CN1626703A - Electrolytic copper-stripping liquid and electrolytic stripping method - Google Patents
Electrolytic copper-stripping liquid and electrolytic stripping method Download PDFInfo
- Publication number
- CN1626703A CN1626703A CNA2004100860305A CN200410086030A CN1626703A CN 1626703 A CN1626703 A CN 1626703A CN A2004100860305 A CNA2004100860305 A CN A2004100860305A CN 200410086030 A CN200410086030 A CN 200410086030A CN 1626703 A CN1626703 A CN 1626703A
- Authority
- CN
- China
- Prior art keywords
- copper
- silver
- stripping
- electrolytic
- electrolytic solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F5/00—Electrolytic stripping of metallic layers or coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Lead Frames For Integrated Circuits (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention provides an electrolytic copper-stripping liquid free from a cyan compound, which comprises a copper compound or an aromatic nitro compound as a copper-oxidizing agent, and which has a pH of from 9 to 12. Also disclosed is an electrolytic stripping method using the electrolytic stripping liquid.
Description
Technical field
The present invention relates to a kind of copper-stripping electrolytic solution and a kind of electrolytic stripping method.In more detail, the present invention relates to a kind of copper-stripping electrolytic solution that to peel off from the copper plating film that silver-plated film exposes by electrolytic stripping of being used for, wherein silver-plated membrane portions covers and is formed on the whole lip-deep copper plating film of element, also relates to the electrolytic stripping method of realizing this electrolytic stripping.
Background technology
As shown in Figure 1, be used for the lead frame of semiconducter device (lead frame), inner lead 12 has constituted the lead frame of being made by ferrous alloy material (as iron nickel alloy (42 alloy)) 10.Be positioned at the end (hereinafter abbreviating this end sections as end) of crystal grain pad (die pad) 14 1 sides at each inner lead 12, formed the connection portion 12a that links to each other with a tail end of gold thread.Another tail end of gold thread links to each other with semiconductor element on being installed in the crystal grain pad.
Form silver-plated film on this connection portion 12a, a tail end of aforesaid gold thread is connected with connection portion 12a.
As shown in Figure 1, when on forming it, being formed with the crystal grain connection portion 12a of silver-plated film,, around lead frame 10 whole, form copper plating film by copper electroplating in the end of each inner lead 12 of the lead frame of making by ferrous alloy 10.
Shown in Fig. 2 A, the lead frame 10 that is formed with this copper plating film on it is placed between rubber system mask sheet 18a and the 18b, its mode is that the part copper plating film 16 that only is used to form connection portion 12a is come out at 20 places, end of inner lead 12, and it is silver-plated to carry out electrolysis on the copper plating film 16 that exposes, to form silver-plated film.
Then, shown in Fig. 2 B, remove mask sheet 18a and 18b after finishing in that electrolysis is silver-plated, the silver-plated film 22 of part just only forms in the part of the connection portion 12a that is used to form inner lead 12 ends 20.
Then, lead frame 10 being immersed in the electrolytic stripping liquid, is anode with lead frame 10, and the copper plating film 16 that will expose by electrolytic stripping, do not covered by the silver-plated film 22 of part is removed.Thereby shown in Fig. 2 C, only the part at the connection portion 12a that is used to form inner lead 12 ends 20 forms the connection portion 12a that comprises copper plating film 16 and the silver-plated film 22 of part.
When lead frame 10 being placed between mask sheet 18a and the 18b and form silver-plated film on the copper plating film 16 that is exposing, shown in Fig. 2 B, reasons such as strain owing to mask sheet 18a and 18b, electrolysis silver plating liquid generation seepage is also being formed flash plating silverskin 24 (hereinafter being sometimes referred to as " seepage silver 24 ") by the part of mask sheet 18a and 18b covering.Seepage silver 24 is also removed by the electrolytic stripping of copper plating film 16, and shown in Fig. 2 C, the silver-plated film 22 of part only is used to form connection portion 12a in the end 20 of inner lead 12 part forms.
For silver 24 of electrolytic stripping seepage under the situation of the silver-plated film 22 of not substantive released part and copper plating film 16, as described in following patent documentation 1, used the electrolytic stripping liquid that contains cyano compound.
Patent documentation 1:JP 59-031900 A (the 2nd to 3 page).
As described in patent documentation 1, the lead frame 10 that only forms the silver-plated film 22 of part on the end 20 of inner lead 12 is immersed the electrolytic stripping liquid that contains cyano compound, and be anode, be that catholyte is peeled off copper with the stainless steel substrates with lead frame 10, can the electrolytic stripping seepage silver 24 and copper plating film 16, and the silver-plated film 22 of released part substantially not.
Yet if use the electrolytic stripping liquid that contains cyano compound continuously, in the electrolytic stripping process of seepage silver 24 and copper plating film 16, the detachment rate of copper plating film 16 and seepage silver 24 will descend in the relative short time.Therefore, need the frequent this electrolytic stripping liquid of changing.
And, for safety, when replacing contains the electrolytic stripping liquid etc. of cyano compound, pay particular attention to.
Brief summary of the invention
Therefore, a theme of the present invention provides electrolytic stripping liquid, and this electrolytic stripping liquid is the cyano-containing compound not, and compares significant prolongation in its with the electrolytic stripping liquid that contains cyano compound in work-ing life.
Another theme of the present invention provides a kind of electrolytic stripping method that uses this copper-stripping electrolytic solution.
According to following description, other purposes of the present invention and effect will be tangible.
In order to realize above-mentioned target, the present inventor has carried out extensive studies.Found that, by using cyano-containing compound not, containing the copper-stripping electrolytic solution that copper compound or aromatic nitro compound are made oxygenant, and the lead frame 10 that only forms the silver-plated film 22 of parts in the end 20 of inner lead 12 shown in Fig. 2 B carried out electrolytic stripping, can electrolytic stripping seepage silver 24 and copper plating film 16 and can the silver-plated film 22 of substantive released part.
In addition, we find that also the work-ing life of this electrolytic stripping liquid is longer than the electrolytic stripping liquid that contains cyano compound, thereby have finished the present invention.
Specifically, the present invention relates to a kind of copper-stripping electrolytic solution, it is the cyano-containing compound not, contains copper compound or aromatic nitro compound as copper oxidant, and the pH value is 9 to 12.
The invention still further relates to a kind of method of electrolytic stripping copper, comprise and adopt above-mentioned copper-stripping electrolytic solution, the copper plating film that electrolytic stripping comes out from the silver-plated film that partly covers copper plating film (copper plating film is formed on the whole surface of element) wherein, immerses in the copper-stripping electrolytic solution element also as anode.
Among the present invention, the copper oxidant that contains in the electrolytic stripping liquid is preferably cuprammonium complex.In electrolytic stripping liquid, add ammoniacal liquor or ammonium salt as the ammonium source, add copper sulfate, copper carbonate, cupric oxalate or copper hydroxide, can prepare cuprammonium complex as the copper source.
In electrolytic stripping liquid, add at least a following compound that is selected from addition again, can adjust the specific conductivity of electrolytic stripping liquid: phosphoric acid and salt thereof, organic acid (comprising citric acid and tartrate) and salt, carbonate, supercarbonate and aminocarboxylic acid (comprising L-glutamic acid and aspartic acid) and salt thereof.
The compound of interpolation and silver-colored reacting generating complex can also be peeled off seepage silver etc. fast as silver-colored stripper in electrolytic stripping liquid.Comprise pyridine carboxylic acid, thiocyanate-, T10 and succinimide with the example of the compound of silver-colored reacting generating complex.
In addition, in electrolytic stripping liquid, add tensio-active agent, can strengthen the wettability that will carry out the element of electrolytic stripping.The example of the tensio-active agent that is suitable for using comprises the tensio-active agent that contains polyoxyethylene chain and fluorine-containing tensio-active agent.
As for the element that uses according to electrolytic stripping liquid of the present invention, the lead frame of being made by ferrous alloy material is suitable for using.For carrying out electrolytic stripping, preferred use can not made negative electrode by the metal electrode of wash-out in electrolytic stripping liquid.
The work-ing life of the electrolytic stripping liquid that contains cyano compound of use is shorter always up to now, and its reason can be made description below.
Along with the increase of electrolytic stripping treatment capacity, the cyano compound in the electrolytic stripping liquid will improve the concentration of silver in the electrolytic stripping liquid gradually.When the concentration of silver in the electrolytic stripping liquid raises, the copper generation replacement(metathesis)reaction in the silver ions in the electrolytic stripping liquid and the copper plating film of being stripped from, thus reduced the detachment rate of copper.
And, form complex compound with silver easily because cyano compound is same, so not only copper plating film is stripped from, the silver-plated film of part also is stripped from.Therefore, after peeling off of copper plating film finished, it is coarse that the surface of the silver-plated film of part becomes usually, thereby make appearance degradation.
And according to electrolytic stripping liquid of the present invention cyano-containing compound not, and contain copper compound or aromatic nitro compound is made copper oxidant.
Like this, owing to do not add the cyano compound that may generate complex compound with silver according to electrolytic stripping liquid of the present invention, thereby can in the electrolytic stripping process, peel off copper plating film selectively with respect to the silver-plated film of part.
Yet to the greatest extent let it be, and detachment rate is compared slowly with copper plating film, even also can peel off the seepage silver that is formed on the copper plating film according to electrolytic stripping liquid of the present invention.
Although there is a certain amount of silver ions from wash-outs such as silver-plated film of part and seepage silver in electrolytic stripping liquid according to the present invention, the silver-colored major part of wash-out is deposited on the negative electrode, thereby can suppress the increase of silver concentration in the electrolytic stripping liquid.
Therefore, use electrolytic stripping liquid of the present invention, can prevent reduction, and the silver-plated film appearance of part is coarse because of the copper plating film detachment rate that causes of accumulation of silver in the electrolytic stripping liquid.Thereby, compare with traditional electrolytic stripping liquid that contains cyano compound, can significant prolongation its work-ing life.
Description of drawings
Fig. 1 is the part plan view, is used to illustrate the lead frame as carrying out the element of electrolytic stripping.
Fig. 2 A is a partial cross sectional view to 2C, is used to illustrate the silver-plated and seepage silver of the part that forms on lead frame as shown in Figure 1.
Fig. 3 is a graphic representation, shows after the copper and silver of handling predetermined amount, and electrolytic stripping liquid according to the present invention is to the measuring result of the detachment rate of copper and silver.
Fig. 4 is a graphic representation, shows after the copper and silver of handling predetermined amount, contains the measuring result of the electrolytic stripping liquid of cyano compound to the detachment rate of copper and silver.
The implication of used mark is as follows respectively in the accompanying drawing:
10: lead frame
12: inner lead
12a: connect part
14: the crystal grain pad
16: copper plating film
20: the end of inner lead
22: the silver-plated film of part
24: seepage silver
The detailed content of invention
According to electrolytic stripping liquid of the present invention cyano-containing compound not, and contain copper compound and aromatic nitro compound is made copper oxidant, this is very important.
About the copper compound as copper oxidant, cuprammonium complex is fit to. Add ammoniacal liquor or ammonium salt in the electrolytic stripping liquid as the ammonium source, add copper sulphate, copper carbonate, cupric oxalate or Kocide SD as the copper source, can produce this cuprammonium complex.
Add the cuprammonium complex that ammonium source and copper source form therein in the electrolytic stripping liquid and comprise [Cu (NH3)
2]
2+、[Cu(NH
3)
4]
2+、[Cu(NH
3)
6]
2+In at least a.
About aromatic nitro compound, what be suitable for using has chloronitrobenzene formic acid, 2-chloro-4-nitrobenzoic acid, o-nitrobenzoic acid, m-Nitrobenzoic Acid, paranitrobenzoic acid, ethyl p-nitrobenzoate and a sodium paranitrobenzoate.
Contain copper compound or aromatic nitro compound as copper oxidant but added the electrolytic stripping liquid of cyano compound, expect can not prolong its service life, although it can provide the good silver-plated film outward appearance of part.
The amount of the copper oxidant that electrolytic stripping liquid of the present invention uses is generally 1 to 100 grams per liter, preferred 5 to 40 grams per liters.
In addition, the pH value of electrolytic stripping liquid of the present invention need to be adjusted to 9 to 12. Use ammoniacal liquor as the ammonium source that adds with the compound that can form cupric ammine complex, or adopt pH adjusting agent (such as NaOH), can regulate the pH value.
When the pH of electrolytic stripping liquid value less than 9, perhaps when the pH of electrolytic stripping liquid value greater than 12 the time, the detachment rate of copper plating film will reduce.
In electrolytic stripping liquid according to the present invention, add at least a following compound, the electrical conductivity of capable of regulating electrolytic stripping liquid: phosphoric acid and salt thereof, organic acid (comprising citric acid and tartaric acid) and salt, carbonate, bicarbonate and amino carboxylic acid (comprising glutamic acid and asparatate) and salt thereof of being selected to electrolytic stripping liquid.
Used hereinly can effectively regulate the phosphoric acid of electrolytic stripping liquid electrical conductivity and the example of salt comprises phosphoric acid, metaphosphoric acid, orthophosphoric acid and these sour ammonium salts, sylvite and sodium salt (its object lesson comprises ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, triammonium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate and potassium pyrophosphate). Wherein be more suitable for using phosphoric acid, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, triammonium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate.
The organic acid of electrolytic stripping liquid electrical conductivity and the example of salt thereof be can effectively regulate and formic acid, acetic acid, oxalic acid, propionic acid, butyric acid, valeric acid, citric acid, lactic acid, tartaric acid, butanedioic acid, benzoic acid, benzene sulfonic acid, nicotinic acid, isonicotinic acid and these sour ammonium salts, sylvite and sodium salt (its object lesson comprises ammonium formate, potassium formate, ammonium acetate, potassium acetate, ammonium binoxalate, ammonium dihydrogen citrate, diammonium hydrogen citrate, Triammonium citrate, potassium citrate dihydrogen, citric acid tri potassium, ammonium tartrate, potassium tartrate, ammonium succinate and Potassium Suceinate) comprised. In these organic acids and salt thereof, be particularly suited for using formic acid, citric acid, tartaric acid, butanedioic acid, ammonium formate, ammonium dihydrogen citrate, diammonium hydrogen citrate, Triammonium citrate, potassium citrate dihydrogen, citric acid tri potassium, ammonium tartrate, potassium tartrate, ammonium citrate, potassium citrate.
The carbonate of electrolytic stripping liquid electrical conductivity and the example of bicarbonate be can effectively regulate and ammonium carbonate, carbonic hydroammonium, potash, saleratus, sodium carbonate and sodium acid carbonate comprised. In these compounds, be suitable for using ammonium carbonate, carbonic hydroammonium, potash and saleratus.
Glycine and amino carboxylic acid (comprising glutamic acid and asparatate) and salt thereof can effectively be regulated the electrical conductivity of electrolytic stripping liquid equally, and its example comprises glycine, glutamic acid, asparatate, cysteine, methionine, threonine, serine, alginine and these sour ammonium salts, sylvite and sodium salt. In these compounds, be suitable for using glycine, glutamic acid and asparatate.
In electrolytic stripping liquid of the present invention, the amount that can be used as the above-mentioned salt of above-mentioned at least a compound is generally 10 to 300 grams per liters, preferred 50 to 200 grams per liters. The pH value that the amount of above-mentioned acid is adjusted to the electrolytic stripping liquid that can make acquisition is 9 to 12.
Incidentally, for each surface of strengthening the copper plating film that to peel off and seepage silver wettability with respect to electrolytic stripping liquid, for example, can add the surfactant that contains polyoxyethylene chain or fluorine based surfactant as surfactant.
Like this, using according to electrolytic stripping liquid of the present invention, when wherein being formed at lead frame 10 on the copper plating film 16 and carrying out electrolysis stripping just like the seepage silver 24 shown in Fig. 2 B, can in the seepage silver 24 of peeling off shown in Fig. 2 B, peel off copper plating film 16.
At this moment, for having a mind to further to improve the detachment rate of seepage silver 24, can add the compound with silver-colored reacting generating complex, be used as silver-colored remover such as picolinic acid, rhodanate, dimethyl hydantoin and succinimide. Add the amount with compound silver-colored reacting generating complex electrolytic stripping liquid of the present invention to and be generally 0.1 milligram to 100 grams per liters.
There is no particular restriction to prepare the method for electrolytic stripping liquid of the present invention, and simple mixing said ingredients can obtain electrolytic stripping liquid in normal way.
Using described electrolytic stripping liquid of the present invention, when the seepage silver 24 in the lead frame 10 of electrolysis stripping shown in Fig. 2 B and copper plating film 16, doing to pass to direct current between anode lead frame 10 and the negative electrode (the two all is dipped in the peel container that stores electrolytic stripping liquid), but electrolysis stripping seepage silver 24 and copper plating film 16.
In the electrolysis stripping process, with can in electrolytic stripping liquid, not being suitable for use as negative electrode by the metal electrode (such as platinum electrode or stainless steel electrode) of wash-out. Like this, by use this can be in electrolytic stripping liquid the metal electrode of wash-out as negative electrode, the silver ion in the electrolytic stripping liquid can be deposited on the negative electrode; The concentration of silver in the electrolytic stripping liquid can be controlled at low concentration; And can easily reclaim silver.
Incidentally, in the electrolytic stripping process, current density is generally about 0.01 to 20A/dm
2, and be preferably about 0.1 to 10A/dm
2And the treatment time is preferably from about 2 to 30 seconds.
Embodiment
The present invention will be described in more detail with reference to the following example, but the present invention should not be interpreted as being limited in the scope of these embodiment.
Embodiment 1
By copper electroplating, form copper plating film 16 with thickness from 0.1 to 0.2 μ m on the whole surface of the lead frame 10 that constitutes by iron nickel alloy (42 alloy).Then shown in Fig. 2 A, lead frame 10 is placed between the mask sheet 18a and 18b of rubber system, the part copper plating film 16 that only is used to form connection portion 12a is come out at 20 places, end of inner lead 12, and silver-plated to form thickness on the copper plating film that exposes be the silver-plated film 22 of part of 3 to 6 μ m by electrolysis then.
Subsequently, when removing mask sheet 18a and 18b, shown in Fig. 2 B, just on the connection portion 12a that is used to form inner lead 12 ends 20, formed the silver-plated film 22 of part.
Yet, shown in Fig. 2 B, can be formed seepage silver 24 by the position of mask sheet 18a and 18b covering in part.
The lead frame immersion is stored in the peel container of electrolytic stripping liquid as shown in table 1 below, between the negative electrode of making anodic lead frame 10 and making, pass to galvanic current then, seepage silver 24 and copper plating film 16 are carried out electrolytic stripping by platinum electrode.
Table 1
| Electrolytic stripping liquid 1 | Triammonium phosphate: the ammoniacal liquor of 50g/L p-nitrobenzoic acid: 20g/L 25% (being used for pH regulator) pH:9.5 |
| Electrolytic stripping liquid 2 | Triammonium phosphate: 50g/L copper hydroxide (II): the ammoniacal liquor of 5g/L 25% (being used for pH regulator) pH:11.0 |
| Electrolytic stripping liquid 3 | L-L-glutamic acid: 100g/L p-nitrobenzoic acid: 10g/L potassium hydroxide (being used for pH regulator) |
| pH：????????????10.0 | |
| Electrolytic stripping liquid 4 | Ammonium tartrate: 50g/L copper hydroxide (II): the ammoniacal liquor of 5g/L Yi Yansuan: 20g/L 25% (being used for pH regulator) pH:9.5 |
| Electrolytic stripping liquid 5 | Triammonium phosphate: 100g/L copper hydroxide (II): the ammoniacal liquor of 5g/L polyoxyethylene glycol: 1g/L 25% (being used for pH regulator) pH:10.0 |
| Electrolytic stripping liquid 6 | Volatile salt: the ammoniacal liquor of 200g/L copper carbonate: 20g/L 25% (being used for pH regulator) pH:10.0 |
| Electrolytic stripping liquid 7 | Triammonium phosphate: 100g/L copper hydroxide (II): the ammoniacal liquor of 2g/L ammonium thiocyanate: 1g/L 25% (being used for pH regulator) pH:10.0 |
| Electrolytic stripping liquid 8 | Triammonium phosphate: 100g/L p-nitrobenzoic acid: the ammoniacal liquor of 10g/L nicotinic acid: 20g/L 25% (being used for pH regulator) pH:9.0 |
| Electrolytic stripping liquid 9 | Potassium cyanate: 80g/L p-nitrobenzoic acid: 10g/L pH:11.0 |
The electrolytic stripping liquid, current density and the treatment time that are used for electrolytic stripping are as shown in table 2 below.Equally, the result of electrolytic stripping is also shown in the following table 2.On each level as shown in table 2, do not observe fading and forming the corrosion of 42 alloys of lead frame 10 of residual exposure copper plating film 16 and the residual silver-plated film 22 of seepage silver 24, part.
Table 2
| Numbering | Electrolytic stripping liquid | Current density (A/dm 2) | Treatment time (sec) | The silver-plated film of part | |
| Whether there is spot | Whether glossiness changes | ||||
| ????1 | Electrolytic stripping liquid 1 | ????1 | ????10 | Not | Not |
| ????2 | The same | ????0.5 | ????10 | Not | Not |
| ????3 | Electrolytic stripping liquid 2 | ????0.5 | ????4 | Not | Not |
| ????4 | The same | ????0.5 | ????10 | Not | Not |
| ????5 | Electrolytic stripping liquid 3 | ????1 | ????30 | Not | Not |
| ????6 | Electrolytic stripping liquid 4 | ????0.5 | ????3 | Not | Not |
| ????7 | Electrolytic stripping liquid 5 | ????1 | ????2 | Not | Not |
| ????8 | The same | ????2 | ????5 | Not | Not |
| ????9 | Electrolytic stripping liquid 6 | ????1 | ????3 | Not | Not |
| ????10 | Electrolytic stripping liquid 7 | ????0.3 | ????10 | Not | Not |
| ????11 | Electrolytic stripping liquid 8 | ????0.5 | ????20 | Not | Not |
| ????12 * | Electrolytic stripping liquid 9 | ????1 | ????2 | Not | Not |
| ????13 * | The same | ????2 | ????5 | Be | Be (burning) |
Annotate: numbering 1-11 is embodiment; Numbering 12
*With 13
*Be the comparative example.
" burning " speech representative as local etching result's silver surface because of uneven sur-face peeling become hackly phenomenon and state.
As seeing that from table 2 is clear adopt the 1st to No. 12 condition, the result is very good, do not observe on the silver-plated film 22 of part spottiness or glossiness and change.On the contrary, adopt No. 13 condition, observed spottiness or glossiness variation on the silver-plated film 22 of part.
Embodiment 2
Adopt electrolytic stripping liquid 5 as shown in table 1, the copper and the silver of specified amount are handled, then, measure subsequently copper and silver-colored detachment rate.Detachment rate is to obtain like this: the copper and the silver of anticipating equivalent in electrolytic stripping liquid 5, in table 2, make the anodic copper sheet in the electrolytic stripping liquid 5 or silver strip carries out electrolytic stripping to immersing under No. 7 electrolytic stripping condition again, measure the minimizing of copper sheet or silver strip weight after electrolytic stripping.
Fig. 3 shows the result who measures the relevant copper that obtains and silver-colored detachment rate with the treatment capacity of electrolytic stripping liquid 5 pretreated copper and silver by changing.
Can know from table 3 and to find out, even when the pre-treatment amount of copper and silver increases, detachment rate silver is tending towards becoming slow slightly although the detachment rate of copper is tending towards becoming fast slightly, but (directly electrolyzer is initial constitute after) copper and silver-colored detachment rate are compared when pre-treatment amount when copper and silver is zero respectively, and front and back almost are identical speed.
Like this, use electrolytic stripping liquid 5, even copper increases with silver-colored treatment capacity, the detachment rate of copper and silver and the speed in the direct electrolytic stripping liquid after the initial formation of electrolyzer are consistent, thereby can prolong the replacing pitch time of electrolytic stripping liquid 5.
Comparative Examples
Fig. 4 shows at table 2 the 12nd
*Number the electrolytic stripping condition under with embodiment 2 in identical mode measure the result of the detachment rate of the relevant copper of acquisition and silver.
Can know from table 4 and to find out, even the detachment rate of (directly after the initial formation of electrolyzer) copper and silver is fine when the pre-treatment amount of copper and silver is respectively zero, but along with the increase of copper and silver-colored pre-treatment amount, the detachment rate of copper sharply descends, and becomes a constant subsequently.
Can think that this phenomenon all generates this fact of complex compound easily because of cyano compound and copper and silver and causes.That is to say, although contain the electrolytic stripping liquid of cyano compound in the time of can thinking beginning copper and silver all had very high stripping ability, but when the concentration of silver in the electrolytic stripping liquid increases, copper generation replacement(metathesis)reaction in silver ions in the electrolytic stripping liquid and the copper plating film that will peel off causes the detachment rate of copper to reduce.
Can clearly be seen that from Fig. 4, for keep electrolytic stripping liquid 9 directly electrolyzer is initial constitute after to the detachment rate of copper and silver, need frequent replacing electrolytic stripping liquid 9.
The present invention is illustrated in detail and with reference to specific embodiments, and those skilled in the art is very clear, can make various changes and modification and without prejudice to the spirit and scope of the invention.
The application is based on Japanese Patent JP 2003-413387 (application on December 11st, 2003), and its content is incorporated in herein as a reference.
Claims (10)
1. copper-stripping electrolytic solution of cyano-containing compound not, this electrolytic solution contains copper compound or aromatic nitro compound is made copper oxidant, and its pH value is 9 to 12.
2. copper-stripping electrolytic solution according to claim 1, wherein copper compound is by following material deutero-cuprammonium complex:
Be selected from the ammonium source of the group of forming by ammoniacal liquor and ammonium salt; And
Be selected from the copper source of the group of forming by copper sulfate, copper carbonate, cupric oxalate and copper hydroxide.
3. copper-stripping electrolytic solution according to claim 1, this electrolytic solution also comprise at least a following compound that is selected from: phosphoric acid and salt thereof, organic acid and salt thereof, carbonate, supercarbonate and aminocarboxylic acid and salt thereof.
4. copper-stripping electrolytic solution according to claim 1, this electrolytic solution also comprise a kind ofly can make silver-colored stripper with the compound of silver-colored reacting generating complex.
5. copper-stripping electrolytic solution according to claim 4, wherein said can be pyridine carboxylic acid, thiocyanate-, T10 or succinimide with the compound of silver-colored reacting generating complex.
6. copper-stripping electrolytic solution according to claim 1, this electrolytic solution also comprises a kind of tensio-active agent.
7. copper-stripping electrolytic solution according to claim 6, wherein said tensio-active agent are to contain the tensio-active agent of polyoxyethylene chain or fluorine-containing tensio-active agent.
8. the method for an electrolytic stripping copper, this method comprise the copper plating film that adopts copper-stripping electrolytic solution electrolytic stripping according to claim 1 to expose from silver-plated film, and this silver-plated membrane portions covers on the copper plating film that is formed at the whole surface of element,
Wherein described element is immersed in the copper-stripping electrolytic solution also as anode.
9. the method for electrolytic stripping copper according to claim 8 is wherein used and can not made negative electrode by the metal electrode of wash-out in electrolytic stripping liquid.
10. the method for electrolytic stripping copper according to claim 8, the lead frame of wherein said element for making by ferrous alloy material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003413387A JP4264338B2 (en) | 2003-12-11 | 2003-12-11 | Copper electrolytic stripping solution and electrolytic stripping method |
| JP413387/2003 | 2003-12-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1626703A true CN1626703A (en) | 2005-06-15 |
Family
ID=34650502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004100860305A Pending CN1626703A (en) | 2003-12-11 | 2004-10-22 | Electrolytic copper-stripping liquid and electrolytic stripping method |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20050126926A1 (en) |
| JP (1) | JP4264338B2 (en) |
| KR (1) | KR20050058184A (en) |
| CN (1) | CN1626703A (en) |
| TW (1) | TWI385283B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102168290A (en) * | 2011-04-08 | 2011-08-31 | 哈尔滨工业大学 | Cyanide-free silver plating electroplating solution and preparation method and electroplating method thereof |
| CN103397373A (en) * | 2010-06-25 | 2013-11-20 | 张红雨 | Deplating solution |
| CN104404611A (en) * | 2014-11-28 | 2015-03-11 | 江门市瑞期精细化学工程有限公司 | Electrolytic stripping agent for copper alloy surface coating and preparation method thereof |
| CN105543948A (en) * | 2015-12-23 | 2016-05-04 | 苏州卓融新能源科技有限公司 | Copper stripping process for dummy plates/corrugated plates for PCB electroplating |
| EP3168332B1 (en) | 2015-03-13 | 2019-03-13 | Okuno Chemical Industries Co., Ltd. | Electrolytic stripping agent for removing palladium from a jig |
| CN109778299A (en) * | 2019-02-22 | 2019-05-21 | 江门市瑞期精细化学工程有限公司 | A kind of release agent for electrolytic of iron-based material copper coating layer and preparation method thereof and stripping technology |
| CN111487267A (en) * | 2020-04-09 | 2020-08-04 | 哈尔滨工业大学 | Method for stripping double-layer oxide film defect in aluminum bronze alloy |
| CN113652694A (en) * | 2021-06-24 | 2021-11-16 | 广东桐鸣环保科技有限公司 | Copper plating layer stripping liquid and stripping method |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009108922A1 (en) * | 2008-02-28 | 2009-09-03 | Aeromet Technologies, Inc. | Methods for removing precious metal-containing coatings and recovery of precious metals therefrom |
| US8647492B2 (en) | 2009-07-23 | 2014-02-11 | Ceramatec, Inc. | Method of producing coupled radical products from biomass |
| US9957622B2 (en) | 2009-07-23 | 2018-05-01 | Field Upgrading Limited | Device and method of obtaining diols and other chemicals using decarboxylation |
| US9493882B2 (en) * | 2010-07-21 | 2016-11-15 | Ceramatec, Inc. | Custom ionic liquid electrolytes for electrolytic decarboxylation |
| KR101915824B1 (en) | 2011-01-25 | 2018-11-06 | 필드 업그레이딩 리미티드 | Production of fuel from chemicals derived from biomass |
| DE102011005918A1 (en) * | 2011-03-22 | 2012-09-27 | Airbus Operations Gmbh | Peelable anodizing agent, especially for local anodic oxidation of metal surfaces |
| CN104882494B (en) * | 2015-04-27 | 2017-02-22 | 中国科学院光电技术研究所 | Film stripping technology for removing silver reflecting film using chromium-containing material as adhesive layer |
| KR102226075B1 (en) | 2017-04-05 | 2021-03-11 | 단국대학교 산학협력단 | A hydrogen gas filter using proton beam |
| CN113122906B (en) * | 2021-03-23 | 2022-11-15 | 广州市睿承科技有限公司 | Electric release oil synergist |
| KR102534371B1 (en) * | 2021-08-30 | 2023-05-26 | 이강익 | Portable Electrolytic polisher Using Neutral Salt Electrolyte |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2596307A (en) * | 1947-11-05 | 1952-05-13 | Charles Litzenberg | Process of electrostripping electrodeposited metals |
| US4264420A (en) * | 1979-10-29 | 1981-04-28 | Oxy Metal Industries Corporation | Electrolytic stripping bath and process |
| JPS6056800B2 (en) * | 1982-08-11 | 1985-12-11 | 新光電気工業株式会社 | Method for removing protruding parts of base copper plating in partial silver plating and method for finishing surface of silver plating |
| US7128825B2 (en) * | 2001-03-14 | 2006-10-31 | Applied Materials, Inc. | Method and composition for polishing a substrate |
-
2003
- 2003-12-11 JP JP2003413387A patent/JP4264338B2/en not_active Expired - Fee Related
-
2004
- 2004-10-15 KR KR1020040082415A patent/KR20050058184A/en not_active Application Discontinuation
- 2004-10-22 TW TW093132148A patent/TWI385283B/en not_active IP Right Cessation
- 2004-10-22 US US10/971,898 patent/US20050126926A1/en not_active Abandoned
- 2004-10-22 CN CNA2004100860305A patent/CN1626703A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103397373A (en) * | 2010-06-25 | 2013-11-20 | 张红雨 | Deplating solution |
| CN102168290A (en) * | 2011-04-08 | 2011-08-31 | 哈尔滨工业大学 | Cyanide-free silver plating electroplating solution and preparation method and electroplating method thereof |
| CN102168290B (en) * | 2011-04-08 | 2012-10-17 | 哈尔滨工业大学 | Cyanide-free silver plating electroplating solution and preparation method and electroplating method thereof |
| CN104404611A (en) * | 2014-11-28 | 2015-03-11 | 江门市瑞期精细化学工程有限公司 | Electrolytic stripping agent for copper alloy surface coating and preparation method thereof |
| EP3168332B1 (en) | 2015-03-13 | 2019-03-13 | Okuno Chemical Industries Co., Ltd. | Electrolytic stripping agent for removing palladium from a jig |
| US11649558B2 (en) | 2015-03-13 | 2023-05-16 | Okuno Chemical Industries Co., Ltd. | Electrolytic stripping agent for jig |
| CN105543948A (en) * | 2015-12-23 | 2016-05-04 | 苏州卓融新能源科技有限公司 | Copper stripping process for dummy plates/corrugated plates for PCB electroplating |
| CN105543948B (en) * | 2015-12-23 | 2017-10-31 | 苏州卓融新能源科技有限公司 | It is a kind of for PCB electroplate accompany plating plate/drag cylinder plate move back process for copper |
| CN109778299A (en) * | 2019-02-22 | 2019-05-21 | 江门市瑞期精细化学工程有限公司 | A kind of release agent for electrolytic of iron-based material copper coating layer and preparation method thereof and stripping technology |
| CN111487267A (en) * | 2020-04-09 | 2020-08-04 | 哈尔滨工业大学 | Method for stripping double-layer oxide film defect in aluminum bronze alloy |
| CN111487267B (en) * | 2020-04-09 | 2023-04-14 | 哈尔滨工业大学 | Method for stripping double-layer oxide film defect in aluminum bronze alloy |
| CN113652694A (en) * | 2021-06-24 | 2021-11-16 | 广东桐鸣环保科技有限公司 | Copper plating layer stripping liquid and stripping method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005171320A (en) | 2005-06-30 |
| TWI385283B (en) | 2013-02-11 |
| KR20050058184A (en) | 2005-06-16 |
| TW200519238A (en) | 2005-06-16 |
| US20050126926A1 (en) | 2005-06-16 |
| JP4264338B2 (en) | 2009-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1626703A (en) | Electrolytic copper-stripping liquid and electrolytic stripping method | |
| CN1170963C (en) | Cyanide-free monovalent copper eletroplating solutions | |
| CN1084396C (en) | Silver plating bath and silver plating method using same | |
| CN1263570A (en) | Process for manufacture of high quality very low profile copper foil and copper foil produced thereby | |
| CN1553970A (en) | Method of anodizing of magnesium and magnesium alloys and producing conductive layers on an anodized surface | |
| CN101041904A (en) | Magnesium product and its film plating method | |
| CN1327489A (en) | Electrolytic copper foil with carrier foil and method for manufacturing the same and copper-clad laminate using the electrolytic copper foil with carrier foil | |
| CN100343423C (en) | Electrolytic copper plating method phosphorous cooper anode for electrolytic copper plating method said semiconductor wafer having low particle adhension plated with said method and anode | |
| CN1196391C (en) | Method for surface treatment of copper foil | |
| CN1944716A (en) | Non-cyanogen type electrolytic gold plating bath for bump forming | |
| CN1194587C (en) | Production method of copper foil for fine line use | |
| CN1309881A (en) | Method for metal coating of substrates | |
| CN1432074A (en) | Electrolyte and method for depositing tin-silver alloy layers | |
| CN1524132A (en) | Regeneration method for a plating solution | |
| FR2807450A1 (en) | ELECTROLYTIC BATH INTENDED FOR THE ELECTROCHEMICAL DEPOSIT OF PALLADIUM OR ITS ALLOYS | |
| CN1302155C (en) | Method and device for electrolytic treatment of electrically conducting surfaces separated plates and film material pieces in addition to uses of said method | |
| CN1381616A (en) | Electrolytic phosphate chemical treatment method | |
| CN112176366A (en) | Electrolyte of high-ductility electrolytic copper foil and application | |
| CN1543517A (en) | Magnesium anodisation system and methods | |
| CN1638198A (en) | Terminal having surface layer ,and part and product having the same | |
| CN110528042B (en) | Semiconductor device electroplating method and activation tank for electroplating | |
| JP4462851B2 (en) | Manufacturing method of conductive member | |
| CN1392289A (en) | Regenerating method for corrosion liquid and corrosion device | |
| CN109252197B (en) | Method for electroplating silver on carburized part | |
| CN1714176A (en) | Plain or zinc-plated steel plate coated with a zinc or zinc alloy layer comprising a polymer, and method for making same by electroplating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20050615 |