Electrolytic stripping method
The present invention provides an electrolytic stripping method comprising electrolytically stripping: a copper plating film exposed from a silver plating film that partially covers a copper plating film formed on the entire surface of a member; and leaking silver formed on an exposed portion of the copper plating film and having a smaller thickness than the silver plating film, using the copper plating film as an anode, wherein the electrolytic stripping is carried out using a cyan compound-free electrolytic copper-stripping liquid, and the electrolytic stripping liquid comprises a compound capable of forming, with silver, a complex ion that is more easily dissociated than a complex ion of silver and cyan; and wherein silver and copper are deposited on a cathode which is used as a counter electrode to the anode and which is made of a metal that is chemically stable against the electrolytic stripping liquid.
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The present invention relates to an electrolytic stripping method. In more detail, the invention relates to an electrolytic stripping method of stripping: a copper plating film exposed from a silver plating film that partially covers a copper plating film formed on the entire surface of a member; and leaking silver formed on an exposed portion of the copper plating film and having a smaller thickness than the silver plating film, by electrolytic stripping using the copper plating film and leaking silver as an anode.
BACKGROUND OF THE INVENTION In a lead frame to be used in semiconductor devices, as illustrated in
On such a bonding portion 12a, a silver plating film is formed, and the foregoing one end portion of the gold wire is connected to the bonding portion 12a.
As illustrated in
As illustrated in
Next, as illustrated in
Thereafter, the lead frame 10 is dipped in an electrolytic stripping liquid, and the copper plating film 16 which is exposed without being covered by the silver plating film 22 is removed by electrolytic stripping using the lead frame 10 as an anode. Thus, as illustrated in
Now, in putting the lead frame 10 between the mask plates 18a and 18b and forming a silver plating film on the exposed copper plating film 16, leaking silver 24 having a smaller thickness than the silver plating film 22 is also formed at a portion having covered by the mask plates 18a and 18b as illustrated in
For electrically stripping the leaking silver 24 and the copper plating film 16 without substantially stripping the silver plating film 22, an electrolytic stripping liquid containing a cyan compound has been used as described in the following Patent Document 1.
Patent Document 1: JP 59-031900 A (pages 2 to 3)
As described in Patent Document 1, by dipping the lead frame 10, on which the silver plating film 22 is formed only at the tip portion 20 of the inner lead 12, in an electrolytic stripping liquid containing a cyan compound and carrying out electrolytic stripping of copper using this lead frame 10 as an anode and a stainless steel plate as a cathode, it is possible to electrolytically strip the leaking silver 24 and the copper plating film 16 without substantially stripping the silver plating film 22.
However, if the electrolytic stripping liquid containing a cyan compound is continuously used, in electrolytically stripping the leaking silver 24 and the copper plating film 16, a stripping rate of the copper plating film 16 and the leaking silver 24 is reduced within a relatively short period of time. For this reason, it is required to frequently exchange such an electrolytic stripping liquid.
Further, if it is intended to recover silver as a noble metal from the cyan compound-containing electrolytic stripping liquid to be exchanged and disposed, another special recover step is required.
SUMMARY OF THE INVENTIONAccordingly, an object of the invention is to provide an electrolytic stripping method using an electrolytic stripping liquid which is a cyan compound-free electrolytic stripping liquid and the life of which can be greatly extended as compared to that of cyan compound-electrolytic stripping liquids.
Other objects and effects of the invention will become apparent from the following description.
To achieve the foregoing objects, the present inventors made extensive investigations. As a result, electrolytic stripping was carried out using, as an anode, the lead frame 10 in which the silver plating film 22 is formed only at the tip portion 20 of the inner lead 12 as illustrated in
Further, it has been found that in this way, by carrying out electrolytic stripping while depositing silver and copper on the cathode, the life of the electrolytic stripping liquid is prolonged as compared to that of cyan compound-containing electrolytic stripping liquids, thus leading to accomplishment of the invention.
Specifically, the invention relates to an electrolytic stripping method comprising electrolytically stripping:
-
- a copper plating film exposed from a silver plating film that partially covers a copper plating film formed on the entire surface of a member; and
- leaking silver formed on an exposed portion of the copper plating film and having a smaller thickness than the silver plating film, using the copper plating film as an anode,
- wherein the electrolytic stripping is carried out using a cyan compound-free electrolytic copper-stripping liquid, and the electrolytic stripping liquid comprises a compound capable of forming, with silver, a complex ion that is more easily dissociated than a complex ion of silver and cyan, and
- wherein silver and copper are deposited on a cathode which is used as a counter electrode to the anode and which is made of a metal that is chemically stable against the electrolytic stripping liquid.
In the invention, the compound capable of forming, with silver, a complex ion that is more easily dissociated than a complex ion of silver and cyan is preferably a compound capable of forming, with silver, a complex ion having a lower complex stability constant than the complex ion of silver and cyan.
As this compound, at least one compound selected from the group consisting of ammonia water, an ammonium salt, a tartaric acid salt, phosphoric acid, and a citric acid salt can be used.
Also, since the electrolytic stripping liquid to be used in the invention is an electrolytic copper-stripping liquid for electrically stripping a copper plating film, it is preferable that the electrolytic stripping liquid contains a copper compound or an aromatic nitro compound as a copper-oxidizing agent and is adjusted so as to have a pH of from 9 to 12.
Here, the copper compound is preferably derived from an ammonium source and a copper source capable of forming a copper ammonium complex, added to the electrolytic stripping liquid.
Further, by surrounding the cathode by a cathode bag, it is possible to collect silver and copper particles, comprising silver and copper deposited on the cathode, respectively, by the cathode bag; and by taking out the cathode bag from the electrolytic stripping liquid, it is possible to recover silver and copper comprising silver and copper deposited on the cathode.
Incidentally, a lead frame made of an iron based alloy can be suitably used as the member.
The reasons why the life of cyan compound-containing electrolytic stripping liquids which have been used so far is short may be considered as follows.
Since a cyan ion in an electrolytic stripping liquid forms a stable complex ion with a silver ion in the electrolytic stripping liquid, a silver concentration in the electrolytic stripping liquid rises with an increase of the electrolytic stripping treatment amount of leaking silver. As the silver concentration in the electrolytic stripping liquid rises, the stripping rate of leaking silver and a copper plating film is reduced.
On the other hand, in the invention, the electrolytic stripping is carried out using an electrolytic stripping liquid which is a cyan compound-free electrolytic copper-stripping liquid containing a compound capable of forming, with silver, a complex ion that is more easily dissociated than a complex ion of silver and cyan, while depositing silver and copper on a cathode used as a counter electrode to a copper plating film and leaking silver serving as an anode.
As a result, in accordance with the electrolytic stripping method according to the invention, it is possible to prevent a reduction in the stripping rate of the copper plating film and leaking silver caused by accumulation of silver in the electrolytic stripping liquid; and it is possible to greatly extend the life of the electrolytic stripping liquid as compared to conventional cyan compound-containing electrolytic stripping liquids.
BRIEF DESCRIPTION OF THE DRAWINGS
The reference numerals used in the drawings denote the followings, respectively.
-
- 10: Lead frame
- 12: Inner lead
- 12a: Bonding portion
- 14: Die pad
- 16: Copper plating film
- 22: Silver plating film
- 24: Leaking silver
- 30: Electrolytic stripping liquid
- 36: Direct current source
- 38: Cathode
- 40: Cathode bag
- 42: Circulation pump
- 44: Circulation line
- 46: Filter
The electrolytic stripping liquid to be used in the invention is a cyan compound-free electrolytic copper-stripping liquid. As the electrolytic stripping solution, an electrolytic stripping liquid containing a copper compound or an aromatic nitro compound as a copper-oxidizing agent can be suitably used.
For the copper compound as the copper-oxidizing agent, a copper ammonium complex is suitable. Such a copper ammonium complex can be formed by adding, to the electrolytic stripping liquid, ammonia water or an ammonium salt as an ammonium source and copper sulfate, copper carbonate, copper oxalate or copper hydroxide as a copper source.
The copper ammonium complex that is formed in the electrolytic stripping liquid having an ammonium source and a copper source added thereto comprises at least one of [Cu(NH3)2]2+, [Cu(NH3)4]2+, and [Cu(NH3)6]2+.
As the aromatic nitro compound, chloronitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, ethyl p-nitro-benzoate, and sodium p-nitrobenzoate can be suitably used.
An electrolytic stripping liquid which contains an aromatic nitro compound as a copper-oxidizing agent but to which a cyan compound is added cannot be expected to have a prolonged life.
The amount of the copper-oxidizing agent used in the electrolytic stripping liquid of the present invention is generally from 1 to 100 g/liter, preferably from 5 to 40 g/liter.
Further, it is preferable that such an electrolytic stripping liquid is adjusted so as to have a pH of from 9 to 12. The pH adjustment may be achieved by using ammonia water as the ammonium source to be added as a compound capable of forming a copper ammonium complex, or using a pH adjustor such as sodium hydroxide.
Here, in the case where the pH of the electrolytic stripping liquid is less than 9, or in the case where the pH of the electrolytic stripping liquid exceeds 12, the stripping rate of the copper plating film tends to be reduced.
A compound capable of forming, with silver, a complex ion that is more easily dissociated than a complex ion of silver and cyan is added to the electrolytic copper-stripping liquid to be used in the invention. Examples of such a compound include compounds capable of forming, with silver, a complex ion having a lower complex stability constant than the complex ion of silver and cyan. Specifically, one or more compounds selected from the group consisting of ammonia water, an ammonium salt, a tartaric acid salt, phosphoric acid, and a citric acid salt can be used.
Incidentally, ammonia water or an ammonium salt which is a compound capable of forming a complex ion with silver may be also used as an ammonium source for forming a copper ammonium complex.
The amount of the compound capable of forming, with silver, a complex ion that is more easily dissociated than a complex ion of silver and cyan, in the electrolytic stripping liquid is generally from 0.1 mg to 100 g/liter.
The term “complex stability constant” as referred to herein means a constant expressing the degree of dissociation of a complex ion. Lower values thereof mean that the formed complex ion is more instable and more easily dissociated.
For example, the complex ion of silver and cyan is based on an equilibrium reaction between a silver ion and a cyan ion as shown in the following formula 1, and the complex ion of silver and ammonium is based on an equilibrium reaction between a silver ion and ammonia as shown in the following formula 2.
Ag++2CN−<- >Ag(CN)2− Formula 1
Ag++2NH3<->Ag(NH3)2+ Formula 2
In these equilibrium reactions, the stability constant (KCN) as an index expressing hardness of dissociation of the complex ion of silver and cyan can be expressed by the following equation 1, and its value (KCN) is 1×1021.
KCN=[Ag(CN)2−]/{[Ag+][CN−]2} Equation 1
On the other hand, the stability constant (KNH3) as an index expressing hardness of dissociation of the complex ion of silver and ammonium can be expressed by the following equation 2, and its value (KNH3) is 1.5×107.
KNH3=[Ag(NH3)2+]/{[Ag+][NH3]2} Equation 2
In this way, since KCN is larger than KNH3, the complex ion of silver and ammonium is easily dissociated, as compared to the complex ion of silver and cyan, into a silver ion and ammonia.
By removing the silver ion in the electrolytic stripping liquid, the complex ion of silver and ammonium is more easily dissociated into a silver ion and ammonia.
The silver ion in the electrolytic stripping liquid can be easily removed by depositing silver on a cathode, which is a counter electrode to the lead frame 10 serving as an anode, in carrying out electrolytic stripping with respect to the copper plating film 16 and leaking silver 24 as illustrated in
The electrolytic stripping using such an electrolytic liquid can be carried out using a device illustrated in
This lead frame 10 is connected to an anode of a direct current source 36, and a cathode 38 made of platinum to be connected to a cathode of the direct current source 36 is dipped as a counter electrode of the lead frame 10 (the anode) in the electrolytic stripping liquid 30. Such a cathode 38 is surrounded by a cathode bag 40. The cathode bag 40 collects silver and copper particles comprising silver and copper deposited on the cathode 38, respectively, and the like, and is made of fibers having durability against the electrolytic stripping liquid 30, such as fibers made of PTFE (polytetrafluoroethylene) or PP (polypropylene) and formed into a bag shape.
The electrolytic stripping liquid 30 stored in the electrolytic stripping vessel 32 is circulated by a circulation pump 42, and a filter 46 for separating particles floating in the electrolytic stripping liquid 30 and the like is provided in the way of a circulation line 44.
By passing a direct current between the lead frame 10 as the anode and the cathode 38, each dipped in the electrolytic stripping liquid 30 stored in the electrolytic stripping vessel 32 as illustrated in
In this way, by separating the silver ion in the electrolytic stripping liquid 30 as silver particles comprising silver or the like, it is possible to reduce the silver concentration in the electrolytic stripping liquid. For this reason, the method of the invention is free from the formation of a stable complex ion of cyan and silver in an electrolytic stripping liquid as seen in the conventionally employed electrolytic stripping using a cyan compound-containing electrolytic stripping liquid. Also, according to the method of the invention, it is possible to prevent a reduction in the stripping rate of the copper plating film and the leaking silver due to accumulation of silver in the electrolytic stripping liquid; and it is possible to greatly extend the life of the electrolytic stripping liquid as compared to that of conventional cyan compound-containing electrolytic stripping liquids.
In
The present invention will be illustrated in greater detail with reference to the following Examples, but the invention should not be construed as being limited thereto.
Example 1After forming a copper plating film by electrolytic copper plating on the entire surface of a lead frame made of an iron-nickel alloy (42 alloy), a silver plating film was formed on the copper plating film by electrolytic silver plating.
Next, using the device illustrated in
In the electrolytic stripping using any of the electrolytic stripping liquids shown in Table 2, silver in the form of particles or the like was collected by the cathode 38, the cathode 40 and the filter 46, and the silver concentration in the electrolytic stripping liquid 30 was low.
When the electrolytic stripping was carried out using the electrolytic stripping liquid 1, the silver concentration in the particles or the like which adhered to the cathode 38, silver concentration in the particles or the like which were collected by the cathode bag 40, and silver concentration in the particles or the likw which were collected by the filter 46 were measured. The results obtained are shown in Table 3. This silver concentration was measured by dissolving the particles or the like which adhered to the cathode 38 or which were collected by the cathode bag 40 or the filter 46 in 50% nitric acid.
The copper plating film and the silver plating film formed on the lead frame 10 were continuously electrically stripped using the electrolytic stripping liquid 1 under the same current density and bath temperature as those in the case of the electrolytic stripping liquid 1 of Example 1 in the same manner as in Example 1, except that the cathode bag 40 was removed. When the treatment amount of silver reached 1,000 ppm, the silver concentration in the electrolytic stripping liquid 30 stored in the electrolytic stripping vessel 32, silver concentration in the particles or the like which adhered to the cathode 38, and silver concentration in the particles or the like which were collected by the filter 46 were measured. The results obtained are shown in Table 4. The measurement of the silver concentration was carried out in the same manner as in Example 1.
As is clear from Table 4, it is understood that likewise Example 1, the silver concentration in the electrolytic stripping liquid 30 was low, and silver was collected by the cathode 38 and the filter 46.
Comparative Example 1 The copper plating film and the silver plating film formed on the lead frame 10 were continuously electrically stripped in the same manner as in Example 2 under the same current density and bath temperature as those in the case of the electrolytic stripping liquid 1 of Example 1, except that a cyan based electrolytic stripping liquid (potassium cyanide: 80 g/L, p-nitrobenzoic acid: 10 g/L, pH: 11) was used as the electrolytic stripping liquid. When the treatment amount of silver reached 1,000 ppm, the silver concentration in the electrolytic stripping liquid 30 stored in the electrolytic stripping vessel 32, silver concentration in the particles or the like which adhered to the cathode 38, and silver concentration in the particles or the like which were collected by the filter 46 were measured. The results obtained are shown in Table 5. The measurement of the silver concentration was carried out in the same manner as in Example 1.
As is clear from Table 5, in the cyan based electrolytic stripping liquid, though silver was somewhat deposited on the cathode 38, the silver was not deposited to such extent that particles or the like collectable by the filter 46 were formed. For this reason, the silver concentration in the electrolytic stripping liquid 30 is high.
While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
This application is based on Japanese patent application No. 2003-433701 filed Dec. 26, 2003, the contents thereof being herein incorporated by reference.
Claims
1. An electrolytic stripping method comprising electrolytically stripping:
- a copper plating film exposed from a silver plating film that partially covers a copper plating film formed on the entire surface of a member; and
- leaking silver formed on an exposed portion of the copper plating film and having a smaller thickness than the silver plating film, using the copper plating film as an anode,
- wherein the electrolytic stripping is carried out using a cyan compound-free electrolytic copper-stripping liquid, and the electrolytic stripping liquid comprises a compound capable of forming, with silver, a complex ion that is more easily dissociated than a complex ion of silver and cyan; and
- wherein silver and copper are deposited on a cathode which is used as a counter electrode to the anode and which is made of a metal that is chemically stable against the electrolytic stripping liquid.
2. The electrolytic stripping method according to claim 1, wherein the compound capable of forming, with silver, a complex ion that is more easily dissociated than a complex ion of silver and cyan is a compound capable of forming, with silver, a complex ion having a lower complex stability constant than the complex ion of silver and cyan.
3. The electrolytic stripping method according to claim 1, wherein the compound capable of forming, with silver, a complex ion that is more easily dissociated than the complex ion of silver and cyan comprises at least one compound selected from the group consisting of ammonia water, an ammonium salt, a tartaric acid salt, phosphoric acid, and a citric acid salt.
4. The electrolytic stripping method according to claim 1, wherein the electrolytic stripping liquid further comprises a copper compound or an aromatic nitro compound as a copper-oxidizing agent and has a pH of from 9 to 12.
5. The electrolytic stripping method according to claim 4, wherein the copper compound is a copper ammonium complex derived from an ammonium source and a copper source.
6. The electrolytic stripping method according to claim 1, wherein the cathode is surrounded by a cathode bag for collecting silver particles comprising the deposited silver.
7. The electrolytic stripping method according to claim 1, wherein the member is a lead frame made of an iron based alloy.
8. The electrolytic stripping method according to claim 1, further comprising
- circulating the electrolytic stripping liquid in the vicinity of the cathode through a circulation line equipped with a filter, thereby collecting silver particles comprising the deposited silver.
Type: Application
Filed: Oct 22, 2004
Publication Date: Jun 30, 2005
Applicant: SHINKO ELECTRIC INDUSTRIES CO., LTD. (Nagano-shi)
Inventors: Yoko Ogihara (Nagano-shi), Masao Nakazawa (Nagano-shi)
Application Number: 10/972,138