WO2018180192A1

WO2018180192A1 - Plating liquid

Info

Publication number: WO2018180192A1
Application number: PCT/JP2018/007997
Authority: WO
Inventors: 眞美渡邉; 中矢　清隆; 康今野
Original assignee: 三菱マテリアル株式会社
Priority date: 2017-03-27
Filing date: 2018-03-02
Publication date: 2018-10-04
Also published as: CN110462108A; TW201843354A; TWI742262B; CN110462108B

Abstract

This plating liquid contains (A) a soluble salt that contains at least a first tin salt, (B) an acid selected from among organic acids and inorganic acids or a salt thereof, and (C) two surfactants, namely an amine-based surfactant (C1) and a nonionic surfactant (C2 and/or C3). The amine-based surfactant (C1) is a polyoxyethylene alkyl amine represented by general formula (1); and the nonionic surfactant (C2 and/or C3) is a condensation product of a polyoxyethylene and a polyoxypropylene represented by general formula (2) or general formula (3). In formula (1), x is 12-18 and y is 4-12. In formula (2), m is 15-30 and (n1 + n2) is 40-50. In formula (3), (m1 + m2) is 15-30 and n is 40-50.

Description

Plating solution

The present invention relates to a plating solution for forming a tin or tin alloy plating film. More specifically, the present invention relates to a tin or tin alloy plating solution that is suitable for forming solder bumps for semiconductor wafers and printed circuit boards, has a uniform bump height over a wide current density range, and suppresses the generation of voids during bump formation. It is. This international application includes Japanese Patent Application No. 61175 (Japanese Patent Application No. 2017-61175) filed on March 27, 2017 and Japanese Patent Application No. 31865 (Japanese Patent Application No. 31865) filed on February 26, 2018. The contents of Japanese Patent Application No. 2017-61175 and Japanese Patent Application No. 2018-31865 are incorporated in this international application.

Conventionally, a lead-tin alloy solder plating solution comprising an aqueous solution containing at least one selected from acids and salts thereof, a soluble lead compound, a soluble tin compound, a nonionic surfactant and a formalin condensate of naphthalenesulfonic acid or a salt thereof Is disclosed (for example, see Patent Document 1). In this plating solution, a formalin condensate of naphthalenesulfonic acid or a salt thereof as an additive contains 0.02 to 1.50% by mass with respect to lead ions. Patent Document 1 states that even if plating is performed with this plating solution at a high current density, a lead-tin alloy protruding electrode having a small surface height variation, smoothness, and a small variation in the lead / tin composition ratio can be formed. Are listed.

Further, (A) a soluble salt composed of any of a tin salt and a mixture of a tin salt and a predetermined metal salt such as silver, copper, bismuth and lead, (B) an acid or a salt thereof, and (C) a specific A tin or tin alloy plating bath containing a phenanthrolinedione compound is disclosed (for example, see Patent Document 2). In Patent Document 2, since this plating bath contains a specific phenanthrolinedione compound as an additive, the plating bath can have excellent uniform electrodeposition and a good film appearance in a wide range of current densities. It is described that a uniform synthetic composition can be obtained in the current density region.

Furthermore, a tin plating solution containing a tin ion source, at least one nonionic surfactant, and imidazoline dicarboxylate and 1,10-phenanthroline as additives is disclosed (for example, see Patent Document 3). ). Patent Document 3 states that this tin plating solution does not cause discoloration even in the plating of highly complicated printed circuit boards, has excellent uniformity of in-plane film thickness distribution, and excellent uniformity of through-hole plating. Has been.

JP 2005-290505 A (Claim 1, paragraph [0004]) Japanese Patent Laying-Open No. 2013-044001 (Summary, paragraph [0010]) JP 2012-087393 A (summary, paragraph [0006])

For tin or tin alloy plating solution for forming solder bumps as plating films for semiconductor wafers and printed circuit boards, the thickness uniformity of the plating film, that is, the height of the solder bumps (within- die; WID) uniformity is required. Although the height uniformity of solder bumps has been improved by the conventional tin or tin alloy plating solution containing the additives described in Patent Documents 1 to 3 above, in recent years, there has been a demand for the quality of the plating film. Accordingly, there is a demand for further improvement in solder bump height uniformity.

In addition, when bumps provided on a substrate for connecting semiconductor devices in flip chip mounting are formed by plating, voids called voids may be formed inside the bumps after reflow treatment, which may cause poor bonding. There is a need to not form this void. However, there is a contradictory relationship between improving the height uniformity of the solder bumps and suppressing the generation of voids when the bumps are formed, and there is an additive for the plating solution that solves both of these problems. It has been sought.

An object of the present invention is to provide a plating solution in which the height of solder bumps is uniform in a wide current density range, and generation of voids is suppressed when the bumps are formed.

A first aspect of the present invention is a plating solution containing (A) a soluble salt containing at least a stannous salt, (B) an acid selected from organic acids and inorganic acids or salts thereof, and (C) an additive. . The characteristic point is that the additive contains two types of surfactants, an amine surfactant (C1) and a nonionic surfactant (C2 and / or C3), and the amine surfactant (C1). Is a polyoxyethylene alkylamine represented by the following general formula (1), and the nonionic surfactant (C2 or C3) is a polyoxyethylene alkylamine represented by the following general formula (2) or general formula (3) It is a condensate of oxyethylene and polyoxypropylene.

However, in the formula (1), x is 12 to 18, and y is 4 to 12.

However, in the formula (2), m is 15 to 30, and n1 + n2 is 40 to 50.

However, in the formula (3), m1 + m2 is 15 to 30, and n is 40 to 50.

A second aspect of the present invention is an invention based on the first aspect, wherein the additive is a surfactant other than the two types of surfactants (C1, C2 and / or C3), complexing The plating solution further contains two or more other additives among the agent, brightener and antioxidant.

In the plating solution according to the first aspect of the present invention, the amine surfactant (C1) and the nonionic surfactant (C2 and / or C3) both suppress the precipitation of Sn ions during plating, and the surface to be plated. It is possible to plate well. The amine surfactant (C1) alone has too little effect of suppressing the precipitation of Sn ions at a low current density, resulting in variations in bump height when solder bumps are formed. In addition, when only the nonionic surfactant (C2 and / or C3) is used, when the current density is increased and the plating rate is increased, Sn ions near the surface to be plated are depleted, resulting in poor plating. By including both amine-based surfactant (C1) and nonionic surfactant (C2 and / or C3) as additives, the defects of both surfactants can be compensated for each other, and a wide range of current can be achieved even at high plating rates. Bump height (WID) uniformity is achieved in the density range, and void generation is suppressed when bumps are formed.

In the plating solution according to the second aspect of the present invention, two of surfactants, complexing agents, brighteners and antioxidants different from the two kinds of surfactants (C1, C2 and / or C3) are used. By further including the above other additives, the following effects are obtained. A surfactant other than the two types of surfactants (C1, C2 and / or C3) has effects such as stabilizing the plating solution and improving solubility. Further, when the plating solution contains a noble metal such as silver, the complexing agent stabilizes the noble metal ions and the like in the bath and makes the precipitated alloy composition uniform. The brightener imparts gloss to the plating film. Furthermore, the antioxidant prevents oxidation of the soluble stannous salt to the stannic salt.

It is a top view of the wafer which has the resist layer produced in the Example.

Next, a mode for carrying out the present invention will be described.

The plating solution of the present invention is a plating solution of tin or a tin alloy, (A) a soluble salt containing at least a stannous salt, (B) an acid selected from an organic acid and an inorganic acid or a salt thereof, (C ) Contains additives. This additive contains two types of surfactants, an amine surfactant (C1) and a nonionic surfactant (C2 and / or C3). The amine surfactant (C1) is represented by the above general formula (1). The nonionic surfactant (C2 or C3) is a condensate of polyoxyethylene and polyoxypropylene represented by the above general formula (2) or general formula (3). is there. The soluble salt is composed of any one of a stannous salt and a mixture of the stannous salt and a metal salt selected from the group consisting of silver, copper, bismuth, nickel, antimony, indium, and zinc.

The tin alloy of the present invention is an alloy of tin and a predetermined metal selected from silver, copper, bismuth, nickel, antimony, indium, and zinc. For example, tin-silver alloy, tin-copper alloy, tin-bismuth Examples include alloys, tin-nickel alloys, tin-antimony alloys, tin-indium alloys, tin-zinc alloy binary alloys, ternary alloys such as tin-copper-bismuth and tin-copper-silver alloys.

Accordingly, the soluble salt (A) of the present invention contains Sn ²⁺ , Ag ⁺ , Cu ⁺ , Cu ²⁺ , Bi ³⁺ , Ni ²⁺ , Sb ³⁺ , In ³⁺ , Zn ^{2+ and the} like in the plating solution. It means any soluble salt that generates various metal ions, and examples thereof include the metal oxides, halides, inorganic acids, and organic acids of the metals.

Examples of metal oxides include stannous oxide, copper oxide, nickel oxide, bismuth oxide, antimony oxide, indium oxide, and zinc oxide. Metal halides include stannous chloride, bismuth chloride, and bromide. Examples thereof include bismuth, cuprous chloride, cupric chloride, nickel chloride, antimony chloride, indium chloride, and zinc chloride.

Metal salts of inorganic or organic acids include copper sulfate, stannous sulfate, bismuth sulfate, nickel sulfate, antimony sulfate, bismuth nitrate, silver nitrate, copper nitrate, antimony nitrate, indium nitrate, nickel nitrate, zinc nitrate, copper acetate , Nickel acetate, nickel carbonate, sodium stannate, stannous borofluoride, stannous methanesulfonate, silver methanesulfonate, copper methanesulfonate, bismuth methanesulfonate, nickel methanesulfonate, indium metasulfonate, bismethane Examples thereof include zinc sulfonate, stannous ethanesulfonate, and bismuth 2-hydroxypropanesulfonate.

The acid or salt (B) of the present invention is selected from organic acids and inorganic acids, or salts thereof. Examples of the organic acid include organic sulfonic acids such as alkane sulfonic acid, alkanol sulfonic acid, and aromatic sulfonic acid, and aliphatic carboxylic acids. Inorganic acids include borohydrofluoric acid, silicohydrofluoric acid, and sulfamine. Acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and the like can be mentioned. The salts include alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, sulfonates, and the like. The component (B) is preferably an organic sulfonic acid from the viewpoint of the solubility of the metal salt and the ease of wastewater treatment.

As the alkanesulfonic acid, those represented by the chemical formula C _n H _{2n + 1} SO ₃ H (for example, n = 1 to 5, preferably 1 to 3) can be used. Specifically, methanesulfonic acid, ethane In addition to sulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid, and the like, hexanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, and the like can be given.

As the alkanol sulfonic acid, those represented by the chemical formula C _p H _{2p + 1} —CH (OH) —C _q H _2q —SO ₃ H (for example, p = 0 to 6, q = 1 to 5) can be used. Specifically, in addition to 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid, 2-hydroxybutane-1-sulfonic acid, 2-hydroxypentane-1-sulfonic acid, etc. -Hydroxypropane-2-sulfonic acid, 3-hydroxypropane-1-sulfonic acid, 4-hydroxybutane-1-sulfonic acid, 2-hydroxyhexane-1-sulfonic acid, 2-hydroxydecane-1-sulfonic acid, 2 -Hydroxydodecane-1-sulfonic acid and the like.

The aromatic sulfonic acid is basically benzene sulfonic acid, alkylbenzene sulfonic acid, phenol sulfonic acid, naphthalene sulfonic acid, alkyl naphthalene sulfonic acid, etc., specifically, 1-naphthalene sulfonic acid, 2-naphthalene. Examples include sulfonic acid, toluenesulfonic acid, xylenesulfonic acid, p-phenolsulfonic acid, cresolsulfonic acid, sulfosalicylic acid, nitrobenzenesulfonic acid, sulfobenzoic acid, diphenylamine-4-sulfonic acid, and the like.

Examples of the aliphatic carboxylic acid include acetic acid, propionic acid, butyric acid, citric acid, tartaric acid, gluconic acid, sulfosuccinic acid, and trifluoroacetic acid.

The amine surfactant (C1) contained in the additive (C) of the present invention is a polyoxyethylene alkylamine represented by the following general formula (1).

However, in the formula (1), x is 12 to 18, and y is 4 to 12.

The nonionic surfactant (C2 or C3) contained in the additive (C) of the present invention is a condensate of polyoxyethylene and polyoxypropylene represented by the following general formula (2) or general formula (3) It is.

However, in the formula (2), m is 15 to 30, and n1 + n2 is 40 to 50.

However, in the formula (3), m1 + m2 is 15 to 30, and n is 40 to 50.

The plating solution of the present invention preferably further contains two or more of other surfactants, complexing agents, brighteners and antioxidants other than those described above as other additives.

Examples of other surfactants in this case include ordinary anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants.

Examples of anionic surfactants include polyoxyethylene (ethylene oxide: containing 12 mol) nonyl ether sulfate polyoxyalkylene alkyl ether sulfate such as sodium sulfate, polyoxyethylene (ethylene oxide: containing 12 mol) dodecyl phenyl ether sodium sulfate, etc. Polyoxyalkylene alkylphenyl ether sulfates, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, naphthol sulfonates such as 1-naphthol-4-sulfonic acid sodium, 2-naphthol-3,6-disulfonic acid disodium salt (Poly) alkylnaphthalene sulfonates such as sodium diisopropyl naphthalene sulfonate, sodium dibutyl naphthalene sulfonate, sodium dodecyl sulfate, sodium oleyl sulfate Alkyl sulfates such as Um like.

Cationic surfactants include mono-trialkylamine salts, dimethyldialkylammonium salts, trimethylalkylammonium salts, dodecyltrimethylammonium salts, hexadecyltrimethylammonium salts, octadecyltrimethylammonium salts, dodecyldimethylammonium salts, octadecenyl Dimethylethylammonium salt, dodecyldimethylbenzylammonium salt, hexadecyldimethylbenzylammonium salt, octadecyldimethylbenzylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt, hexadecylpyridinium salt, dodecylpyridinium salt, dodecylpicolinium salt, dodecylimidazo Linium salt, oleylimidazolinium salt, octadecylamine acetate DOO, and the like dodecylamine acetate.

Nonionic surfactants include sugar ester, fatty acid ester, C ₁ -C ₂₅ alkoxyl phosphoric acid (salt), sorbitan ester, silicon-based polyoxyethylene ether, silicon-based polyoxyethylene ester, fluorine-based polyoxyethylene ether, Examples thereof include a sulfated or sulfonated adduct of a condensation product of fluorine-based polyoxyethylene ester, ethylene oxide and / or propylene oxide and alkylamine or diamine.

Examples of amphoteric surfactants include betaine, carboxybetaine, imidazolinium betaine, sulfobetaine, and aminocarboxylic acid.

The above complexing agent is used to stabilize noble metal ions in a bath with a plating solution containing a noble metal such as silver and to make the composition of the deposited alloy uniform. Examples of the complexing agent include oxycarboxylic acid, polycarboxylic acid, and monocarboxylic acid. Specifically, gluconic acid, citric acid, glucoheptonic acid, gluconolactone, glucoheptlactone, formic acid, acetic acid, propionic acid, butyric acid, ascorbic acid, oxalic acid, malonic acid, succinic acid, glycolic acid, malic acid, Tartaric acid, diglycolic acid, thioglycolic acid, thiodiglycolic acid, thioglycol, thiodiglycol, mercaptosuccinic acid, 3,6-dithia-1,8-octanediol, 3,6,9-trithiadecane-1,11 -Disulfonic acid, thiobis (dodecaethylene glycol), di (6-methylbenzothiazolyl) disulfide trisulfonic acid, di (6-chlorobenzothiazolyl) disulfide disulfonic acid, gluconic acid, citric acid, glucoheptonic acid, gluco Nolactone, glucoheptlactone, dithiodianiline, dipyridyl dis Fido, mercaptosuccinic acid, sulfite, thiosulfate, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), iminodipropionic acid (IDP), Hydroxyethyl ethylenediamine triacetic acid (HEDTA), triethylenetetramine hexaacetic acid (TTHA), ethylenedioxybis (ethylamine) -N, N, N ', N'-tetraacetic acid, glycines, nitrilotrimethylphosphonic acid, or these Examples include salt. Further, there are sulfur-containing compounds such as thioureas and phosphorus compounds such as tris (3-hydroxypropyl) phosphine. Examples of the conductive salt include sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, sodium salt of sulfonic acid, potassium salt, magnesium salt, ammonium salt, and amine salt.

The above brightener is used to give the plating film gloss. Brighteners include benzaldehyde, o-chlorobenzaldehyde, 2,4,6-trichlorobenzaldehyde, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde, furfural, 1-naphthaldehyde, 2-naphthaldehyde, 2- Various aldehydes such as hydroxy-1-naphthaldehyde, 3-acenaphthaldehyde, benzylideneacetone, pyridideneacetone, furfuryldenacetone, cinnamaldehyde, anisaldehyde, salicylaldehyde, crotonaldehyde, acrolein, glutaraldehyde, paraaldehyde, vanillin , Triazine, imidazole, indole, quinoline, 2-vinylpyridine, aniline, phenanthroline, neocuproine, picolinic acid, thiourea 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 benzothiazole, 2-mercaptobenzobenzothiazole, 2-methylbenzothiazole, 2-aminobenzo Thiazole, 2-amino-6-methoxybenzothiazole, 2-methyl-5-chlorobenzothiazole, 2-hydroxybenzothiazole, 2-amino-6-methylbenzothiazole, - chlorobenzothiazole, 2,5-dimethyl benzothiazole, benzothiazole such as 5-hydroxy-2-methyl-benzothiazole.

The above antioxidant is used to prevent oxidation of soluble stannous salt to stannic salt. Antioxidants include hypophosphorous acids, ascorbic acid or a salt thereof, phenolsulfonic acid (Na), cresolsulfonic acid (Na), hydroquinonesulfonic acid (Na), hydroquinone, α or β-naphthol, catechol, Examples include resorcin, phloroglucin, hydrazine, phenolsulfonic acid, catecholsulfonic acid, hydroxybenzenesulfonic acid, naphtholsulfonic acid, and salts thereof.

The content of the amine surfactant (C1) of the present invention in the plating solution is 1 to 10 g / L, preferably 3 to 5 g / L. If the content is less than the appropriate range, the effect of suppressing Sn ions is weak. If the amount is too large, the effect of suppressing the precipitation of Sn ions at a low current density is further reduced, and the bump height may be nonuniform.

The content of the nonionic surfactant (C2 and / or C3) of the present invention in the plating solution is 1 to 10 g / L, preferably 1 to 5 g / L. If the content is less than the appropriate range, the effect of suppressing Sn ions is weak. On the other hand, if the amount is too large, the depletion of Sn ions in the vicinity of the surface to be plated is further promoted, and plating defects such as dendrites may occur. When both the nonionic surfactant (C2) and the nonionic surfactant (C3) are contained, the total content of the nonionic surfactant (C2) and the nonionic surfactant (C3) is within the above range. It is better to be inside. The total content of both the amine surfactant (C1) and the nonionic surfactant (C2 and / or C3) in the plating solution is 1 to 10 g / L, preferably 1 to 5 g / L. L.

The predetermined soluble metal salt (A) can be used alone or in combination, and its content in the plating solution is 30 to 100 g / L, preferably 40 to 60 g / L. When the content is less than the appropriate range, productivity is lowered, and when the content is increased, the cost of the plating solution is increased.

The inorganic acid, organic acid or salt thereof (B) can be used alone or in combination, and the content in the plating solution is 80 to 300 g / L, preferably 100 to 200 g / L. If the content is less than the appropriate range, the electrical conductivity is low and the voltage is increased. If the content is increased, the viscosity of the plating solution is increased and the stirring speed of the plating solution is decreased.

It should be noted that the concentration of each of the above components (A) to (C) is arbitrarily adjusted and selected according to the plating method such as barrel plating, rack plating, high-speed continuous plating, rackless plating, and bump plating.

On the other hand, the temperature of the electroplating solution of the present invention is generally 70 ° C. or lower, preferably 10 to 40 ° C. The current density at the time of forming a plating film by electroplating is in the range of 0.1 A / dm ^{2 to} 100 A / dm ² , preferably in the range of 0.5 A / dm ^{2 to} 20 A / dm ² . If the current density is too low, the productivity deteriorates, and if it is too high, the bump height uniformity deteriorates.

A tin or tin alloy plating solution containing both the amine-based surfactant (C1) and the nonionic surfactant (C2 and / or C3) of the present invention as an additive is applied to an electronic component that is an object to be plated. A predetermined metal film can be formed on the electronic component. Examples of the electronic component include a printed board, a flexible printed board, a film carrier, a semiconductor integrated circuit, a resistor, a capacitor, a filter, an inductor, a thermistor, a crystal resonator, a switch, and a lead wire. Further, a coating can be formed by applying the plating solution of the present invention to a part of an electronic component such as a bump of a wafer.

Next, examples of the present invention will be described in detail together with comparative examples.

(Amine surfactant (C1) and nonionic surfactant (C2 or C3) used in Examples and Comparative Examples)
Amine surfactants used in Examples 1-1 to 1-15, Examples 2-1 to 2-12, Comparative Examples 1-1 to 1-11, and Comparative Examples 2-1 to 2-13 (C1 Table 1 shows the structural formulas of polyoxyethylene alkylamines (C1-1 to C1-11).

Nonionic surfactants (C2) used in Examples 1-1 to 1-15, Examples 2-1 to 2-12, Comparative Examples 1-1 to 1-11, and Comparative Examples 2-1 to 2-13 Or the condensate of polyoxyethylene and polyoxypropylene which is C3) is represented by the general formula (2) or the general formula (3) described above. Table 2 shows m, n1 + n2 and molecular weight in the structural formulas (C2-1 to C2-10) of the condensate represented by the general formula (2). Table 3 shows m1 + m2, n and molecular weight in the structural formulas (C3-1 to C3-10) of the condensate represented by the general formula (3). In formula (2) and formula (3), m represents the number of ethylene oxide (EO) groups, and n represents the number of propylene oxide (PO) groups.

(Building bath of Sn plating solution)
<Example 1-1>
After mixing methanesulfonic acid as a free acid and catechol as an antioxidant into a methanesulfonic acid Sn aqueous solution to form a uniform solution, the polyoxyethylene of No. C1-3 above is further used as a surfactant. Condensation of alkylamine (mass average molecular weight: 800) and No. C2-4 polyoxyethylene and polyoxypropylene (mass average molecular weight: 3100, EO group of polyalkylene oxide group: PO group (molar ratio) = 15 : 40) was added. And finally ion-exchange water was added and the Sn plating liquid of the following composition was constructed. The methanesulfonic acid Sn aqueous solution was prepared by electrolyzing a metal Sn plate in a methanesulfonic acid aqueous solution.

(Composition of Sn plating solution)
Methanesulfonic acid Sn (as Sn ²⁺ ): 80 g / L
Methanesulfonic acid (as free acid): 150 g / L
Catechol: 1g / L
Amine-based surfactant C1-3: 5 g / L
Nonionic surfactant C2-4: 5 g / L
Ion-exchange water: balance

<Examples 1-6 to 1-10, Examples 2-1, 2-2, 2-5 to 2-8, 2-11, 2-12, Comparative Examples 1-2, 1-3, 1-5 1-6, 1-9 to 1-11, Comparative Examples 2-1, 2-3 to 2-5, 2-7, 2-9 to 2-11, 2-13>
Examples 1-6 to 1-10, Examples 2-1, 2-2, 2-5 to 2-8, 2-11, 2-12, Comparative Examples 1-2, 1-3, 1-5, In 1-6, 1-9 to 1-11, Comparative Examples 2-1, 2-3 to 2-5, 2-7, 2-9 to 2-11, and 2-13, amine surfactants (C1 ) And nonionic surfactants (C2 or C3), surfactants having properties shown in Tables 1 to 3 were used. Other than that was carried out similarly to Example 1, and bathed the Sn plating solution of the said Example and the said comparative example. In Comparative Example 1-11, the amine surfactant (C1) was not used. In Comparative Example 2-13, the nonionic surfactant (C2 and / or C3) was not used.

(Building bath of SnAg plating solution)
<Example 1-2>
In a methanesulfonic acid Sn aqueous solution, methanesulfonic acid as a free acid, catechol as an antioxidant, thiourea as a complexing agent, and benzaldehyde as a brightener are mixed and dissolved, and further methanesulfonic acid Ag solution And mixed. After mixing to a uniform solution, the polyoxyethylene alkylamine (No. C1-4) (mass average molecular weight: 1300) as a surfactant and a condensate of polyoxyethylene and polyoxypropylene (C2-4) (Mass average molecular weight: 3100, EO group of polyalkylene oxide group: PO group (molar ratio) = 15: 40) was added. And finally, ion-exchange water was added and the SnAg plating solution of the following composition was constructed. In addition, the methanesulfonic acid Sn aqueous solution was prepared by electrolyzing a metal Sn plate, and the methanesulfonic acid Ag aqueous solution was electrolyzed in a methanesulfonic acid aqueous solution, respectively.

(Composition of SnAg plating solution)
Methanesulfonic acid Sn (as Sn ²⁺ ): 80 g / L
Methanesulfonic acid Ag (as Ag ⁺ ): 1.0 g / L
Methanesulfonic acid (as free acid): 150 g / L
Catechol: 1g / L
Thiourea: 2 g / L
Benzaldehyde: 0.01 g / L
Amine surfactant C1-4: 3 g / L
Nonionic surfactant C2-4: 4 g / L
Ion-exchange water: balance

<Examples 1-4, 1-11, 1-13, 1-15, Examples 2-3, 2-9, Comparative Examples 1-1, 1-4, 1-8, Comparative Examples 2-6, 2 -12>
Examples 1-4, 1-11, 1-13, 1-15, Examples 1-6, 2-12, Comparative Examples 1-1, 1-4, 1-8, Comparative Examples 2-6, 2- In No. 12, surfactants having the properties shown in Tables 1 to 3 were used as surfactants. Other than that, the SnAg plating solutions of the above examples and comparative examples were constructed in the same manner as in Example 1-2.

(Building bath of SnCu plating solution)
<Example 1-3>
Methanesulfonic acid as a free acid, catechol as an antioxidant, and thiourea as a complexing agent were mixed and dissolved in a methanesulfonic acid Sn aqueous solution, and then further added with methanesulfonic acid Cu liquid and mixed. . After a uniform solution is obtained by mixing, the polyoxyethylene alkylamine (No. C1-6) (mass average molecular weight: 650) as a surfactant and the condensate of polyoxyethylene and polyoxypropylene of C2-4 are used. (Mass average molecular weight: 3100, EO group of polyalkylene oxide group: PO group (molar ratio) = 15: 40) was added. And finally, ion-exchange water was added and the SnCu plating solution of the following composition was constructed. The methanesulfonic acid Sn aqueous solution was prepared by electrolysis of a metal Sn plate, and the methanesulfonic acid Cu aqueous solution was prepared by electrolysis of a metal Cu plate in a methanesulfonic acid aqueous solution.

(Composition of SnCu plating solution)
Methanesulfonic acid Sn (as Sn ²⁺ ): 80 g / L
Methanesulfonic acid Cu (as Cu ²⁺ ): 0.5 g / L
Methanesulfonic acid (as free acid): 150 g / L
Catechol: 1g / L
Thiourea: 2 g / L
Amine-based surfactant C1-6: 3 g / L
Nonionic surfactant C2-4: 3 g / L
Ion-exchange water: balance

<Examples 1-5, 1-12, 1-14, Examples 2-4, 2-10, Comparative Example 1-7, Comparative Examples 2-2, 2-8>
In Examples 1-5, 1-12, 1-14, Examples 2-4, 2-10, Comparative Examples 1-7, and Comparative Examples 2-2, 2-8, Tables 1 to A surfactant having the properties shown in 3 was used. Other than that was carried out similarly to Example 1-3, and the SnCu plating solution of the said Example and the said comparative example was constructed.

<Example 3-1>
After mixing methanesulfonic acid as a free acid and catechol as an antioxidant into a methanesulfonic acid Sn aqueous solution to form a uniform solution, the polyoxyethylene of No. C1-4 as a surfactant is further added. Alkylamine (mass average molecular weight: 1300) and condensate of C2-4 polyoxyethylene and polyoxypropylene (mass average molecular weight: 3100, EO group of polyalkylene oxide group: PO group (molar ratio) = 15: 40) and a condensate of C3-4 polyoxyethylene and polyoxypropylene (mass average molecular weight: 3100, EO group of polyalkylene oxide group: PO group (molar ratio) = 15: 40). And finally ion-exchange water was added and the Sn plating liquid of the following composition was constructed. The methanesulfonic acid Sn aqueous solution was prepared by electrolyzing a metal Sn plate in a methanesulfonic acid aqueous solution.

(Composition of Sn plating solution)
Methanesulfonic acid Sn (as Sn ²⁺ ): 80 g / L
Methanesulfonic acid (as free acid): 150 g / L
Catechol: 1g / L
Amine-based surfactant C1-3: 5 g / L
Nonionic surfactant C2-4: 3 g / L
Nonionic surfactant C3-4: 2 g / L
Ion-exchange water: balance

<Example 3-2>
In a methanesulfonic acid Sn aqueous solution, methanesulfonic acid as a free acid, catechol as an antioxidant, thiourea as a complexing agent, and benzaldehyde as a brightener are mixed and dissolved, and further methanesulfonic acid Ag solution And mixed. After a uniform solution is obtained by mixing, the polyoxyethylene alkylamine (No. C1-4) (mass average molecular weight: 1300) as a surfactant and a condensate of polyoxyethylene and polyoxypropylene (C2-6) are used. (Mass average molecular weight: 3400, EO group of polyalkylene oxide group: PO group (molar ratio) = 20: 40) and a condensate of C3-7 polyoxyethylene and polyoxypropylene (mass average molecular weight: 3800, EO group of polyalkylene oxide group: PO group (molar ratio) = 30: 40) was added. And finally, ion-exchange water was added and the SnAg plating solution of the following composition was constructed. In addition, the methanesulfonic acid Sn aqueous solution was prepared by electrolyzing a metal Sn plate, and the methanesulfonic acid Ag aqueous solution was electrolyzed in a methanesulfonic acid aqueous solution, respectively.

(Composition of SnAg plating solution)
Methanesulfonic acid Sn (as Sn ²⁺ ): 80 g / L
Methanesulfonic acid Ag (as Ag ⁺ ): 1.0 g / L
Methanesulfonic acid (as free acid): 150 g / L
Catechol: 1g / L
Thiourea: 2 g / L
Benzaldehyde: 0.01 g / L
Amine surfactant C1-4: 3 g / L
Nonionic surfactant C2-6: 2 g / L
Nonionic surfactant C3-7: 2 g / L
Ion-exchange water: balance

<Comparison test and evaluation>
Examples 1-1 to 1-15, Examples 2-1 to 2-12, Comparative Examples 1-1 to 1-11, Comparative Examples 2-1 to 2-13, and Examples 3-1 to 3-2 A plating film (bump) is formed using the three types of plating baths, and the uniformity of the thickness of the plating film inside the die (WID) and the ease of occurrence of voids during the reflow process. evaluated. The results are shown in Tables 4-6.

(1) Uniformity of plating film thickness inside die (WID) A seed layer for electrical conduction of 0.1 μm titanium and 0.3 μm copper is formed on the surface of a wafer (8 inches) by sputtering, and the seed layer A dry film resist (film thickness 50 μm) was laminated on the substrate. Next, the dry film resist was partially exposed through an exposure mask, and then developed. Thus, as shown in FIG. 1, a resist layer 3 having a pattern in which openings 2 having a diameter of 90 μm are formed on the surface of the wafer 1 at different pitch intervals of a: 150 μm, b: 225 μm, and c: 375 μm. Formed.

The wafer 1 on which the resist layer 3 is formed is immersed in a plating apparatus (dip-type paddle stirring apparatus), and the resist is respectively subjected to three conditions: a plating solution temperature: 25 ° C., a current density: 4 ASD, 8 ASD, and 12 ASD. The opening 2 of layer 3 was plated. Next, the wafer 1 was taken out of the plating apparatus, washed and dried, and then the resist layer 3 was peeled off using an organic solvent. In this way, a bumped wafer was produced in which bumps having a diameter of 90 μm were formed in a single die in a pattern in which 150 μm, 225 μm, and 375 μm were arranged at different pitch intervals. The height of the bumps on the wafer was measured using an automatic visual inspection apparatus. From the measured bump height, the uniformity of the plating film thickness inside the die (WID) was calculated by the following formula. The results are shown in the “WID” column of Table 1.
WID = (maximum height-minimum height) / (2 × average height) × 100
When the current density is 4 ASD, the WID is 5 or less, the current density is 8 ASD, the WID is 15 or less, and the current density is 12 ASD, the WID is 20 or less, respectively. The standard was uniform thickness.

(2) Ease of occurrence of voids After etching and removing the seed layer of the bumped wafer prepared in (1) above when the current density is 12 ASD, the wafer is heated to 240 ° C. using a reflow apparatus. The bumps were melted. After cooling, transmission X-ray images were taken of bumps (2000 in total) arranged at intervals of 150 μm, 225 μm, and 375 μm. The photographed image was visually observed, and when one or more voids having a size of 1% or more with respect to the size of the bump was seen, “NG” was indicated, and when no void was seen, “OK” was designated. . The results are shown in the “Void” column of Tables 4-6.

As is clear from Table 1 and Table 4, in Comparative Example 1-1 and Comparative Example 1-6, y in Formula (1) of the amine surfactant (C1-1) is 2, Since some of the bumps were not seen because they were not within the range, the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform.

In Comparative Example 1-2 and Comparative Example 1-7, y in the formula (1) of the amine surfactant (C1-5) was 40 and was not within the range of 4 to 12, and therefore, from 4 ASD to 12 ASD WID exceeded the standard over the current density range, and the plating film thickness was not uniform. Furthermore, voids were also generated.

In Comparative Example 1-3 and Comparative Example 1-8, y in formula (1) of the amine surfactant (C1-7) was 40, which was not within the range of 4 to 12, and therefore, from 4 ASD to 12 ASD WID exceeded the standard over the current density range, and the plating film thickness was not uniform. Furthermore, voids were also generated.

In Comparative Example 1-4 and Comparative Example 1-9, y in formula (1) of the amine surfactant (C1-8) was 2 and was not within the range of 4 to 12. However, the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform.

In Comparative Example 1-5 and Comparative Example 1-10, y in formula (1) of the amine surfactant (C1-11) was 40, and it was not within the range of 4 to 12, so that from 4 ASD to 12 ASD WID exceeded the standard over the current density range, and the plating film thickness was not uniform. In Comparative Example 1-5, no void was observed, but in Comparative Example 1-10, a void was also generated.

In Comparative Example 1-11, since the surfactant was only the nonionic surfactant (C3-5), no void was observed in the bumps, and the WID met the standard at the current densities of 4ASD and 8ASD, and the plating film Although the thickness was uniform, the WID exceeded the standard at a current density of 12 ASD, and the plating film thickness was not uniform. That is, the nonionic surfactant (C2 or C3) has a suppressing effect necessary for suppressing the variation in plating height, but the effect of promoting the supply of Sn ions by itself is low. Depletion occurred and WID deteriorated.

As is clear from Table 2 and Table 5, in Comparative Example 2-1, m of the EO group of the formula (2) of the nonionic surfactant (C2-1) is 10 and is within the range of 15-30. In addition, since n1 + n2 of PO group was 30 and was not within the range of 40-50, no void was seen in the bump, but the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness Was not uniform.

In Comparative Example 2-2, n1 + n2 of the PO group of the formula (2) of the nonionic surfactant (C2-2) was 40 and was in the range of 40 to 50, but the m of the EO group was 10. There was no void in the bump because it was not in the range of 15 to 30, but the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform.

In Comparative Example 2-3, m of the EO group of formula (2) of the nonionic surfactant (C2-3) was 15 and was in the range of 15 to 30, but n1 + n2 of the PO group was 30. There was no void in the bump because it was not in the range of 40-50, but the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform.

In Comparative Example 2-4, the n1 + n2 of the PO group of the formula (2) in the nonionic surfactant (C2-8) was 50 and was in the range of 40 to 50, but the m of the EO group was 40. Yes, because it was not in the range of 15 to 30, the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform. Furthermore, voids were also generated.

In Comparative Example 2-5, m of the EO group of the formula (2) of the nonionic surfactant (C2-9) was 30 and was in the range of 15 to 30, but the n1 + n2 of the PO group was 60. Since it was not in the range of 40 to 50, the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform. Furthermore, voids were also generated.

In Comparative Example 2-6, m of the EO group of the formula (2) in the nonionic surfactant (C2-10) is 50, not in the range of 15 to 30, and n1 + n2 of the PO group is 60. , The WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform. Furthermore, voids were also generated.

As is clear from Tables 3 and 5, in Comparative Example 2-7, m1 + m2 of the EO group of the formula (3) of the nonionic surfactant (C3-1) is 10, which falls within the range of 15-30. In addition, since the n of the PO group was 30 and was not in the range of 40 to 50, no void was found in the bump, but the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness Was not uniform.

In Comparative Example 2-8, n of the PO group of the formula (3) in the nonionic surfactant (C3-2) was 40 and was in the range of 40 to 50, but m1 + m2 of the EO group was 10. There was no void in the bump because it was not in the range of 15 to 30, but the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform.

In Comparative Example 2-9, m1 + m2 of the EO group of the formula (3) of the nonionic surfactant (C3-3) was 15 and was in the range of 15 to 30, but n of the PO group was 30. There was no void in the bump because it was not in the range of 40-50, but the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform.

In Comparative Example 2-10, n of the PO group of the formula (3) of the nonionic surfactant (C3-8) was 50 and was in the range of 40 to 50, but m1 + m2 of the EO group was 40. Yes, because it was not in the range of 15 to 30, the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform. Furthermore, voids were also generated.

In Comparative Example 2-11, m1 + m2 of the EO group of the formula (3) of the nonionic surfactant (C3-9) was 30 and was within the range of 15 to 30, but n of the PO group was 60. Since it was not in the range of 40 to 50, the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform. Furthermore, voids were also generated.

In Comparative Example 2-12, m1 + m2 of the EO group of the formula (3) in the nonionic surfactant (C3-10) is 50, not within the range of 15 to 30, and n of the PO group is 60. , The WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was not uniform. Furthermore, voids were also generated.

In Comparative Example 2-13, since the soot surfactant was only the amine surfactant (C1-4), no void was observed, but the WID exceeded the standard over the current density range from 4 ASD to 12 ASD, and plating was performed. The film thickness was not uniform. That is, the amine-based surfactant (C1) has an effect of promoting the supply of Sn ions, but the suppression effect necessary for suppressing the variation in plating height cannot be obtained by itself, and the WID was high.

On the other hand, as is clear from Tables 4 to 6, in Examples 1-1 to 1-15, Examples 2-1 to 2-12, and Examples 3-1 to 3-2, X in the formula (1) of the activator (C1-3), (C1-4), (C1-6), (C1-9), (C1-10) is in the range of 12-18, and y is It is within the range of 4 to 12, and nonionic surfactants (C2-4), (C2-2), (C2-5), (C2-6), (C2-7), (C3-4) , (C3-5), (C3-6), and (C3-7) EO group: PO group (molar ratio) m: n1 + n2 or m1 + m2: n was in the range of 15-30: 40-50 Voids were not seen in the bumps, and WID was within the standard over the current density range from 4 ASD to 12 ASD, and the plating film thickness was uniform. That is, by appropriately combining the amine surfactant (C1) and the nonionic surfactant (C2 and / or C3), a good WID and a void-free bump were obtained in a wide current density of 4 to 12 ASD. .

The plating solution of the present invention includes printed circuit boards, flexible printed circuit boards, film carriers, semiconductor integrated circuits, resistors, capacitors, filters, inductors, thermistors, crystal resonators, switches, lead wires and other electronic components, and wafer bumps. It can be used for a part of such electronic components.

Claims

(A) a soluble salt containing at least a stannous salt,
(B) an acid selected from organic acids and inorganic acids or salts thereof,
(C) a plating solution containing an additive,
The additive includes two types of surfactants, an amine surfactant (C1) and a nonionic surfactant (C2 and / or C3),
The amine surfactant (C1) is a polyoxyethylene alkylamine represented by the following general formula (1), and the nonionic surfactant (C2 or C3) is the following general formula (2) or general A plating solution, which is a condensate of polyoxyethylene and polyoxypropylene represented by formula (3).

However, in the formula (1), x is 12 to 18, and y is 4 to 12.

However, in the formula (2), m is 15 to 30, and n1 + n2 is 40 to 50.

However, in the formula (3), m1 + m2 is 15 to 30, and n is 40 to 50.
The additive is a surfactant, complexing agent, brightener and antioxidant other than the two types of surfactants (C1, C2 and / or C3), and two or more other additives are added. The plating solution according to claim 1, further comprising: