TREATMENT METHOD AFTER PLATING WITH Sn OR Sn ALLOY

Abstract

A treatment method is for preventing compound contaminations derived from Sn or an Sn alloy, which have precipitated on members, such as a substrate and a conveyance tool, from accumulating after plating with Sn or the Sn alloy. The method includes washing at least one of the members used in a series of plating treatment steps with an acidic solution immediately after the plating with Sn or the Sn alloy. The acidic solution contains at least one acid or salt thereof having a pH of 5 or lower.

Claims

1. A treatment method after plating with Sn or an Sn alloy, comprising: washing at least one of members used in a series of plating treatment steps with an acidic solution immediately after the plating, the acidic solution containing at least one kind selected from acids and salts thereof and having a pH of 5 or lower.

2. The treatment method according to claim 1, wherein the members are a substrate and a conveyance tool for the substrate, and the washing with the acidic solution is performed in a state where the substrate is fixed to the conveyance tool.

3. The treatment method according to claim 1, wherein the at least one kind selected from acids and salts thereof comprises at least one kind selected from organic acids and salts thereof.

4. The treatment method according to claim 1, wherein a content of the at least one kind selected from acids and salts thereof in the acidic solution is 8 g/L to 700 g/L.

5. The treatment method according to claim 1, wherein the acidic solution contains at least one kind selected from complexing agents and chelate agents.

6. The treatment method according to claim 1, wherein the acidic solution contains at least one kind selected from nonionic surfactants or at least one kind selected from ionic surfactants.

Description

DESCRIPTION OF EMBODIMENTS

[0021] Embodiments of the present invention will be described in detail below. The description of the following preferable embodiments are substantially mere examples and do not intend to limit the present invention, application methods thereof, or uses thereof.

[0022] A treatment method after plating with Sn or an Sn alloy of the present invention includes washing at least one of members used in a series of plating treatment steps with a specific acidic solution immediately after the plating.

[0023] The specific acidic solution used in the treatment method of the present invention is a solution containing at least one kind selected from acids and salts thereof, i.e., the acid and/or the salt thereof, and having a pH of 5 or lower. By performing the washing with such specific acidic solution immediately after the plating, there can be realized easy and effective prevention of accumulation of the precipitated compound contaminations derived from Sn or the Sn alloy, which cannot be realized by conventional washing with water or warm water.

[0024] The acid contained in the acidic solution is not particularly limited. Examples of the acid include: organic acids such as organic sulfonic acids, e.g., methanesulfonic acid, ethanesulfonic acid, 2-propanolsulfonic acid, sulfosuccinic acid and p-phenolsulfonic acid, and carboxylic acids, e.g., acetic acid, formic acid, oxalic acid, tartaric acid, citric acid and glyoxylic acid, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, sulfamic acid, and nitric acid; and salts thereof. These acids can be used alone, or two or more kinds of which can be used simultaneously. Among them, from the viewpoint that the precipitated compound contaminations derived from Sn or the Sn alloy can be more effectively prevented from accumulating, the acid and/or the salt thereof contained in the acidic solution is preferably at least one kind selected from the organic acids and the salts thereof, i.e., at least one kind of the organic acid and/or the salt thereof.

[0025] The pH of the acidic solution is 5 or lower, and preferably 2 or lower. The acidic solution is more preferably a strongly acidic solution having the pH of 1 or lower. When the pH of the acidic solution is higher than the upper limit, the acidic solution has no difference from water or warm water and the precipitated compound contaminations derived from Sn or the Sn alloy cannot be effectively prevented from accumulating.

[0026] A content of the acid and/or the salt thereof in the acidic solution is preferably 8 g/L to 700 g/L, and more preferably 10 g/L to 650 g/L. When the content of the acid and/or the salt thereof is less than the lower limit, there is a possibility that the precipitated compound contaminations derived from Sn or the Sn alloy cannot be effectively prevented from accumulating. When the content of the acid and/or the salt thereof is more than the upper limit, there is a possibility that the acid and/or the salt thereof recrystallizes beyond solubility and thus deposits as new contaminations, and that an acid concentration becomes to be too high and a plated coating film is damaged.

[0027] The acidic solution preferably contains at least one kind selected from complexing agents and chelate agents. i.e., at least one kind of the complexing agent and/or the chelate agent. By washing the members with the acidic solution containing the complexing agent and/or the chelate agent together with the acid and/or the salt thereof, the precipitated compound contaminations derived from Sn or the Sn alloy can be more effectively prevented from accumulating.

[0028] Examples of the complexing agent include gluconic acid, glycine, citric acid, malic acid, glucoheptonic acid, gluconolactone, glucoheptolactone, succinic acid, malonic acid, tartaric acid, oxalic acid, erythorbic acid, sorbic acid, ascorbic acid, pyrophosphoric acid, and a salt thereof.

[0029] Examples of the chelate agent include ethylenediamine, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), iminodipropionic acid (IDP), hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylenetetraminehexaacetic acid (TTHA), 1,3-propanediamine-N,N,N,N-tetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropanol-N,N,N,N-tetraacetic acid (DPTA), N-(2-hydroxyethyl)iminodiacetic acid (HIDA), N,N-bis(2-hydroxyethyl)glycine (DHEG), glycoletherdiaminetetraacetic acid (GEDTA), ethylenediamine-N,N-disuccinic acid (EDDS), and a salt thereof.

[0030] A content of the complexing agent and/or the chelate agent in the acidic solution is preferably 1 g/L to 30 g/L, and more preferably 2 g/L to 25 g/L. When the content of the complexing agent and/or the chelate agent is less than the lower limit, there is a possibility that effect of preventing the precipitated compound contaminations derived from Sn or the Sn alloy from accumulating cannot be satisfactorily improved. When the content of the complexing agent and/or the chelate agent is more than the upper limit, there is a possibility that the complexing agent and/or the chelate agent recrystallizes beyond solubility and thus deposits as new contaminations.

[0031] The acidic solution preferably contains at least one kind selected from nonionic surfactants or at least one kind selected from ionic surfactants, i.e., at least one kind of: the nonionic surfactant; or the ionic surfactant. By washing the members with the acidic solution containing the nonionic surfactant or the ionic surfactant together with the acid and/or the salt thereof, the precipitated compound contaminations derived from Sn or the Sn alloy can be more effectively prevented from accumulating.

[0032] Examples of the nonionic surfactant include surfactants obtained by an addition condensation reaction of: C1 to C20 alkanols, phenols, naphthols, bisphenols, C1 to C25 alkyl phenols, arylalkyl phenols, C1 to C25 alkyl naphthols, C1 to C25 alkoxyl phosphoric acids (salts), sorbitan esters, polyalkylene glycols, C1 to C22 aliphatic amides, and the like; with ethylene oxide (EO) and/or propylene oxide (PO).

[0033] Examples of the ionic surfactant include: anionic surfactants such as alkyl sulfates, polyoxyethylene alkylether sulfates, polyoxyethylene alkylphenylether sulfates, alkylbenzene sulfonates, and alkylnaphthalene sulfonates; and cationic surfactants such as mono- to tri-alkylamine salts, dimethyldialkylammonium salts, and trimethylalkylammonium salts.

[0034] A content of the nonionic surfactant or the ionic surfactant in the acidic solution is preferably 1 g/L to 30 g/L, and more preferably 2 g/L to 25 g/L. When the content of the nonionic surfactant or the ionic surfactant is less than the lower limit, there is a possibility that effect of preventing the precipitated compound contaminations derived from Sn or the Sn alloy from accumulating cannot be satisfactorily improved. When the content of the nonionic surfactant or the ionic surfactant is more than the upper limit, there is a possibility that a large amount of the nonionic surfactant or the ionic surfactant depositing on the members remains even after a subsequent washing step and causes adverse effects on subsequent steps.

[0035] The specific acidic solution used in the treatment method of the present invention can optionally contain various kinds of other additives such as a lubricating agent, an antiseptic agent, a defoaming agent, and an antifungal agent, in addition to the acid and/or the salt thereof, the complexing agent and/or the chelate agent, and the nonionic surfactant or the ionic surfactant.

[0036] A preparation method of the acidic solution is not particularly limited. For example, there can be adopted a method in which: the acid and/or the salt thereof is suitably selected, and the complexing agent and/or the chelate agent, the nonionic surfactant or the ionic surfactant, the various kinds of other additives and the like are optionally and suitably selected; the content of each component in the acidic solution is adjusted to, for example, the range mentioned above such that the pH of the acidic solution is within the range mentioned above: and these components are dissolved in distilled water or the like.

[0037] In the treatment method of the present invention, the members to be washed with the acidic solution are at least members used in a series of plating treatment steps with Sn or the Sn alloy, and are not particularly limited. For example, the members to be washed with the acidic solution are members on which the compound contaminations derived from Sn or the Sn alloy may precipitate and accumulate, such as: a substrate such as a wafer; a printed substrate; a conveyance tool for the substrates; a contact part of the substrates; and a nonconductive member for protecting the contact parts. In particular, the precipitated compound contaminations derived from Sn or the Sn alloy easily accumulate on the conveyance tool, and such accumulation cannot be prevented by conventional methods. However, the accumulation can be easily and effectively prevented by the treatment method of the present invention.

[0038] In the treatment method of the present invention, when the members are a substrate such as a wafer, a printed substrate and a conveyance tool for the substrates, the washing with the acidic solution is preferably performed in a state where each substrate is fixed to the conveyance tool. By performing the washing with the acidic solution in a state where the substrate is fixed to the conveyance tool as mentioned above, the compound contaminations derived from Sn or the Sn alloy, which have precipitated on both the conveyance tool and the substrate, can be simultaneously and easily removed. Therefore, for, in particular, the conveyance tool on which the precipitated compound contaminations derived from Sn or the Sn alloy easily accumulate, such accumulation can be effectively prevented.

[0039] A method of washing the members with the acidic solution is not particularly limited. For example, there can be adopted: a method of immersing the members in an acidic solution of about 20 C. to about 60 C. for about 0.5 minutes to about 3 minutes; a method of spraying the acidic solution onto the members; or a method of bringing the members into contact with the acidic solution by using a shower method.

[0040] In the treatment method of the present invention, the members are washed with the acidic solution immediately after the plating with Sn or the Sn alloy, and as mentioned above, after the washing with the acidic solution, the members may be washed with water or warm water and dried.

[0041] Conditions and a method of the washing with water or warm water are not particularly limited. For example, there can be adopted: a method of immersing the members in water of about 20 C. to about 35 C. or warm water of about 35 C. to about 60 C. for about 0.5 minutes to about 3 minutes; a method of spraying water or warm water onto the members as in the case of the washing with the acidic solution, or a method of bringing the members into contact with water or warm water by using a shower method as in the case of the washing with the acidic solution.

[0042] Conditions and a method of the drying are not particularly limited. For example, a method of drying the members at about 20 C. to about 150 C. with cold air, warm air, or compressed air can be adopted.

[0043] In the present invention, the series of plating treatment steps with Sn or the Sn alloy is not particularly limited, and steps of general plating treatment can be adopted. An Sn plating bath used in the plating may be a bath containing at least a soluble tin salt which is, for example, a tin salt of an organic sulfonic acid such as methanesulfonic acid, ethanesulfonic acid, 2-propanolsulfonic acid, sulfosuccinic acid, or p-phenolsulfonic acid, and optionally containing: an acid and a salt thereof; and various kinds of additives such as an antioxidizing agent, a stabilizing agent, a complexing agent, a surfactant, a brightener, a lubricating agent, a pH adjuster, a conductive salt, and an antiseptic agent. An Sn alloy plating bath used in the plating may be the Sn plating bath further containing soluble metal salts such as a soluble silver salt, a soluble copper salt, a soluble bismuth salt, and a soluble indium salt. The plating may be electroplating or electroless plating, and conditions for each plating are not particularly limited.

EXAMPLES

[0044] Examples for explaining the treatment method after the plating with Sn or the Sn alloy of the present invention in detail and comparative examples are shown below.

Reference Example

(1) Reference Example 1: Sn Plating

[0045] An Sn electroplating bath having the following composition was initially made. Plating conditions are also shown.

[Plating Bath Composition]

[0046] Stannous methanesulfonate (as Sn.sup.2+): 60 g/L

[0047] Methanesulfonic acid (as free acid): 150 g/L

[0048] 1-(2-Dimethylaminoethyl)-5-mercaptotetrazole: 2 g/L

[0049] 3,6-Dithiaoctane-1,8-diol: 2 g/L

[0050] Bisphenol A polyethoxylate (EO: 13 moles): 10 g/L

[0051] Catechol: 5 g/L

[Plating Conditions]

[0052] Bath temperature: 30 C.

[0053] Cathode current density: 1.0 A/dm.sup.2

[0054] Plating time: about 1800 seconds

(2) Reference Example 2: SnAg Alloy Plating

[0055] An SnAg alloy electroplating bath having the following composition was initially made. Plating conditions are also shown.

[Plating Bath Composition]

[0056] Stannous methanesulfonate (as Sn.sup.2+): 60 g/L

[0057] Silver methanesulfonate (as Ag.sup.+): 0.8 g/L

[0058] Methanesulfonic acid (as free acid): 150 g/L

[0059] 1-(2-Dimethylaminoethyl)-5-mercaptotetrazole: 2 g/L

[0060] 3,6-Dithiaoctane-1,8-diol: 2 g/L

[0061] Bisphenol A polyethoxylate (EO: 13 moles): 10 g/L

[0062] Catechol: 5 g/L

[Plating Conditions]

[0063] Bath temperature: 30 C.

[0064] Cathode current density: 1.0 A/dm.sup.2

[0065] Plating time: about 1800 seconds

Example and Comparative Example

(1) Example 1

[0066] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0067] Methanesulfonic acid: 100 g/L

[0068] pH: 1 or lower

[Steps]

[0069] Step 1: Fixing a wafer onto a conveyance tool

[0070] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0071] Step 3: Plating (Reference Example 1)

[0072] Step 4: Washing with the acidic solution (25 C., immersion for 1 minute)

[0073] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0074] Step 6: Drying (60 C., for 0.5 minutes)

[0075] Step 7: Detaching the wafer from the conveyance tool

(2) Example 2

[0076] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0077] Methanesulfonic acid: 100 g/L

[0078] Gluconic acid: 5 g/L

[0079] pH: 1 or lower

[Steps]

[0080] Step 1: Fixing a wafer onto a conveyance tool

[0081] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0082] Step 3: Plating (Reference Example 1)

[0083] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0084] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0085] Step 6: Drying (60 C., for 0.5 minutes)

[0086] Step 7: Detaching the wafer from the conveyance tool

(3) Example 3

[0087] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0088] Methanesulfonic acid: 100 g/L

[0089] Glycine: 10 g/L

[0090] pH: 1 or lower

[Steps]

[0091] Step 1: Fixing a wafer onto a conveyance tool

[0092] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0093] Step 3: Plating (Reference Example 1)

[0094] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0095] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0096] Step 6: Drying (60 C., for 0.5 minutes)

[0097] Step 7: Detaching the wafer from the conveyance tool

(4) Example 4

[0098] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0099] Methanesulfonic acid: 100 g/L

[0100] Citric acid: 20 g/L

[0101] pH: 1 or lower

[Steps]

[0102] Step 1: Fixing a wafer onto a conveyance tool

[0103] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0104] Step 3: Plating (Reference Example 1)

[0105] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0106] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0107] Step 6: Drying (60 C., for 0.5 minutes)

[0108] Step 7: Detaching the wafer from the conveyance tool

(5) Example 5

[0109] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0110] Methanesulfonic acid: 100 g/L

[0111] EDTA: 8 g/L

[0112] pH: 1 or lower

[Steps]

[0113] Step 1: Fixing a wafer onto a conveyance tool

[0114] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0115] Step 3: Plating (Reference Example 1)

[0116] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0117] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0118] Step 6: Drying (60 C., for 0.5 minutes)

[0119] Step 7: Detaching the wafer from the conveyance tool

(6) Example 6

[0120] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0121] Methanesulfonic acid: 250 g/L

[0122] pH: 1 or lower

[Steps]

[0123] Step 1: Fixing a wafer onto a conveyance tool

[0124] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0125] Step 3: Plating (Reference Example 1)

[0126] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0127] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0128] Step 6: Drying (60 C., for 0.5 minutes)

[0129] Step 7; Detaching the wafer from the conveyance tool

(7) Example 7

[0130] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0131] Methanesulfonic acid: 500 g/L

[0132] pH: 1 or lower

[Steps]

[0133] Step 1: Fixing a wafer onto a conveyance tool

[0134] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0135] Step 3: Plating (Reference Example 1)

[0136] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0137] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0138] Step 6: Drying (60 C., for 0.5 minutes)

[0139] Step 7: Detaching the wafer from the conveyance tool

(8) Example 8

[0140] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0141] Methanesulfonic acid: 100 g/L

[0142] Sodium gluconate: 10 g/L

[0143] pH: 1 or lower

[Steps]

[0144] Step 1: Fixing a wafer onto a conveyance tool

[0145] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0146] Step 3: Plating (Reference Example 1)

[0147] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0148] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0149] Step 6: Drying (60 C., for 0.5 minutes)

[0150] Step 7: Detaching the wafer from the conveyance tool

(9) Example 9

[0151] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0152] Methanesulfonic acid: 100 g/L

[0153] Sodium malate: 10 g/L

[0154] pH: 1 or lower

[Steps]

[0155] Step 1: Fixing a wafer onto a conveyance tool

[0156] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0157] Step 3: Plating (Reference Example 1)

[0158] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0159] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0160] Step 6: Drying (60 C., for 0.5 minutes)

[0161] Step 7: Detaching the wafer from the conveyance tool

(10) Example 10

[0162] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0163] Methanesulfonic acid: 100 g/L

[0164] NTA: 10 g/L

[0165] pH: 1 or lower

[Steps]

[0166] Step 1: Fixing a wafer onto a conveyance tool

[0167] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0168] Step 3: Plating (Reference Example 1)

[0169] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0170] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0171] Step 6: Drying (60 C., for 0.5 minutes)

[0172] Step 7: Detaching the wafer from the conveyance tool

(11) Example 11

[0173] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0174] Methanesulfonic acid: 100 g/L

[0175] pH: 1 or lower

[Steps]

[0176] Step 1: Fixing a wafer onto a conveyance tool

[0177] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0178] Step 3: Plating (Reference Example 2)

[0179] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0180] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0181] Step 6: Drying (60 C., for 0.5 minutes)

[0182] Step 7: Detaching the wafer from the conveyance tool

(12) Example 12

[0183] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0184] Methanesulfonic acid: 600 g/L

[0185] Polyvinylpyrrolidone: 20 g/L

[0186] pH: 1 or lower

[Steps]

[0187] Step 1: Fixing a wafer onto a conveyance tool

[0188] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0189] Step 3: Plating (Reference Example 2)

[0190] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0191] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0192] Step 6: Drying (60 C., for 0.5 minutes)

[0193] Step 7: Detaching the wafer from the conveyance tool

(13) Example 13

[0194] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0195] Methanesulfonic acid: 10 g/L

[0196] Polyethylene glycol (average molecular weight: 1000): 20 g/L

[0197] EDTA: 20 g/L

[0198] pH: 1 or lower

[Steps]

[0199] Step 1: Fixing a wafer onto a conveyance tool

[0200] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0201] Step 3: Plating (Reference Example 2)

[0202] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0203] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0204] Step 6: Drying (60 C., for 0.5 minutes)

[0205] Step 7; Detaching the wafer from the conveyance tool

(14) Example 14

[0206] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0207] Sulfuric acid: 100 g/L

[0208] pH: 1 or lower

[Steps]

[0209] Step 1: Fixing a wafer onto a conveyance tool

[0210] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0211] Step 3: Plating (Reference Example 1)

[0212] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0213] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0214] Step 6: Drying (60 C., for 0.5 minutes)

[0215] Step 7: Detaching the wafer from the conveyance tool

(15) Example 15

[0216] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0217] Sulfuric acid: 100 g/L

[0218] EDTA: 20 g/L

[0219] pH: 1 or lower

[Steps]

[0220] Step 1: Fixing a wafer onto a conveyance tool

[0221] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0222] Step 3: Plating (Reference Example 1)

[0223] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0224] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0225] Step 6: Drying (60 C., for 0.5 minutes)

[0226] Step 7: Detaching the wafer from the conveyance tool

(16) Example 16

[0227] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0228] Methanesulfonic acid: 100 g/L

[0229] Alkyl dimethylaminopropyl amide: 10 g/L

[0230] pH: 1 or lower

[Steps]

[0231] Step 1: Fixing a wafer onto a conveyance tool

[0232] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0233] Step 3: Plating (Reference Example 1)

[0234] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0235] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0236] Step 6: Drying (60 C., for 0.5 minutes)

[0237] Step 7; Detaching the wafer from the conveyance tool

(17) Example 17

[0238] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0239] Methanesulfonic acid: 100 g/L

[0240] Benzalkonium chloride: 5 g/L

[0241] Gluconic acid: 10 g/L

[0242] pH: 1 or lower

[Steps]

[0243] Step 1: Fixing a wafer onto a conveyance tool

[0244] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0245] Step 3: Plating (Reference Example 1)

[0246] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0247] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0248] Step 6: Drying (60 C., for 0.5 minutes)

[0249] Step 7: Detaching the wafer from the conveyance tool

(18) Example 18

[0250] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 7 was repeated 30 times.

[Acidic Solution Composition]

[0251] Sodium methanesulfonate: 100 g/L

[0252] Methanesulfonic acid: 5 g/L

[0253] Gluconic acid: 10 g/L

[0254] pH: 3.5

[Steps]

[0255] Step 1: Fixing a wafer onto a conveyance tool

[0256] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0257] Step 3: Plating (Reference Example 1)

[0258] Step 4: Washing with the acidic solution (50 C., immersion for 1 minute)

[0259] Step 5: Washing with warm water (50 C., immersion for 0.5 minutes)

[0260] Step 6: Drying (60 C., for 0.5 minutes)

[0261] Step 7: Detaching the wafer from the conveyance tool

(19) Comparative Example 1

[0262] A series of the following step 1 to step 6 was repeated 30 times.

[Steps]

[0263] Step 1: Fixing a wafer onto a conveyance tool

[0264] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0265] Step 3: Plating (Reference Example 1)

[0266] Step 4: Washing with water (25 C. immersion for 1 minute)

[0267] Step 5: Drying (60 C., for 1 minute)

[0268] Step 6: Detaching the wafer from the conveyance tool

(20) Comparative Example 2

[0269] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 8 was repeated 30 times.

[Acidic Solution Composition]

[0270] Methanesulfonic acid: 100 g/L

[0271] pH: 1 or lower

[Steps]

[0272] Step 1: Fixing a wafer onto a conveyance tool

[0273] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0274] Step 3: Plating (Reference Example 1)

[0275] Step 4: Washing with water (25 C., immersion for 0.5 minutes)

[0276] Step 5: Washing with the acidic solution (50 C., immersion for 1 minute)

[0277] Step 6: Washing with water (25 C., immersion for 0.5 minutes)

[0278] Step 7: Drying (60 C., for 0.5 minutes)

[0279] Step 8: Detaching the wafer from the conveyance tool

(21) Comparative Example 3

[0280] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 9 was repeated 30 times.

[Acidic Solution Composition]

[0281] Methanesulfonic acid: 100 g/L

[0282] pH: 1 or lower

[Steps]

[0283] Step 1: Fixing a wafer onto a conveyance tool

[0284] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0285] Step 3: Plating (Reference Example 1)

[0286] Step 4: Washing with water (25 C. immersion for 0.5 minutes)

[0287] Step 5: Drying (60 C., for 0.5 minutes)

[0288] Step 6: Detaching the wafer from the conveyance tool

[0289] Step 7: Washing with the acidic solution (50 C., immersion for 1 minute)

[0290] Step 8: Washing with water (25 C., immersion for 0.5 minutes)

[0291] Step 9: Drying (60 C. for 0.5 minutes)

(22) Comparative Example 4

[0292] An acidic solution having the following composition was prepared. Then, a series of the following step 1 to step 8 was repeated 30 times.

[Acidic Solution Composition]

[0293] Methanesulfonic acid: 100 g/L

[0294] pH: 1 or lower

[Steps]

[0295] Step 1: Fixing a wafer onto a conveyance tool

[0296] Step 2: Washing with water (room temperature of 20 C. to 30 C., immersion for 0.5 minutes)

[0297] Step 3: Plating (Reference Example 2)

[0298] Step 4: Washing with water (25 C., immersion for 0.5 minutes)

[0299] Step 5: Washing with the acidic solution (50 C., immersion for 1 minute)

[0300] Step 6: Washing with water (25 C., immersion for 0.5 minutes)

[0301] Step 7: Drying (60 C., for 0.5 minutes)

[0302] Step 8: Detaching the wafer from the conveyance tool

Test Example

[0303] A surface of each conveyance tool after the steps in Examples 1 to 18 and Comparative Examples 1 to 4 was observed by using Field Emission Scanning Electron Microscope (FE-SEM, magnification of 50K, S-4800, commercially available from Hitachi High-Tech Corporation). After an area thus observed was divided into 45 squares, a surface coverage of the conveyance tool with the compound contaminations derived from Sn or the Sn alloy was obtained in accordance with the following equation, and prevention of accumulation of the compound contaminations was evaluated. The results are shown in Table 1.

Surface coverage (%)=(Number of squares to which contamination particles have adhered/Total number of squares)100

TABLE-US-00001 TABLE 1 Surface coverage (%) Example 1 30 Example 2 0 Example 3 0 Example 4 10 Example 5 15 Example 6 30 Example 7 30 Example 8 5 Example 9 5 Example 10 15 Example 11 30 Example 12 5 Example 13 5 Example 14 30 Example 15 5 Example 16 0 Example 17 0 Example 18 30 Comparative Example 1 100 Comparative Example 2 100 Comparative Example 3 100 Comparative Example 4 100

[0304] As shown in Table 1, the wafer and the conveyance tool in each of Examples 1 to 18 were washed with the acidic solution containing the acid immediately after the plating with Sn or the Sn alloy in accordance with the treatment method of the present invention. In each of Examples 1 to 18, even after the plating and the washing with the acidic solution were repeated 30 times, the surface coverage of the conveyance tool with the compound contaminations derived from Sn or the Sn alloy was as low as 0% to 30%, and the compound contaminations were thus satisfactorily prevented from accumulating.

[0305] On the other hand, in Comparative Examples 1 to 4, the washing with the acidic solution was not performed (Comparative Example 1), or the washing with the acidic solution was performed not immediately after the plating with Sn or the Sn alloy but: immediately after the washing with water (Comparative Examples 2 and 4); or after the washing with water and the drying (Comparative Example 3). Therefore, the compound contaminations derived from Sn or the Sn alloy accumulated on the entire surface of each conveyance tool.

[0306] Like Example 1 in which the washing was performed with the acidic solution containing only the organic acid, also in each of Examples 2 to 5, 8 to 10 and 18 in which the washing was performed with the acidic solution containing the complexing agent and/or the chelate agent in addition to the organic acid, the surface coverage of the conveyance tool with the compound contaminations derived from Sn was as low as 0% to 30%, and the compound contaminations were thus satisfactorily prevented from accumulating.

[0307] As compared with Example 1 in which the washing was performed with the acidic solution containing only the organic acid, in each of: Example 16 in which the washing was performed with the acidic solution containing the surfactant in addition to the organic acid: and Example 17 in which the washing was performed with the acidic solution containing the complexing agent and the surfactant in addition to the organic acid, the surface coverage of the conveyance tool with the compound contaminations derived from Sn was 0%, and the compound contaminations were thus completely prevented from accumulating.

[0308] Also when the plating with the SnAg alloy was performed as in Examples 11 to 13, by performing the washing with: the acidic solution containing only the organic acid (Example 11); the acidic solution containing the surfactant in addition to the organic acid (Example 12); or the acidic solution containing the complexing agent and the surfactant in addition to the organic acid (Example 13), immediately after the plating, the surface coverage of the conveyance tool with the compound contaminations derived from the SnAg alloy was as low as 5% to 30%, and the compound contaminations were thus satisfactorily prevented from accumulating.

[0309] As in Examples 14 to 15, also when the washing was performed with: the acidic solution containing only the inorganic acid (Example 14); or the acidic solution containing the complexing agent in addition to the inorganic acid (Example 15), immediately after the plating, the surface coverage of the conveyance tool with the compound contaminations derived from Sn was as low as 5% to 30%, and the compound contaminations were thus satisfactorily prevented from accumulating.

INDUSTRIAL APPLICABILITY

[0310] The treatment method after plating with Sn or an Sn alloy of the present invention can easily and effectively prevent compound contaminations derived from Sn or the Sn alloy, which have precipitated on a substrate, a conveyance tool and the like, from accumulating. Therefore, the treatment method of the present invention can be suitably used in a series of plating treatment steps with Sn or the Sn alloy.