WO2021245766A1 - Intermittent electroplating method - Google Patents

Abstract

The present invention provides technology for improving the filling properties of micropores in intermittent electroplating.　This intermittent electroplating method is for performing intermittent electroplating of a plated object having micropores and includes the use of a plating liquid containing polyvalent metal ions.

Description

Intermittent electroplating method

The present invention relates to an intermittent electroplating method or the like.

In recent years, with the increasing functionality and speed of electronic devices, there is a demand for higher densities in printed wiring boards. The build-up process is indispensable for increasing the density of printed wiring boards, and via filling is an important plating technology. In such a build-up process, conventionally, non-penetrating vias are uniformly plated and then filled with insulating resin or conductive paste to form a circuit, but in this method, vias are placed on the vias. It cannot be formed and deprives the degree of freedom in circuit design. For this reason, in recent years, a method of stacking wiring layers by performing via filling in which the inside of the via hole is filled with plating has been adopted.

On the other hand, the intermittent electroplating method may be adopted from the viewpoint of improving the efficiency of the electroplating process, especially from the viewpoint of efficiently electroplating a long object to be plated. This intermittent plating method is performed using a plurality of plating tanks on a reel-to-reel line, for example, as shown in FIG.

Japanese Unexamined Patent Publication No. 2011-058093

The present inventor is advancing research, and when intermittent electroplating is performed on an object to be plated having micropores such as via holes, the degree of metal precipitation (filling property) in the micropores is remarkably low. I found.

Therefore, it is an object of the present invention to provide a technique for improving the filling property of micropores in intermittent electroplating.

As the present inventor further researches, the deterioration of the filling property in the intermittent electroplating is a phenomenon peculiar to the intermittent plating method, that is, the object to be plated discharged from the plating tank and the object to be plated supplied to the plating tank. It has been found that this is caused by the problem of low current density due to the plating solution slightly adhering to the object (in the case of the embodiment shown in FIG. 1, the plating solution slightly leaking from the side surface of the plating tank). Then, the present inventor has found that the above-mentioned problems can be solved by using a plating solution containing polyvalent metal ions while further researching. The present inventor has completed the present invention as a result of further research based on these findings.

That is, the present invention includes the following aspects.

Item 1. Intermittent electroplating method for objects to be plated with micropores, including the use of a plating solution containing polyvalent metal ions.

Item 2. Item 2. The intermittent electroplating method according to Item 1, wherein the polyvalent metal ion has a valence of 3 or more.

Item 3. At least one of the polyvalent metal ions selected from the group consisting of ^{Fe 3+} , V ⁵⁺ , Mn ⁷⁺ , Mo ⁶⁺ , W ⁶⁺ , Ce ⁴⁺ , Cr ³⁺ , Cr ⁶⁺ , Ti ⁴⁺ , Sn ⁴⁺ , and Co ^3+. Item 1. The intermittent electroplating method according to Item 1 or 2.

Item 4. Item 6. The intermittent electroplating method according to any one of Items 1 to 3, wherein the multivalent metal ion is ^{at least one selected from the group consisting of Fe 3+} and V ^5+.

Item 5. The long object to be plated is continuously supplied to the plating tank on the line, and the discharge of the object to be plated from the plating tank and the supply of the object to be plated to the plating tank are repeated a plurality of times. The intermittent electroplating method according to any one of 4.

Item 6. Item 5. The intermittent electroplating method according to Item 5, wherein the object to be plated passes through a plurality of plating tanks.

Item 7. Item 5. The intermittent electroplating method according to Item 5 or 6, wherein the discharge and the supply are performed on the side surface of the plating tank.

Item 8. The intermittent electroplating method according to any one of Items 5 to 7, which is performed on a reel-to-reel line.

Item 9. Item 6. The intermittent electroplating method according to any one of Items 1 to 8, wherein the micropores are microvias.

Item 10. Item 6. The intermittent electroplating method according to any one of Items 1 to 9, wherein the metal deposited on the object to be plated contains at least one selected from the group consisting of Cu, Ni, and Sn.

Item 11. Item 6. The intermittent electroplating method according to any one of Items 1 to 10, wherein the plating solution further contains an additive for beer filling.

Item 12. A plating solution containing polyvalent metal ions for use in the intermittent electroplating method according to any one of Items 1 to 11.

According to the present invention, it is possible to provide a technique for improving the filling property of micropores in intermittent electroplating, specifically, an intermittent electroplating method, a method for filling micropores, a plating solution, and the like.

A schematic diagram showing an embodiment of the intermittent electroplating method and a current pattern in the electroplating method are shown. It is sectional drawing of the substrate used in Test Example 1-2. It is a graph which shows an example of the electroplating cycle of Test Example 1-3. It is sectional drawing of the via part of the object to be plated after the completion of electroplating which shows the object (the amount of dents) to be measured in the filling property evaluation. It is sectional drawing of the via part of the object to be plated after the completion of electroplating of Example 2 and Comparative Example 3. FIG.

In the present specification, the expressions "contains" and "contains" include the concepts of "contains", "contains", "substantially consists" and "consists only".

In one aspect of the present invention, an intermittent electroplating method for an object to be plated having micropores, which comprises using a plating solution containing a polyvalent metal ion (in the present invention, "intermittently of the present invention". It may be referred to as "electroplating method").

Further, the present invention relates to a plating solution containing polyvalent metal ions for use in the intermittent electroplating method of the present invention in one aspect thereof.

Further, the present invention relates to a micropore filling (via filling) method by intermittent electroplating on an object to be plated having micropores, which comprises using a plating solution containing polyvalent metal ions.

These will be explained below.

The multivalent metal ion is not particularly limited as long as it is a metal ion having a valence of 2 or more.

The valence of the multivalent metal ion is preferably 3 or more. By using a multivalent metal ion having a valence of 3 or more, the filling property of the micropores can be significantly improved. The upper limit of the valence of the multivalent metal ion is not particularly limited, and is, for example, 7, 6, 5, and 4.

Specific examples of the multivalent metal ion include Fe ³⁺ , V ⁵⁺ , Mn ⁷⁺ , Mo ⁶⁺ , W ⁶⁺ , Ce ⁴⁺ , Cr ³⁺ , Cr ⁶⁺ , Ti ⁴⁺ , Sn ⁴⁺ , Co ^{3+ and the} like. Among these, from the viewpoint of the filling property of the micropores, Fe ³⁺ , V ⁵⁺ , Mn ⁷⁺ , Mo ⁶⁺ , W ⁶⁺ , Ce ⁴⁺ , Cr ^{3+ and the} like are preferable. ^{Of these, Fe 3+} and V ⁵⁺ are particularly preferable, and Fe ³⁺ is particularly preferable, from the viewpoint of the filling property of the micropores.

The multivalent metal ion may be one kind alone or a combination of two or more kinds.

A plating solution containing polyvalent metal ions can be obtained by adding a metal compound when preparing the plating solution. Examples of the metal compound used include iron sulfate (III) hydrate / anhydride, iron nitrate (III) nine hydrate, and iron bromide (III) in the case of obtaining a plating solution containing ^{Fe 3+.} ) Anhydrous, ammonium iron citrate, iron (III) citrate hydrate, iron (III) oxide, iron (III) ammonium sulfate hydrate, etc.; for example, when obtaining a plating solution containing ^{V5 +.} Examples thereof include sodium metavanadate, potassium metavanadate, ammonium metavanadate, etc .; in the ^{case of obtaining a plating solution containing Mn 7+,} for example, potassium permanganate, sodium permanganate, etc. may be mentioned; Mo ⁶⁺ containing plating solution may be used. Examples thereof include sodium molybdenate, potassium molybdenate, lithium molybdenate, ^{hexaammonium hexaammonium} tetrahydrate tetrahydrate and the like in the case of obtaining; for example, tungsten (IV) acid in the case of obtaining a plating solution containing W 6+. Examples thereof include sodium dihydrate, sodium metatungstate, potassium tungstate, etc .; in the ^{case of obtaining a plating solution containing Ce4 +,} for example, cerium (IV) nitrate, ammonium sulphate (IV) hydrate / anhydride, etc. , Tetraammonium sulphate cerium (IV) dihydrate and the like; in the ^{case of obtaining a plating solution containing Cr 3+,} for example, chromium sulfate hydrate / anhydride, chromium acetate, potassium chromium sulfate and the like can be mentioned; When ^{obtaining a plating solution containing Cr 6+,} for example, sodium dichromate, potassium dichromate and the like can be mentioned; ^{when obtaining a plating solution containing Ti 4+,} for example, titanyl sulfate and the like can be mentioned; Sn ⁴⁺ containing. ^{In the case of obtaining a plating solution containing Co 3+,} for example, sodium nitrate trihydrate and the like can be mentioned; and in the case of obtaining a plating solution containing Co 3+, for example, hexaammine cobalt (III) chloride and the like can be mentioned.

Among these metal compounds, iron sulfate (III) hydrate / anhydride, iron nitrate (III) nine hydrate, iron bromide (III) anhydrous, and quen are particularly preferable from the viewpoint of the filling property of micropores. Examples thereof include iron ammonium acid, iron (III) citrate hydrate, iron (III) oxide, iron (III) sulfate hydrate, sodium metavanadate, potassium metavanadate, ammonium metavanadate, and the like, and more preferably sulfuric acid. Iron (III) hydrate / anhydride, iron nitrate (III) nine hydrate, iron bromide (III) anhydrous, iron ammonium citrate, iron (III) citrate hydrate, iron oxide (III), Examples thereof include iron (III) sulfate hydrate and the like, and particularly preferably iron (III) sulfate hydrate and anhydride.

The polyvalent metal ion contained in the plating solution may have a valence changed in the plating solution after the addition of the metal compound (the above metal compound or other metal compound).

The metal compound may be one kind alone or a combination of two or more kinds.

The concentration of the multivalent metal ion in the plating solution is not particularly limited, but is, for example, 0.01 to 20 g / L. The concentration is preferably 0.05 to 10 g / L, more preferably 0.1 to 5 g / L, still more preferably 0.2 to 3 g / L, still more preferably 0, from the viewpoint of the filling property of the micropores. .5 to 3 g / L. The concentration is particularly preferably 0.7 to 2.5 g / L (more preferably 0.9 to 2.2 g / L) from the viewpoint of being able to greatly improve the filling property of the micropores.

In the intermittent plating method of the present invention, the metal deposited on the object to be plated is not particularly limited. Examples of the metal include Cu, Ni, Sn and the like. Of these, Cu is particularly preferred. The metal to be deposited on the object to be plated may be one kind alone or a combination of two or more kinds.

Depending on the metal to be deposited, the plating solution contains other components such as ions of the metal to be deposited and components to be blended as needed. Other components include known electroplating solutions (eg Cu plating solutions (eg copper sulfate baths, bubbling copper baths, copper cyanide baths, copper pyrophosphate baths, etc.), Ni plating solutions (eg compound salt baths, ordinary baths, etc.). , Rotating bath, High sulfate bath, Watt bath, Total chloride bath, Sulfate-chloride bath, Total sulfate bath, High quality bath, Strike nickel bath, Nickel sulfamate bath, Copperified nickel bath, etc.), It can be appropriately set according to or according to the composition of the Sn plating solution (for example, an alkaline bath, a sulfate bath, a sulfonic acid bath, a pyrophosphate bath, a buffalo bath, etc.).

Representatively, the Cu plating solution will be described below. As the Cu plating solution, an acidic copper plating solution containing copper ions and at least one acid component selected from organic acids and inorganic acids as essential components can be used as other components.

As the copper ion source in the acidic copper plating solution, any copper compound 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, copper alkanesulfonate, copper alkanolsulfonate, and organic copper acid. The copper compound may be used alone or in combination of two or more. The concentration of the copper compound in the acidic copper plating solution is not particularly limited, but can be, for example, in the range of about 20 to 280 g / L. The concentration is preferably 100 to 250 g / L, more preferably 150 to 230 g / L.

As the acid component in the acidic copper plating solution, at least one selected from the group consisting of organic acids and inorganic acids can be used. Specific examples of the organic acid include alkane sulfonic acid such as methane sulfonic acid, alkanol sulfonic acid and the like, and specific examples of the inorganic acid include sulfuric acid and the like. These acid components can be used alone or in admixture of two or more. The concentration of the acid component in the acidic copper plating solution is not particularly limited, but may be, for example, about 10 to 400 g / L. The concentration is preferably 40 to 200 g / L, more preferably 70 to 150 g / L.

The acidic copper plating solution preferably contains chloride ions. The concentration may be usually about 10 to 200 mg / L. The concentration is preferably 25 to 100 mg / L, more preferably 40 to 70 mg / L. In order to obtain such a concentration range, the chloride ion concentration in the plating solution may be adjusted by using hydrochloric acid, sodium chloride or the like, if necessary.

The acidic copper plating solution may contain various additives. Among the additives, the beer filling additive is preferable.

The object to be plated is an object to be plated having micropores and is not particularly limited as long as it can be electroplated. Examples of the object to be plated include a substrate having a via hole.

The micropores are preferably microvias. The size of the micropores is, for example, 300 to 5 μm in diameter (preferably 150 to 30 μm) and 150 to 5 μm in depth (preferably 100 to 20 μm). According to the intermittent electroplating method of the present invention, good filling property can be exhibited even for micro vias.

In the intermittent electroplating method of the present invention, it is preferable that the object to be plated is pretreated. The pretreatment method is not particularly limited and may follow a conventional method. For example, a material to be plated that has been subjected to a conductive treatment (for example, electroless plating treatment, carbon treatment, sputtering treatment, Sn-Pd colloidal catalyst treatment, conductive polymer treatment, etc.) is subjected to, for example, degreasing treatment, stains adhering in the previous step. The product obtained through the removal treatment of the above, the removal of the oxide film by pickling, etc. can be used as the object to be plated.

Further, the object to be plated may already have a plating film formed by electroplating.

The intermittent electroplating method of the present invention is a method in which the current addition cycle is repeated intermittently, and the plating solution slightly adhered to the object to be plated discharged from the plating tank and the object to be plated supplied to the plating tank. (In the case of the embodiment shown in FIG. 1, the method is not particularly limited as long as the method causes the problem of generation of low current density due to the plating solution slightly leaking from the side surface of the plating tank).

In the intermittent electroplating method of the present invention, preferably, a long object to be plated is continuously supplied to the plating tank on the line, and the object to be plated is discharged from the plating tank and the object to be plated to the plating tank. Is a method in which the supply of is repeated multiple times.

"A long object to be plated is continuously supplied to the plating tank on the line" means that a plurality of objects to be plated that are separated from each other are not sequentially supplied to the plating tank, but one long object to be plated. It means a mode in which the object to be plated is supplied to the plating tank from one end side of the object to be plated while being conveyed by a roller or the like.

The mode of discharging the object to be plated from the plating tank and supplying the object to be plated to the plating tank is not particularly limited. It is preferable that the discharge and the supply are performed on the side surface of the plating tank. In this case, when the object to be plated is discharged from the side wall of the plating tank and when the object to be plated is supplied through the side wall of the plating tank, the plating solution inside the plating tank passes through the object to be plated. As a result, it leaks to the outside of the plating tank, which causes a problem (generation of low current density) in the present invention.

The number of times the supply and discharge of the object to be plated to the plating tank is repeated is, for example, 2 to 30 times, preferably 5 to 25 times, and more preferably 10 to 20 times.

The intermittent electroplating method of the present invention is preferably a method in which the object to be plated passes through a plurality of plating tanks. The number of plating tanks to pass through is, for example, 2 to 30, preferably 5 to 25, and more preferably 10 to 20.

The intermittent electroplating method of the present invention is preferably a method performed on a reel-to-reel line.

The stirring method of the plating solution is not particularly limited, and air stirring, jet stirring, mechanical stirring, etc. can be performed, and a plurality of stirring methods may be combined.

When performing the plating process, either a soluble anode or an insoluble anode can be used as the anode. For example, as the soluble anode, for example, phosphorus-containing copper having a phosphorus content of about 0.02 to 0.06% can be used. As the insoluble anode, titanium coated with iridium oxide, titanium plated with platinum, or the like can be used. The shape of the anode is not particularly limited, and various shapes such as rod-shaped, spherical, plate-shaped, and mesh-shaped anodes can be used.

When performing the plating process, an object to be plated can be used as the cathode.

The temperature of the plating solution is usually about 10 to 50 ° C. The temperature is preferably 20 to 35 ° C.

The current density (current density in the plating tank) in the intermittent electroplating method of the present invention is, for example, 2 to 15 A / dm ² , preferably 2 to 10 A / dm ² .

In the intermittent electroplating method of the present invention, the time per current addition (time in which one point in the object to be plated is immersed in the plating solution in the plating tank) is, for example, 5 to 120 seconds, preferably 10 to 10. 60 seconds, more preferably 20-40 seconds.

In the intermittent electroplating method of the present invention, the number of current addition cycles is, for example, 2 to 30, preferably 5 to 25, and more preferably 10 to 20.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples.

Test example 1. Intermittent electroplating test 1
<Test Example 1-1. Preparation of electroplating solution>
An electroplating solution having the composition shown in Table 1 below was prepared.

<Test Example 1-2. Pretreatment>
A copper foil resin substrate having a thickness of 64 μm (layer structure: copper foil 7 μm / resin (polyimide) layer 50 μm / copper foil 7 μm) has a large number of via holes with a diameter of 100 μm and a depth of 57 μm. A substrate (Fig. 2) made conductive by a ting system is used as an object to be plated, and this is used in a degreasing solution (trade name: DP-320 Clean, manufactured by Okuno Pharmaceutical Co., Ltd., 100 ml / L aqueous solution) at 45 ° C. 5 After soaking for 1 minute, it was washed with water for 1 minute and then immersed in 100 g / L dilute sulfuric acid for 1 minute for pretreatment.

<Test Example 1-3. Electroplating>
The object to be plated after the pretreatment was immersed in the electroplating solution obtained above, and electroplating was performed in the cycle shown in Table 2. The plating conditions are as shown in Table 3. Specific values of the low current density and its energization time in Table 2 are shown in Table 4. Further, a graph showing an example of this cycle (low current density = 0.2 A / dm ² , energization time 5 seconds) is shown in FIG.

<Test Example 1-4. Filling property evaluation>
After the completion of electroplating, the cross section of the via portion of the object to be plated was observed, and the amount of dent in the via portion shown in FIG. 4 was measured. Based on the measured values, the filling property was evaluated according to the following evaluation criteria (◯: dent amount 48 μm or less, Δ: dent amount: 48 to 53 μm, ×: dent amount 53 μm or more).

<Test Example 1-5. Result>
The results are shown in Table 4. In Table 4, the low current density represents the low current density in the cycle of Table 2, and the energization time represents the energization time (X) of the low current density in the cycle of Table 2.

As shown in Table 4, when electroplating was performed in a cycle that did not generate a low current density (Comparative Example 1), the filling property was relatively good. However, intermittent electroplating, especially a long object to be plated, is continuously supplied to the plating tank on the line, and the discharge of the object to be plated from the plating tank and the supply of the object to be plated to the plating tank are not possible. In intermittent electroplating that is repeated multiple times, low current density is unavoidable due to the plating solution slightly adhering to the object to be plated discharged from the plating tank and the object to be plated supplied to the plating tank. It was found that when such a case was simulated (Comparative Examples 2 to 5), the filling property was significantly deteriorated.

Test example 2. Intermittent electroplating test 2
An electroplating solution was prepared in the same manner as in Test Example 1-1 except that ferric sulfate n-hydrate was added to the electroplating solution to adjust the Fe ^{3+ concentration to the concentration shown in Table 5.} Other than that, pretreatment, electroplating, and filling property evaluation were performed in the same manner as in Test Example 1.

The results are shown in Table 5. In Table 5, the low current density represents the low current density in the cycle of Table 2, and the energization time represents the energization time (X) of the low current density in the cycle of Table 2. Further, FIG. 5 shows a cross-sectional observation view of the via portion of the object to be plated after the completion of electroplating in Example 2 and Comparative Example 3.

As shown in Table 5, deterioration of filling property due to generation of low current density (comparison between Comparative Example 1 and Comparative Examples 2 to 5) is significantly improved by using a plating solution containing ^{Fe 3+.} It turned out.

Test example 3. Intermittent electroplating test 3
An electroplating solution was prepared in the same manner as in Test Example 1-1 except that various metal compounds were added to the electroplating solution to adjust the polyvalent metal ion concentration to the concentration shown in Table 6. Other than that, pretreatment, electroplating, and filling property evaluation were performed in the same manner as in Test Example 1. The low current density in this test is 0.2 A / dm ² , and the energization time is 5 seconds.

The results are shown in Table 6.

As shown in Table 6, the deterioration of the filling property due to the generation of low current density (comparison between Comparative Example 1 and Comparative Examples 2 to 5) is significantly deteriorated by using the plating solution containing the polyvalent metal ion. It turned out to improve.

Claims (12)

An intermittent electroplating method for an object to be plated having micropores, which comprises using a plating solution containing polyvalent metal ions. The intermittent electroplating method according to claim 1, wherein the polyvalent metal ion has a valence of 3 or more. At least one of the polyvalent metal ions selected from the group consisting of ^{Fe 3+} , V ⁵⁺ , Mn ⁷⁺ , Mo ⁶⁺ , W ⁶⁺ , Ce ⁴⁺ , Cr ³⁺ , Cr ⁶⁺ , Ti ⁴⁺ , Sn ⁴⁺ , and Co ^3+. The intermittent electroplating method according to claim 1 or 2. The intermittent electroplating method according to any one of claims 1 to 3, wherein the multivalent metal ion is ^{at least one selected from the group consisting of Fe 3+} and V ^5+. Claim 1 in which a long object to be plated is continuously supplied to a plating tank on a line, and discharge of the object to be plated from the plating tank and supply of the object to be plated to the plating tank are repeated a plurality of times. The intermittent electroplating method according to any one of 4 to 4. The intermittent electroplating method according to claim 5, wherein the object to be plated passes through a plurality of plating tanks. The intermittent electroplating method according to claim 5 or 6, wherein the discharge and the supply are performed on the side surface of the plating tank. The intermittent electroplating method according to any one of claims 5 to 7, which is performed on a reel-to-reel line. The intermittent electroplating method according to any one of claims 1 to 8, wherein the micropores are microvias. The intermittent electroplating method according to any one of claims 1 to 9, wherein the metal to be deposited on the object to be plated contains at least one selected from the group consisting of Cu, Ni, and Sn. The intermittent electroplating method according to any one of claims 1 to 10, wherein the plating solution further contains an additive for beer filling. A plating solution containing polyvalent metal ions for use in the intermittent electroplating method according to any one of claims 1 to 11.

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