JPWO2007086454A1 - Additive for electrolytic copper plating solution using phosphorous copper as anode, electrolytic copper plating solution and electrolytic copper plating method - Google Patents

Abstract

The present invention is characterized by containing an additive for an electrolytic copper plating solution having phosphorous copper containing at least one component selected from the group consisting of alkenes and alkynes as an anode, and the above-mentioned additive. An electrolytic copper plating solution for performing electrolysis using phosphorous copper as an anode is provided. The additive for electrolytic copper plating of the present invention can suppress the generation of anode sludge even when electrolytic treatment is continuously performed in an electrolytic copper plating solution using phosphorus-containing copper as an anode. It is also effective in suppressing alteration.

Description

  The present invention relates to an additive for an electrolytic copper plating solution containing phosphorous copper as an anode, an electrolytic copper plating solution containing the additive, and an electrolytic copper plating method.

  Conventionally, in a copper sulfate plating solution, a soluble anode capable of supplying the copper component into the plating solution by dissolving the anode itself and an insoluble anode in which the anode itself is not dissolved are used as the anode for electrolytic plating.

  Of these, when using an insoluble anode, it is necessary to compensate for the decrease in copper ions associated with the electrolytic treatment by replenishment. However, since the solubility of the copper salt in the copper sulfate plating solution is not good, copper is usually used. A copper dissolution treatment tank or the like for dissolving the salt is separately provided. Moreover, insoluble anodes are more expensive than soluble anodes.

  For this reason, soluble anodes are widely used in copper sulfate plating solutions. As a soluble anode, an anode made of oxygen-free copper and an anode made of phosphorous copper are known. Among these, when an anode made of oxygen-free copper is used, when electrolytic treatment is performed, a large amount of monovalent copper is generated on the anode surface, which causes sludge.

  On the other hand, when phosphorous copper containing about 0.02 to 0.06% of phosphorus is added to copper as an anode, a black film made of CuCl2, Cu2O, Cu3P, or the like, a so-called black film is formed on the anode surface. Thereby, generation | occurrence | production of monovalent copper is suppressed and formation of sludge is prevented.

  However, even when phosphorus-containing copper is used as the anode, anode sludge may accumulate after long-term continuous electrolytic treatment. This anode sludge is considered to be generated by the dropping of the black film on the surface of the phosphorous copper or the production of monovalent copper generated on the anode surface as the black film is dropped. When such anode sludge is generated, the sludge accumulates in the lower part of the anode bag installed covering the anode, and the conductivity of the lower part of the anode is obstructed. It becomes the cause that the variation of becomes large. Normally, when sludge is formed in the copper sulfate plating solution, this removal is performed manually, causing a decrease in productivity and an increase in cost.

  In recent years, in order to cope with such a problem, removal of anode sludge by improving the plating apparatus has been studied (Patent Document 1 below). However, since this method requires a large-scale apparatus, it is economical. Is not preferable. In addition, there is a report that the anode sludge is dissolved by adding chloride ions to the electroplating solution (Patent Document 2 below). However, when the concentration of chloride ions is high, no cuprous chloride is present on the anode surface. Since a conductor film is formed and poor conduction occurs, a sufficient effect is not obtained.

  As described above, when phosphorous copper is used as the anode, the generation of monovalent copper during electrolysis is suppressed, but the phosphorous copper anode is left immersed in the copper sulfate plating solution. It is known that monovalent copper is formed on the anode surface. The monovalent copper produced on the anode surface has the effect of reducing the brightener contained in the copper sulfate plating solution, and the brightener component altered by the reduction is reduced in throwing power and via filling properties. Cause deterioration of the In particular, in the case of using a copper sulfate plating solution for the purpose of via filling, it has been reported that the embedding property is remarkably lowered even by the presence of a small amount of monovalent copper, and it is desired to suppress the alteration of Brightner. .

In recent years, various studies have been conducted on methods for suppressing the alteration of Brightner, and it has been reported that, for example, the alteration of Brightner is suppressed by performing air agitation on the anode side ( Patent Document 3). However, this method requires improvement of the electrolyzer, which causes an increase in cost.
JP 2005-76100 A JP 2005-256120 A JP 2004-332094

  The present invention has been made in view of the current state of the prior art described above, and its main object is to provide an anode even when electrolytic treatment is continuously performed in an electrolytic copper plating solution using phosphorous copper as an anode. It is an object to provide an additive for electrolytic copper plating that can suppress the generation of sludge and is also effective in suppressing the alteration of the brightener component.

  As a result of earnest research to achieve the above-mentioned object, the present inventor has added at least one component selected from the group consisting of alkenes and alkynes to the electrolytic copper plating solution, thereby containing phosphorous copper-containing copper. It has been found that even when electrolysis is carried out continuously for a long period of time using anode as an anode, the generation of anode sludge can be suppressed, and further, the alteration of the brightener component can also be suppressed.

That is, the present invention provides an additive for an electrolytic copper plating solution having the following phosphorous copper as an anode, an electrolytic copper plating solution, and an electrolytic copper plating method.
1. An additive for an electrolytic copper plating solution having phosphorous copper containing at least one component selected from the group consisting of alkenes and alkynes as an anode.
2. Alkenes are represented by the following general formula (I):

(Wherein R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom, a lower alkyl group, a hydroxyl group, a carboxyl group, a group: —SO ₃ M ¹ (wherein M ¹ is a hydrogen atom or an alkali metal) ), Group: —CONH ₂ , or group: —COOR (wherein R is a lower alkyl group which may have a hydroxyl group as a substituent), and the lower alkyl group includes a hydroxyl group, a carboxyl group, and a group: -SO ₃ M ¹ (wherein M ¹ may have at least one substituent selected from the group consisting of a hydrogen atom or an alkali metal).
Alkynes are represented by the following general formula (II):

(Wherein R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a lower alkyl group, a hydroxyl group, a carboxyl group, an alkoxy group which may have a substituent, a group: —NR ⁷ ₂ (provided that R ⁷ is a hydrogen atom or a lower alkyl group), group: —SO ₃ M ¹ (where M ¹ is a hydrogen atom or an alkali metal), or group: — (O (CH ₂ ) _n ) _m —OH Wherein n is 2 or 3, and m is an integer of 1 to 5, and the lower alkyl group is a carboxyl group, a hydroxyl group, an alkoxy group that may have a substituent, a group: —NR ⁷ ₂ ( Where R ⁷ is a hydrogen atom or a lower alkyl group), a group: — (O (CH ₂ ) _n ) _m —OH (where n is 2 or 3, m is an integer of 1 to 5), and groups: _-SO 3 ^{M 1} (where, ^{M 1} is a hydrogen atom or an alkali And an addition for an electrolytic copper plating solution using the phosphorous copper according to Item 1 as an anode, which is a compound represented by (1), which may have at least one substituent selected from the group consisting of: Agent.
3. An electrolytic copper plating solution having a basic plating bath with an aqueous solution containing at least one acid component selected from copper ions and organic acids and inorganic acids as essential components,
An electrolytic copper plating solution for electrolysis using phosphorous-containing copper as an anode, comprising the additive according to item 1 or 2.
4). The basic plating bath is (i) at least one acid component selected from copper ions, (ii) organic acids and inorganic acids, (iii) chloride ions, and (iv) nonionic polyether polymer surfactants. And (v) the electrolytic copper plating solution according to item 3, which is an aqueous solution containing a sulfur-containing organic compound.
5. The basic plating bath is (i) at least one acid component selected from copper ions, (ii) organic acids and inorganic acids, (iii) chloride ions, and (iv) nonionic polyether polymer surfactants. Item 4. The electrolytic copper plating solution according to Item 3, which is an aqueous solution containing (v) a sulfur-containing organic compound and (vi) a nitrogen-containing compound.
6). The electrolytic copper plating solution according to any one of Items 3 to 5, which contains 1 mg / L to 100 g / L of the additive according to Item 1 or 2.
7). 7. An electrolytic copper plating method, wherein the electrolytic copper plating solution according to any one of items 3 to 6 is subjected to electrolytic treatment using phosphorous copper as an anode and an object to be plated as a cathode.

  The additive for electrolytic copper plating of the present invention comprises at least one selected from the group consisting of alkenes and alkynes. According to the electrolytic copper plating solution containing such an additive, generation of anode sludge can be greatly suppressed even when electrolytic treatment is continuously performed for a long time using phosphorous copper, which is a soluble anode, as an anode. As a result, the sludge removal work can be reduced, and furthermore, the anode sludge can be prevented from accumulating in the anode bag installed around the phosphorous-containing copper anode, resulting from a decrease in the conductivity of the lower part of the anode due to the accumulated sludge. Variations in plating film thickness can be prevented.

  Moreover, the said additive can suppress the quality change of a brightener component, when performing an electrolytic process using a phosphorous copper anode. For this reason, problems associated with the alteration of the brightener during long-term electrolysis, such as a decrease in throwing power and a decrease in via filling properties, can be greatly reduced.

  Although there is no limitation in particular about alkenes used as an additive, in particular the following general formula (I):

(Wherein R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom, a lower alkyl group, a hydroxyl group, a carboxyl group, a group: —SO ₃ M ¹ (wherein M ¹ is a hydrogen atom or an alkali metal) ), A group: —CONH ₂ , or a group: —COOR (R is a lower alkyl group which may have a hydroxyl group as a substituent), and the alkyl group includes a hydroxyl group, a carboxyl group, and a group: —SO _3. A compound represented by M ¹ (wherein M ¹ may have at least one substituent selected from the group consisting of a hydrogen atom or an alkali metal) is preferable.

  The alkynes are not particularly limited, but in particular, the following general formula (II):

(Wherein R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a lower alkyl group, a hydroxyl group, a carboxyl group, an alkoxy group which may have a substituent, a group: —NR ⁷ ₂ (provided that R ⁷ is a hydrogen atom or a lower alkyl group), group: —SO ₃ M ¹ (where M ¹ is a hydrogen atom or an alkali metal), or group: — (O (CH ₂ ) _n ) _m —OH Wherein n is 2 or 3, and m is an integer of 1 to 5, and the lower alkyl group is a carboxyl group, a hydroxyl group, an alkoxy group that may have a substituent, a group: —NR ⁷ ₂ ( Where R ⁷ is a hydrogen atom or a lower alkyl group), a group: — (O (CH ₂ ) _n ) _m —OH (where n is 2 or 3, m is an integer of 1 to 5), and groups: _-SO 3 ^{M 1} (where, ^{M 1} is a hydrogen atom or an alkali May have at least one substituent selected from the group consisting of a is) genus.) Is a compound represented by the preferred.

  In the above general formulas (I) and (II), the lower alkyl group is preferably a linear or branched alkyl group having about 1 to 5 carbon atoms, and specific examples thereof include methyl, ethyl, propyl , Isopropyl, butyl, isobutyl, tert-butyl, pentyl and the like.

Moreover, as an alkoxy group which may have a substituent in general formula (II), a C1-C5 alkoxy group is preferable. The alkoxy group may have one or two or more substituents selected from the group consisting of a hydroxyl group and —SO ₃ M ¹ (where M ¹ is a hydrogen atom or an alkali metal).

In the present invention, among the above alkenes and alkynes, alkenes having at least one water-soluble functional group such as hydroxyl group, carboxyl group, group: —SO ₃ M ¹ , group: —CONH ₂ ; , Alkynes having at least one water-soluble functional group such as carboxyl group, group: —NR ⁷ ₂ , group: —SO ₃ M ¹ , and the like are preferable.

With respect to specific examples of alkenes used in the present invention, compound names and chemical formulas are shown in Tables 1 and 2 below.

Moreover, about the specific example of alkynes, a compound name and chemical formula are described in Table 3 and Table 4 below.

  The above alkenes and alkynes can be used singly or in combination of two or more.

  The concentration of the additive consisting of at least one component selected from the group consisting of the alkenes and alkynes in the electrolytic copper plating solution is not particularly limited, but is usually about 1 mg / L to 100 g / L. Preferably, it is more preferably about 10 mg / L to 10 g / L.

  The additive of the present invention is used as an additive for an electrolytic copper plating solution having phosphorous copper as an anode.

  The phosphorous copper used as the anode is not particularly limited as long as it is usually used as an anode material for electrolytic copper plating. For example, phosphorus-containing copper having a phosphorus content of about 0.02 to 0.06% by weight can be used. There is no particular limitation on the shape of the anode, and various shapes of anodes such as a rod shape, a spherical shape, and a plate shape can be used.

  There are no particular limitations on the type of electrolytic copper plating solution that serves as a basic bath using the additive of the present invention, and it contains at least one acid component selected from copper ions and organic and inorganic acids as an essential component. A copper plating solution can be used.

  As the copper ion source, any copper compound that is soluble in the plating solution can be used without particular limitation. Specific examples of such a copper compound include copper sulfate, copper oxide, copper chloride, copper carbonate, copper pyrophosphate, alkane sulfonate copper, alkanol sulfonate copper, and organic acid copper. A copper compound can be used individually by 1 type or in mixture of 2 or more types.

  Although there is no limitation in particular about copper ion concentration, For example, it can be set as the range of about 10-80 g / L.

  As the acid component, at least one selected from the group consisting of organic acids and inorganic acids can be used. Specific examples of organic acids include alkane sulfonic acids such as methane sulfonic acid, alkanol sulfonic acids, and the like, and specific examples of inorganic acids include sulfuric acid and the like. These acid components can be used singly or in combination of two or more. Although there is no limitation in particular about the density | concentration of an acid component, For example, it can be set as about 20-400 g / L.

  The acidic electrolytic copper plating solution contains chloride ions. The concentration may usually be about 2 to 100 mg / L. In order to obtain such a concentration range, the chloride ion concentration in the plating solution may be adjusted using hydrochloric acid, sodium chloride, or the like, if necessary.

  Further, the acidic electrolytic copper plating solution usually contains a nonionic polyether polymer surfactant, a sulfur-containing organic compound, or the like as an additive. Furthermore, a nitrogen-containing organic compound or the like may be added in order to further improve the throwing power. These additives may be appropriately selected from known additive components in the electrolytic copper plating solution. For example, the additive mix | blended with the copper sulfate plating solution for through-hole plating, the additive mix | blended with the copper sulfate plating for blind via holes, etc. can be used.

  Among such additives, nonionic polyether polymer surfactants are usually referred to as polymer components, such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polyoxyalkylene glycol, etc. A polyether compound or the like can be used. The concentration of the nonionic polyether polymer surfactant is not particularly limited, but can be, for example, in the range of about 0.01 to 10 g / L.

  The sulfur-containing organic compound is usually called a brightener, and may be appropriately selected from known additive components. For example, sulfur compounds such as 3-mercaptopropanesulfonic acid, its sodium salt, bis (3-sulfopropyl) disulfide, its 2 sodium salt, N, N-dimethyldithiocarbamic acid (3-sulfopropyl) ester, its sodium salt, etc. Can be used. Although there is no limitation in particular about a sulfur-containing organic compound density | concentration, For example, it can be set as the range of about 0.1-200 mg / L. The additive of the present invention comprising at least one component selected from the group consisting of the alkenes and alkynes described above has such a brightener, that is, an action of suppressing the alteration of the sulfur-containing organic compound. . As a result, even when electrolytic treatment is continuously performed for a long period of time, it is possible to suppress a decrease in uniform electrodeposition, a decrease in via filling properties, and the like, and to stably form a good copper plating film for a long period of time. It becomes possible.

  The nitrogen-containing organic compound is usually referred to as a leveler, and it may be used by appropriately selecting from known additive components. For example, nitrogen compounds such as a phenazine compound, a safranine compound, a polyalkyleneimine, a thiourea derivative, and a polyacrylic acid amide can be used. Although there is no limitation in particular about a nitrogen-containing organic compound density | concentration, For example, it can be set as the range of about 0.1-200 mg / L.

The additive of the present invention can obtain a good effect particularly when the basic bath is a copper sulfate plating solution. Hereinafter, specific examples of the composition of the copper sulfate plating solution are shown.
* Copper sulfate plating solution Copper sulfate pentahydrate 20-300 g / L (preferably 50-250 g / L)
Sulfuric acid 20-300 g / L (preferably 50-250 g / L)
Chloride ion 5-100 mg / L (preferably 30-80 mg / L)
In the electrolytic copper plating solution containing the additive of the present invention, the type of the object to be plated is not particularly limited, and any article that has been conventionally subjected to electrolytic copper plating can be used as the object to be plated. For example, a printed wiring board in which one or both of a small-diameter through hole and a blind via hole are formed, a semiconductor wafer in which a submicron groove (trench) used in a damascene process is formed, and the like can be used as an object to be plated. In addition, plastic products used for decorative plating, for example, various resin products such as ABS resin, PC / ABS resin, and nylon resin can also be used as objects to be plated.

  In the case of performing the plating treatment using the electrolytic copper plating solution containing the additive of the present invention, the pretreatment method is not particularly limited and may be followed by a conventional method. For example, when using a printed wiring board with through-holes or blind via holes as an object to be plated, the object to be plated with electroless copper plating generally used in printed circuit board production is degreased by conventional methods. After removing dirt and the like attached in the previous step, pickling is performed to remove and activate the oxide film, and then the substrate is immersed in the plating solution of the present invention for electrolysis. Also, when plastic products are to be plated, electrolytic copper plating may be performed after forming a conductive film by electroless copper plating or the like according to a conventional method.

The electrolytic conditions (plating conditions) are not particularly limited. For example, by setting the cathode current density to a range of about 0.1 to 10 A / dm ² , good uniform electrodeposition, via filling properties, etc. can be exhibited. it can. About the liquid temperature of a plating solution, what is necessary is usually just about 10-40 degreeC.

  The method for stirring the plating solution is not particularly limited, and air stirring, jet stirring, and the like can be performed.

  As described above, the electrolytic copper plating solution containing the additive of the present invention can suppress the generation of anode sludge when electrolytic treatment is continuously performed using phosphorous copper as an anode. As a result, the anode removal work can be reduced, and further, the anode sludge can be prevented from accumulating in the anode bag placed over the phosphorous copper anode, and the plating film caused by the decrease in the conductivity of the anode lower part due to the anode sludge. Thickness variation can be prevented.

  Furthermore, the electrolytic copper plating solution containing the additive of the present invention can suppress alteration of the brightener component due to monovalent copper that occurs when phosphorous copper is immersed in the electrolytic copper plating solution for a long time. As a result, it is possible to form a stable plating film with good via filling, uniform electrodeposition, etc. for a long period of time by greatly reducing degradation of uniform electrodeposition and via filling due to Brightener alteration. .

Sectional drawing of the measurement part of the filling rate in Examples 1-6. Sectional drawing of the measurement part of the uniform electrodeposition property in Examples 7-12. The schematic of the anode part of the electrolytic cell used in Examples 13-18.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Examples 1 to 6 and Comparative Example 1
Each of the additives shown in Tables 5 and 6 was added to an electrolytic copper plating solution having the following basic composition to prepare an electrolytic copper plating solution.
* Electrolytic copper plating solution composition Copper sulfate: 220 g / L
Sulfuric acid: 60 g / L
Chloride ion: 50 mg / L
Additive: Top Lucina α-M ^{* 1} 4.5ml / L
Top Lucina α-2 ^{* 2} 1ml / L
Top Lucina α-3 ^{* 3} 3ml / L
* 1: Trademark name, polymer surfactant-containing additive (polymer component), manufactured by Okuno Pharmaceutical Co., Ltd.
* 2: Trade name, sulfur-containing organic compound-containing additive (Brightner), manufactured by Okuno Pharmaceutical Co., Ltd.
* 3: Trade name, nitrogen-containing organic compound-containing additive (leveler), manufactured by Okuno Pharmaceutical Co., Ltd.

An anode made of phosphorous copper was immersed in each of these electrolytic copper plating solutions and allowed to stand for 1 day. Thereafter, a substrate having a large number of vias having a diameter of 100 μm and a depth of 60 μm and having an electroless copper plating film having a thickness of 1 μm formed on the entire surface is used as an object to be plated, and this is used as a degreasing solution (trade name: DP-320 Clean). After immersing in Okuno Pharmaceutical Co., Ltd. (100 ml / L aqueous solution) at 45 ° C. for 5 minutes, washing with water for 1 minute and immersing in 100 g / L dilute sulfuric acid for 1 minute, copper plating treatment was performed under the following plating conditions. It went for 2 hours.
* Plating conditions Anode current density: 0.5 A / dm ²
Cathode current density: 1 A / dm ²
Liquid temperature: 25 ° C
Stirring: Air stirring (cathode side)
Cathode: Substrate Anode: Phosphorus copper (phosphorus content 0.043% by weight)
After the electrolytic copper plating treatment was completed, the cross section of the via portion of the object to be plated was observed to evaluate the via portion embeddability. As an evaluation method, as shown in FIG. 1, the filling rate was obtained by the following formula using the thickness from the via bottom to the plating surface as the total thickness and the plating thickness of the via portion as the filling amount.
Filling rate (%) = (embedding amount / total thickness) × 100
In addition, the filling rate was calculated | required with the same method also about the electrolytic copper plating solution before immersing a phosphorus-containing copper anode. The results are shown in Tables 5 and 6 below.

  As is clear from the above results, according to the electrolytic copper plating solutions of Examples 1 to 6 containing alkenes or alkynes as additives, when the electrolytic treatment was performed after immersing the phosphorous-containing copper anode for one day. Also, a good filling rate was obtained in the same manner as before the immersion of the phosphorous copper.

  On the other hand, when using the electrolytic copper plating solution of Comparative Example 1 that does not contain alkenes and alkynes, the via filling properties were significantly reduced in the plating solution after dipping the phosphorous copper anode.

  From these results, it can be seen that the plating solutions of Examples 1 to 6 can maintain the good via filling property by suppressing the alteration of the brightener.

Examples 7-12 and Comparative Example 2
Each of the additives shown in Tables 7 and 8 was added to an electrolytic copper plating solution having the following basic composition to prepare an electrolytic copper plating solution.
* Electrolytic copper plating solution composition Copper sulfate: 60 g / L
Sulfuric acid: 200 g / L
Chloride ion: 50 mg / L
Additive: Top Lucina SF Base R ^{* 4} 5.0ml / L
Top Lucina SF-B ^{* 5} 1.0ml / L
Top Lucina SF Leveler ^{* 6} 5.0ml / L
* 4: Trademark name, polymer surfactant-containing additive (polymer component), manufactured by Okuno Pharmaceutical Co., Ltd.
* 5: Trade name, sulfur-containing organic compound-containing additive (Brightener), manufactured by Okuno Pharmaceutical Co., Ltd.
* 6: Trade name, nitrogen-containing organic compound-containing additive (leveler), manufactured by Okuno Pharmaceutical Co., Ltd.

An anode made of phosphorous copper was immersed in each of these electrolytic copper plating solutions and left for 1 day. Thereafter, a substrate having a number of through-holes having a diameter of 1.6 mm and a depth of 0.3 mm and having an electroless copper plating film having a thickness of 1 μm formed on the entire surface is used as an object to be plated. : DP-320 Clean (Okuno Pharmaceutical Co., Ltd., 100ml / L aqueous solution) immersed at 45 ° C for 5 minutes, washed with water for 1 minute, immersed in 100g / L dilute sulfuric acid for 1 minute, and under the following plating conditions Electrolytic copper plating was performed to form a copper plating film having a thickness of 25 μm.
* Plating conditions Anode current density: 1.5 A / dm ²
Cathode current density: 3 A / dm ²
Liquid temperature: 25 ° C
Stirring: Air stirring (cathode)
Cathode: Substrate Anode: Phosphorus copper (phosphorus content 0.043% by weight)
After completion of the electrolytic copper plating, the plating thickness at the location shown in FIG. 2 was measured for the through-hole portion of the object to be plated, and the uniform electrodeposition was calculated from the following formula to evaluate the uniform electrodeposition. Fig. 2 is a cross-sectional view of the through-hole part, where (1), (2), (3) and (4) are the surface plating thickness, and (5) and (6) are the inner surface of the through-hole. The plating thickness.

Uniform electrodeposition (%) = {((5) + (6)) ÷ 2} ÷ {((1) + (2) + (3) + (4)) ÷ 4} x 100
In addition, also about the electrolytic copper plating solution before immersing a phosphorus containing copper anode, the uniform electrodeposition was evaluated by the same method. The results are shown in Tables 7 and 8 below.

  As is apparent from the above results, according to the electrolytic copper plating solutions of Examples 7 to 12 containing alkenes or alkynes as additives, when electrolytic treatment was performed after the phosphorous copper anode was immersed for one day. In addition, it was possible to maintain good throwing power as before the immersion of the phosphorous copper.

  On the other hand, in the case of using the electrolytic copper plating solution of Comparative Example 2 that does not contain alkenes and alkynes, the throwing power of the plating solution after dipping the phosphorous copper anode was greatly reduced.

  From these results, according to the plating solutions of Examples 7 to 12, it is clear that the quality of brightener can be suppressed and good throwing power can be maintained.

Examples 13 to 18 and Comparative Example 3
Each of the additives shown in Tables 9 and 10 was added to an electrolytic copper plating solution having the following basic composition to prepare an electrolytic copper plating solution.
* Electrolytic copper plating solution composition Copper sulfate: 70 g / L
Sulfuric acid: 200 g / L
Chloride ion: 50 mg / L
Additive: Top Lucina SF Base R ^{* 4} 5.0ml / L
Top Lucina SF-B ^{* 5} 1.0ml / L
Top Lucina SF Leveler ^{* 6} 5.0ml / L
These electrolytic copper plating solutions were subjected to long-term continuous electrolytic treatment under the following conditions. As the anode, as shown in FIG. 3, an anode case containing spherical phosphorous copper having a diameter of 45 mm and covered with an anode bag having a diameter of 50 mm and a length of 100 cm was used.
* Plating conditions Anode current density: 1.5 A / dm ²
Cathode current density: 3 A / dm ²
Liquid temperature: 25 ° C
Stirring: Air stirring (cathode side)
Anode: Phosphorus copper (phosphorus content 0.043% by weight)
Cathode: Substrate A long-term electrolytic treatment was performed under the conditions described above, and the height of sludge deposited in the anode bag was measured every month. The results are shown in Tables 9 and 10 below.

  As is clear from the above results, according to the electrolytic copper plating solutions of Examples 13 to 18 containing alkenes or alkynes as additives, even when electrolytic treatment is performed continuously for a long period of time, anode sludge is not generated. In the case of using the electrolytic copper plating solution of Comparative Example 3 containing no alkenes and alkynes, sludge starts to be generated by continuous electrolysis for 2 months, and after 2 or 3 months, the anode is hardly generated. The bottom of was covered with sludge.

  From this result, it is clear that according to the electrolytic copper plating solutions of Examples 13 to 18, the generation of anode sludge can be suppressed when electrolytic treatment is continuously performed using phosphorous copper as an anode.

Claims (7)

An additive for an electrolytic copper plating solution having phosphorous copper containing at least one component selected from the group consisting of alkenes and alkynes as an anode. Alkenes are represented by the following general formula (I):

(Wherein R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom, a lower alkyl group, a hydroxyl group, a carboxyl group, a group: —SO ₃ M ¹ (wherein M ¹ is a hydrogen atom or an alkali metal) ), Group: —CONH ₂ , or group: —COOR (wherein R is a lower alkyl group which may have a hydroxyl group as a substituent), and the lower alkyl group includes a hydroxyl group, a carboxyl group, and a group: -SO ₃ M ¹ (wherein M ¹ may have at least one substituent selected from the group consisting of a hydrogen atom or an alkali metal).
Alkynes are represented by the following general formula (II):

(Wherein R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a lower alkyl group, a hydroxyl group, a carboxyl group, an alkoxy group which may have a substituent, a group: —NR ⁷ ₂ (provided that R ⁷ is a hydrogen atom or a lower alkyl group), group: —SO ₃ M ¹ (where M ¹ is a hydrogen atom or an alkali metal), or group: — (O (CH ₂ ) _n ) _m —OH Wherein n is 2 or 3, and m is an integer of 1 to 5, and the lower alkyl group is a carboxyl group, a hydroxyl group, an alkoxy group that may have a substituent, a group: —NR ⁷ ₂ ( Where R ⁷ is a hydrogen atom or a lower alkyl group), a group: — (O (CH ₂ ) _n ) _m —OH (where n is 2 or 3, m is an integer of 1 to 5), and groups: _-SO 3 ^{M 1} (where, ^{M 1} is a hydrogen atom or an alkali 2. It may have at least one substituent selected from the group consisting of (a genus), and a compound represented by (2): an addition for an electrolytic copper plating solution using phosphorous-containing copper as an anode according to claim 1. Agent. An electrolytic copper plating solution having a basic plating bath with an aqueous solution containing at least one acid component selected from copper ions and organic acids and inorganic acids as essential components,
An electrolytic copper plating solution for performing electrolysis using phosphorous-containing copper as an anode, comprising the additive according to claim 1. The basic plating bath is (i) at least one acid component selected from copper ions, (ii) organic acids and inorganic acids, (iii) chloride ions, and (iv) nonionic polyether polymer surfactants. And (v) an electrolytic copper plating solution according to claim 3, which is an aqueous solution containing a sulfur-containing organic compound. The basic plating bath is (i) at least one acid component selected from copper ions, (ii) organic acids and inorganic acids, (iii) chloride ions, and (iv) nonionic polyether polymer surfactants. The electrolytic copper plating solution according to claim 3, which is an aqueous solution containing (v) a sulfur-containing organic compound and (vi) a nitrogen-containing compound. The electrolytic copper plating solution of Claim 3 which contains 1 mg / L-100 g / L of the additive of Claim 1. 4. An electrolytic copper plating method, wherein the electrolytic copper plating solution according to claim 3 is subjected to electrolytic treatment using phosphorous copper as an anode and an object to be plated as a cathode.

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