2-mercaptobenzothiazole, 5-hydroxy -2-methylbenzothiazole, 2-benzothiazolethioacetic acid and the like can be used.
- various acids such as hydrochloric acid and sulfuric acid, various bases such as aqueous ammonia, potassium hydroxide and sodium hydroxide can be used.
- Acids, boric acids, phosphoric acids, dicarboxylic acids such as oxalic acid and succinic acid, and oxycarboxylic acids such as lactic acid and tartaric acid can also be used.
- conductive salt sodium salts, potassium salts, magnesium salts, ammonium salts, amine salts of sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, sulfonic acid, etc. can be used. Sometimes you can.
- antiseptic examples include boric acid, 5-chloro-2-methyl-4-isothiazolin-3-one, benzalkonium chloride, phenol, phenol polyethoxylate, thymol, resorcinol, isopropylamine, guaiacol, and the like. can.
- the UBM 11 is provided to suppress the formation of an intermetallic compound 13 due to the reaction between the metal contained in the base material 10 and Sn or In of the solder layer 12 due to metal diffusion.
- the UBM 11 is an alloy layer containing Fe and Co, and preferably contains Fe at a mass ratio of 10% or more. Such a configuration can improve the effect of suppressing the generation of the intermetallic compound 13 of the UBM 11 .
- the UBM 11 can be formed by methods such as plating, sputtering, vapor deposition, ball mounting, and paste printing.
- a solution in which at least one of water-soluble Co salt, Rh salt, Fe salt, Rh salt and Pd salt is dissolved is mixed with an acid or a salt thereof as a liquid base, Plating containing various additives such as antioxidants, stabilizers, complexing agents, surfactants, brighteners, smoothing agents, pH adjusters, conductive salts, preservatives, etc.
- a liquid can be used.
- the UBM 11 is formed so that its internal stress is 260 Mpa or less. By doing so, it is possible to suppress the breakage of the base material 10, the separation of the UBM 11 from the base material 10, and the occurrence of cracks in the UBM 11 due to the internal stress of the UBM 11, and the like.
- a plating solution containing at least one selected acid and at least one stress reliever can be used.
- the supply source of the iron ions contained in the plating solution is not particularly limited, but examples include iron chloride, iron sulfate, iron nitrate, iron sulfamate, iron acetate, iron bromide, iron sulfide, iron citrate, Salts such as iron ammonium citrate, iron ammonium sulfate, iron lactate, iron oxalate, iron phosphate, iron pyrophosphate, and hydrate salts thereof. These can be used alone or in combination of two or more.
- the supply source of the cobalt ion contained in the plating solution is not particularly limited, but cobalt sulfate, cobalt chloride, cobalt acetate, cobalt fluoroborate, cobalt methanesulfonate, cobalt 2-hydroxypropanesulfonate, and cobalt sulfamate. and salts of these hydrates. These can be used alone or in combination of two or more.
- the acid contained in the plating solution includes acids or salts such as hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, acetic acid, citric acid, lactic acid, oxalic acid, phosphoric acid, and pyrophosphoric acid. These can be used alone or in combination of two or more.
- Examples of the stress relaxation agent contained in the plating solution include sodium saccharin, gluconic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 2-hydroxyethylethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid, 1,3- Propanediaminetetraacetic acid, diaminohydroxypropanetetraacetic acid, 2-hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine-N,N'-disuccinic acid, maleic acid, methanesulfonic acid, ethanesulfonic acid, 2-propanol sulfone acid, sulfosuccinic acid, p-phenolsulfonic acid, formic acid, tartaric acid, glyoxylic acid, phosphorous acid, hypophosphorous acid, boric acid, 1-naphthol-4-s
- the stress relaxation agent is adjusted so that the internal stress of the UBM 11 is 260 Mpa or less and contained in the plating solution. Specifically, in order to achieve the above internal stress, the stress relaxation agent is added to the plating solution at a concentration of 0.5 g/L to 100 g/L, preferably 1 g/L to 40 g/L. added as
- the structure according to the present embodiment is not limited to the following, but for example, a printed wiring board, a semiconductor integrated circuit, a resistor, a capacitor, a filter, a thermistor, a crystal oscillator, a switch, a lead wire, or an electronic device such as a solar cell. Applicable to parts.
- Comparative Example 7 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 40 g/L Cobalt chloride (as Co2 + ): 50 g/L Citric acid: 20g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 1 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 20 g/L Cobalt chloride (as Co2 + ): 80 g/L Citric acid: 20g/L Nitrilotriacetic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 2 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 30 g/L Cobalt chloride (as Co2 + ): 65 g/L Citric acid: 20g/L 2-hydroxyethylethylenediamine triacetic acid: 20 g / L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 3 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 40 g/L Cobalt chloride (as Co2 + ): 50 g/L Citric acid: 20g/L Nitrilotriacetic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 4 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 40 g/L Cobalt chloride (as Co2 + ): 50 g/L Citric acid: 20g/L Ethylenediaminetetraacetic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 5 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 40 g/L Cobalt chloride (as Co2 + ): 10 g/L Citric acid: 20g/L Ethylenediaminetetraacetic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 6 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 40 g/L Cobalt chloride (as Co2 + ): 20 g/L Citric acid: 20g/L 1-naphthol-4-sulfonic acid: 10 g / L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 7 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 90 g/L Cobalt chloride (as Co2 + ): 20 g/L Citric acid: 20g/L Methacrylic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 8 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 100 g/L Cobalt chloride (as Co2 + ): 20 g/L Citric acid: 20g/L Triethylenetetramine hexaacetic acid: 10 g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 9 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 110 g/L Cobalt chloride (as Co2 + ): 20 g/L Citric acid: 20g/L Glycol ether diamine tetraacetic acid: 10 g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 10 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 40 g/L Cobalt chloride (as Co2 + ): 50 g/L Citric acid: 20g/L Boric acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 11 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 90 g/L Cobalt chloride (as Co2 + ): 20 g/L Citric acid: 20g/L Glyoxylic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 12 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 40 g/L Cobalt chloride (as Co2 + ): 50 g/L Citric acid: 20g/L Malic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 13 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 90 g/L Cobalt chloride (as Co2 + ): 20 g/L Citric acid: 20g/L Ethanesulfonic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 14 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 40 g/L Cobalt chloride (as Co2 + ): 50 g/L Citric acid: 20g/L Sodium gluconate: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 15 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 100 g/L Cobalt chloride (as Co2 + ): 20 g/L Citric acid: 20g/L Acrylic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 16 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 90 g/L Cobalt chloride (as Co2 + ): 20 g/L Citric acid: 20g/L Tartaric acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 17 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2+): 40 g/L Cobalt chloride (as Co2+): 50 g/L Citric acid: 20g/L Pyrophosphate: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 18 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 90 g/L Cobalt chloride (as Co2 + ): 20 g/L Citric acid: 20g/L Ethylenediamine-N,N'-disuccinic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 19 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 40 g/L Cobalt chloride (as Co2 + ): 50 g/L Citric acid: 20g/L Thiodiglycolic acid: 10 g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 20 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron chloride (as Fe2 + ): 90 g/L Cobalt chloride (as Co2 + ): 20 g/L Citric acid: 20g/L Sulfosuccinic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 21 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron sulfate (as Fe2 + ): 40 g/L Cobalt chloride (as Co2 + ): 50 g/L Citric acid: 20g/L Thiodiglycolic acid: 10 g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- Example 22 An electric Fe—Co bath was prepared with the following composition. Plating conditions are also shown. [composition] Iron sulfamate (as Fe2 + ): 40 g/L Cobalt sulfamate (as Co2 + ): 50 g/L Citric acid: 20g/L Sulfosuccinic acid: 10g/L pH 3.5 [Plating conditions] (a) Bath temperature: 50°C (b) Cathode current density First cathode current density: 3 A/dm 2 Plating time: about 300 seconds Thickness of formed plating layer: 3 ⁇ m
- a copper layer was applied to the upper surface of a semiconductor wafer to form a base material, and UBM was formed on this base material by the respective methods described above.
- a solder layer was formed on the UBM by electroplating to complete the structure. Electroplating for forming the solder layer is carried out using a normal well-known method, and one or more of water-soluble Sn salts, In salts, Ag salts, Bi salts, and Cu salts are dissolved according to the type of plating film to be formed. A plating solution containing various additives was used in the obtained solution. The plating conditions were 30° C. and 3 A/dm 2 , and the film thickness of the plating film was 10 ⁇ m.
- Examples 1 to 22 and Comparative Examples 1 to 13 formed as described above were subjected to heat treatment at 180° C. for 150 hours, and then Sn layer or Sn alloy layer or In layer or In alloy.
- Table 1 shows the results of measuring the thickness of the intermetallic compound formed under the solder layer. In addition, the thickness of the intermetallic compound is indicated by a ratio based on the result of Comparative Example 1 (100%).
- Table 1 shows the composition of the UBM and solder layer formed in each example and comparative example, the internal stress of the UBM, and the presence or absence of peeling of the UBM from the substrate.
- the numbers in the UBM column of Table 1 indicate mass ratios, and for example, "Fe10-Co90" indicates an alloy containing 10% by mass of Fe and 90% by mass of Co. Also, in the column of the solder layer, the content in parentheses indicates the content of one of the alloys, and the content of the other is the remainder. Further, the internal stress of the UBM is calculated from the following formula by measuring the open leg width of the strip using a strip-type electrodeposition stress tester (683EC Analyzer, Fuji Kasei Co., Ltd.).
- S UKM/3T
- S is the internal stress
- U is the strip width
- K is the calibration constant of the test strip
- M is the M factor (modulus of elasticity of the precipitate/elastic modulus of the test strip material)
- T is the precipitate.
- the structure according to the present invention it is possible to obtain a highly reliable UBM that can further suppress the formation of intermetallic compounds between the base material containing metal and the solder layer.
- the electrical characteristics, connection reliability, and the like are improved, the reliability is high, and it is suitable for use in electronic parts and the like.
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Abstract
Description
下記組成で電気Ni浴を建浴した。また、めっき条件も併せて示す。
[組成]
スルファミン酸ニッケル(Ni2+として):50g/L
ホウ酸:40g/L
サッカリンナトリウム:2g/L
pH4.0
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Ni浴を建浴した。また、めっき条件も併せて示す。
[組成]
スルファミン酸ニッケル(Ni2+として):50g/L
ホウ酸:40g/L
サッカリンナトリウム:1g/L
pH4.0
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Ni浴を建浴した。また、めっき条件も併せて示す。
[組成]
スルファミン酸ニッケル(Ni2+として):50g/L
ホウ酸:40g/L
サッカリンナトリウム:0.70g/L
pH4.0
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Ni浴を建浴した。また、めっき条件も併せて示す。
[組成]
スルファミン酸ニッケル(Ni2+として):50g/L
ホウ酸:40g/L
サッカリンナトリウム:0.50g/L
pH4.0
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Ni浴を建浴した。また、めっき条件も併せて示す。
[組成]
スルファミン酸ニッケル(Ni2+として):50g/L
ホウ酸:40g/L
サッカリンナトリウム:0.20g/L
pH4.0
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):20g/L
塩化コバルト(Co2+として):80g/L
クエン酸:20g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):50g/L
クエン酸:20g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):100g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):45g/L
塩化コバルト(Co2+として):45g/L
クエン酸:20g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):10g/L
クエン酸:20g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):110g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):90g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):20g/L
塩化コバルト(Co2+として):80g/L
クエン酸:20g/L
ニトリロ三酢酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):30g/L
塩化コバルト(Co2+として):65g/L
クエン酸:20g/L
2-ヒドロキシエチルエチレンジアミン三酢酸:20g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):50g/L
クエン酸:20g/L
ニトリロ三酢酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):50g/L
クエン酸:20g/L
エチレンジアミン四酢酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):10g/L
クエン酸:20g/L
エチレンジアミン四酢酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
1-ナフトール-4-スルホン酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):90g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
メタクリル酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):100g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
トリエチレンテトラミン六酢酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):110g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
グリコールエーテルジアミン四酢酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):50g/L
クエン酸:20g/L
ホウ酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):90g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
グリオキシル酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):50g/L
クエン酸:20g/L
リンゴ酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):90g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
エタンスルホン酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):50g/L
クエン酸:20g/L
グルコン酸ナトリウム:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):100g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
アクリル酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):90g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
酒石酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):50g/L
クエン酸:20g/L
ピロリン酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):90g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
エチレンジアミン-N,N’-ジコハク酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):50g/L
クエン酸:20g/L
チオジグリコール酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
塩化鉄(Fe2+として):90g/L
塩化コバルト(Co2+として):20g/L
クエン酸:20g/L
スルホコハク酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
硫酸鉄(Fe2+として):40g/L
塩化コバルト(Co2+として):50g/L
クエン酸:20g/L
チオジグリコール酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
下記組成で電気Fe-Co浴を建浴した。また、めっき条件も併せて示す。
[組成]
スルファミン酸鉄(Fe2+として):40g/L
スルファミン酸コバルト(Co2+として):50g/L
クエン酸:20g/L
スルホコハク酸:10g/L
pH3.5
[めっき条件]
(ア)浴温:50℃
(イ)陰極電流密度
第1陰極電流密度:3A/dm2
めっき時間:約300秒
形成されためっき層の厚さ:3μm
S=UKM/3T
なお、上記式において、Sは内部応力、Uはストリップ開脚幅、Kはテストストリップのキャリブレーション定数、MはMファクター(析出物の弾性率/テストストリップ材の弾性率)、Tは析出物の膜厚である。
11 アンダーバリアメタル(UBM)
12 ソルダー層
13 金属間化合物
Claims (4)
- 基材と、
前記基材の上に形成されたソルダー層と、
前記基材とソルダー層との間に形成されたFeとCoとを含む合金層であるアンダーバリアメタルとを備え、
前記アンダーバリアメタルの内部応力は、260Mpa以下であることを特徴とする構造体。 - 前記アンダーバリアメタルは、Feを10%以上の質量比率で含むことを特徴とする請求項1に記載の構造体。
- 前記ソルダー層は、Sn層若しくはSn合金層、又はIn層若しくはIn合金層であることを特徴とする請求項1又は2に記載の構造体。
- 基材の上にめっき法によりアンダーバリアメタル及びソルダー層を順次形成して、アンダーバリアメタル及びソルダー層を含む構造体を製造する方法であって、
水と、少なくとも1つの鉄イオンの供給源と、少なくとも1つのコバルトイオンの供給源と、無機酸、アルカンスルホン酸及び前記酸の塩からなる群から選択される少なくとも1つの酸と、少なくとも1つの応力緩和剤とを含むめっき溶液を用いて、内部応力が260Mpaであるアンダーバリアメタルを形成するステップを含み、
前記めっき溶液は、前記応力緩和剤を0.5g/L~100g/Lの濃度で含むことを特徴とする構造体の製造方法。
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US18/564,376 US20240258255A1 (en) | 2021-05-27 | 2021-06-15 | Structure comprising under barrier metal and solder layer, and method for producing structure |
EP21943134.3A EP4350748A1 (en) | 2021-05-27 | 2021-06-15 | Structure comprising under barrier metal and solder layer, and method for producing structure |
KR1020237040960A KR20240013746A (ko) | 2021-05-27 | 2021-06-15 | 언더베리어 메탈과 솔더층을 포함하는 구조체 및 구조체의 제조 방법 |
CN202180099511.1A CN117501421A (zh) | 2021-05-27 | 2021-06-15 | 含有下层阻挡金属和焊料层的结构体 |
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JP2021089587A JP7197933B2 (ja) | 2021-05-27 | 2021-05-27 | アンダーバリアメタルとソルダー層とを含む構造体 |
JP2021-089587 | 2021-05-27 |
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