CN1421546A - Palladium electroplating liquid - Google Patents
Palladium electroplating liquid Download PDFInfo
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- CN1421546A CN1421546A CN 01130247 CN01130247A CN1421546A CN 1421546 A CN1421546 A CN 1421546A CN 01130247 CN01130247 CN 01130247 CN 01130247 A CN01130247 A CN 01130247A CN 1421546 A CN1421546 A CN 1421546A
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- palladium
- salt
- plating
- electroplating liquid
- electroplating
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- 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
- H01L2924/01—Chemical elements
- H01L2924/01046—Palladium [Pd]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01078—Platinum [Pt]
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Abstract
The present invention is palladium electroplating solution containing at least soluble palladium salt 1-60 g/L, amino sulfonic acid or its salt 0.1-300 g/L and essentially no lustring agent. With the palladium electroplating solution, one palladium coating of needle crystal may be formed on the surface of electroplated substrate and thus one electrolytic layer with excellent resin attaching capacity may be formed on the surface of the substrate.
Description
Invention field
The invention relates to the palladium electroplating liquid of electroplating usefulness.In more detail, be about forming the palladium electroplating liquid of the good plating face of resin sticking power.
Background technology
Palladium electroplating liquid is practicability in the electroplating processes that electric electronic element is used up to the present, but in recent years, also wish to use palladium electroplating liquid in the field of lead frame.Use the semiconductor element of lead frame, generally be on lead frame, to carry semi-conductor chip, between the internal lead of the electrode of semi-conductor chip and lead frame, implement wire-bonded, then with the press body of sealing resin cover semi-conductor and wire-bonded portion around after, the outside framework of excision lead frame and making.At this moment, silver-plated in order to carry out good wire-bonded in advance in the enforcement of the tip of internal lead, and after semiconductor element constitutes, implement the plating solder on the surface of outer lead.
But, in solder, contain lead, thereby worry that solder is to problems such as environment impact.Therefore, the surrogate as the plating solder of the outer lead of lead frame uses the plating palladium just to come on the scene.In addition, as the silver plated surrogate of internal lead, use the plating palladium also just to come on the scene.
In the lead frame purposes, use the occasion of palladium electroplating liquid, concerning electrolytic coating, the general hope and the resin sticking power of sealing resin, the excellent propertys such as wettability, ductility, wire-bonded, soldering joint reliability, resistance to migration and solidity to corrosion of the solder behind the thermal history.
Especially, be important in the occasion of using palladium electroplating liquid and the resin sticking power of sealing resin to the lead frame purposes.Therefore, wish to improve the resin sticking power of palladium electroplating liquid and sealing resin.
Utilize the means of the sticking power of plating palladium layer (promptly electroplating face) that palladium electroplating liquid forms and sealing resin as raising, for example open in the 2000-077594 communique and disclose the spy, by using acid corrosion lead frame starting material, produce the concavo-convex state of appropriateness on the plated nickel film surface that is becoming ground, utilize consequent anchoring effect to strengthen sticking power between palladium plated film and sealing resin.But, in the method, except the electroplating processes operation, also need to carry out the operation of corrosion treatment in advance, consider from complicacy or the processing cost aspect handled, how much be unsatisfied.In addition, if also consider lead frame purposes in addition, also may not wish roughening by the surface of corrosion generation.
On the other hand, different with the occasion of utilizing palladium electroplating liquid, about the occasion of utilizing copper plating bath to handle, for example open in the 2000-096284 communique and disclose the spy, by separating out needle crystal, improve the resin sticking power of coating and interlaminar resin at coating surface.But, just known to the inventor, also be not implemented in the report that coating surface produces needle crystal about the electroplating processes of utilizing palladium.Copper facing and plating palladium have a great difference on its character, plating condition and use-pattern.
Brief summary of the invention
The inventor, modulation this time contain at least the thionamic acid of the soluble palladium salt of specified quantitative and specified quantitative or its salt, do not contain the palladium electroplating liquid of gloss-imparting agent in fact, by using this electroplate liquid to plate palladium, obtain to form the understanding of plating palladium layer with needle crystal on the surface.The present invention is based on such understanding.
Therefore, the object of the present invention is to provide, can show good resin sticking power, can form the palladium electroplating liquid that the surface is the plating palladium layer of needle crystal shape.
Therefore, be the soluble palladium salt that contains 1～60g/L (converting) at least, thionamic acid or its salt of 0.1～300g/L according to palladium electroplating liquid of the present invention as the palladium amount, do not contain the palladium electroplating liquid of gloss-imparting agent in fact.
In addition, comprise: use above-mentioned palladium electroplating liquid to prepare plating bath, then in this plating bath, make bath temperature reach 30～70 ℃, cathode current density and reach 0.2～20A/dm according to plating palladium method of the present invention
2,, on this ground, form the plating face on surface with needle crystal shape by ground is carried out electroplating processes.
Be to use above-mentioned palladium electroplating liquid according to plating palladium goods of the present invention, electroplating processes forms by ground is carried out.
Use palladium electroplating liquid of the present invention to carry out electroplating processes, can form coating with needle crystal shape surface.By forming such coating, just can expect anchoring effect, therefore to compare with the surface that forms glossiness, formed coating has good resin sticking power.The coating outward appearance of this moment, coating surface becomes the needle crystal shape on microcosmic, therefore comes down to lacklustre usually.In addition, the goods that coating that forms as described above by combination and resin obtain, the mutual sticking power of coating and resin is good, thereby can keep stable rerum natura for a long time.In addition, be that bath life is long, the also good palladium electroplating liquid of current efficiency according to palladium electroplating liquid of the present invention.Therefore, can be suitable as the used for lead frame plating bath according to palladium electroplating liquid of the present invention uses.
Specifying of invention
Palladium electroplating liquid
According to palladium electroplating liquid of the present invention is to contain the thionamic acid of the soluble palladium salt of specified quantitative and specified quantitative or its salt at least, do not contain the palladium electroplating liquid of gloss-imparting agent in fact.And this plating bath uses in electroplating processes usually.
At this, so-called gloss-imparting agent is to be purpose and the additive that adds in plating bath to keep gloss at plating face, typically refers to plate surface is had the inorganic of homogenizing and organic system additive.As such gloss-imparting agent, if those skilled in the art are habitually practised, can comprise, for example can enumerate the gloss-imparting agent of what is called as benzoic sulfimide, benzene sulfonic acid sodium salt, benzsulfamide, sulfocarbolic acid, methylene-bis (naphthalene) sulfonic acid, and picture 2-butyne-1,4-glycol, phenyl aldehyde-O-sodium sulfonate, 2-butylene-1, so-called secondary gloss-imparting agent that 4-glycol, sulfonic acid allyl ester are such etc.
Plating bath of the present invention owing to have specific composition, can form the needle crystal shape at formed coating surface, thereby its outward appearance comes down to lacklustre.Therefore, plating bath does not contain gloss-imparting agent in fact, is forming tarnish, promptly form think on the needle crystal shape surface favourable.Therefore, the feature according to plating bath of the present invention is not contain gloss-imparting agent in fact.At this, so-called " not containing in fact ", comprise the situation that does not contain above-mentioned gloss-imparting agent, also comprise the situation that in plating bath, contains gloss-imparting agent as the amount of gloss-imparting agent effect degree not bringing into play certainly.
In addition,, preferably also contain conductive compound, and as required, also can contain other any compositions except that above-mentioned gloss-imparting agent again according to palladium electroplating liquid of the present invention.
Soluble palladium salt
As the soluble palladium salt that uses in the present invention, if to the plating bath solubility and also can in plating bath, supply with palladium ion, just have no particular limits, for example can enumerate the ammino complex salt class, nitrate, muriate of palladium etc.
Wherein, as the ammino complex salt class of palladium, muriate, bromide, iodide, nitrite, the nitrate of the ammino complex salt of the suitable palladium enumerated, perhaps vitriol etc.In addition, as above-mentioned ammino complex salt, suitable two ammino complex salts or the four ammino complex salts enumerated.
Therefore, the concrete dichloro four ammino palladium (Pd (NH that for example can enumerate
3)
4C1
2), dibromo four ammino palladium (Pd (NH
3)
4Br
2), diiodo-four ammino palladium (Pd (NH
3)
4I
2), two nitrite anions, four ammino palladium (Pd (NH
3)
4(ONO)
2), dinitro acid group four ammino palladium (Pd (NH
3)
4(NO
3)
2), two inferior sulfate radicals, four ammino palladium (Pd (NH
3)
4(SO
3)
2), two sulfate radicals, four ammino palladium (Pd (NH
3)
4(SO
4)
2), dinitrobenzene four ammino palladium (Pd (NH
3)
4(NO
2)
2), dichloro two ammino palladium (Pd (NH
3)
2Cl
2), dibromo two ammino palladium (Pd (NH
3)
2Br
2), diiodo-two ammino palladium (Pd (NH
3)
2I
2), two nitrite anions, two ammino palladium (Pd (NH
3)
2(ONO)
2), dinitro acid group diamino closes palladium (Pd (NH
3)
2(NO
3)
2), two inferior sulfate radicals, two ammino palladium (Pd (NH
3)
2(SO
3)
2), two sulfate radicals, two ammino palladium (Pd (NH
3)
2(SO
4)
2), dinitrobenzene two ammino palladium (Pd (NH
3)
2(NO
2)
2) etc.These salt can synthesize, but also can use commercially available.
According to preferred forms of the present invention, soluble palladium salt is dichloro four ammino palladium (Pd (NH preferably
3)
4Cl
2), two nitrite anions, four ammino palladium (Pd (NH
3)
4(ONO)
2), dinitro acid group four ammino palladium (Pd (NH
3)
4(NO
3)
2), dinitrobenzene four ammino palladium (Pd (NH
3)
4(NO
2)
2), dichloro two ammino palladium (Pd (NH
3)
2Cl
2), two nitrite anions, two ammino palladium (Pd (NH
3)
2(ONO)
2), dinitro acid group diamino closes palladium (Pd (NH
3)
2(NO
3)
2) or dinitrobenzene two ammino palladium (Pd (NH
3)
2(NO
2)
2).
They may be used alone, two or more kinds can also be used.
In the present invention, soluble palladium salt converts as the palladium amount in plating bath, contains 1～60g/L, preferably contains 2～20g/L.
At this, what is called is " it is 1～60g/L that soluble palladium salt converts as the palladium amount " for example, and palladium (Pd) amount in synthetic plating bath that is meant becomes the soluble palladium salt amount of 1～60g/L amount.
Thionamic acid or its salt
According to palladium electroplating liquid of the present invention, as must composition, contain thionamic acid or its salt and constitute.
In the present invention, salt as thionamic acid, the electroconductibility that can supply with thionamic acid and need only electroplate liquid in electroplate liquid does not impact, just have no particular limits, for example can an alkali metal salt of thionamic acid, the alkaline earth salt of thionamic acid and the ammonium salt of thionamic acid etc. be shown example.More particularly, as the suitable thionamic acid enumerated sodium, thionamic acid potassium, Ammonium sulfamate, thionamic acid calcium etc.They may be used alone, two or more kinds can also be used.
In the present invention, thionamic acid or its salt cooperate 0.1～300g/L in plating bath, better cooperate 1～200g/L, fits best 1～100g/L.
Conductive compound
According to palladium electroplating liquid of the present invention, preferably also contain conductive compound and constitute.So-called in the present invention conductive compound for electroconductibility and the electroplating efficiency that improves electroplate liquid adds, if be not deleterious to electroplating processes, just has no particular limits, and for example can use various simple salts, strong acid and highly basic etc.Therefore, as the conductive compound of using in the present invention, do not wish to contain the by product that rerum natura is given baneful influence by the electrolysis generation.According to plating bath of the present invention is the plating bath that can show stable rerum natura continuously for a long time.
In the present invention, as conductive compound, the salt of preferably from the group that nitrate, muriate, vitriol, phosphoric acid salt, oxalate, oxyhydroxide, borate, tartrate and carbonate constitute, selecting for example.Object lesson as such conductive compound, can enumerate picture ammonium nitrate, the nitrate that saltpetre or SODIUMNITRATE are such, picture ammonium chloride, the muriate that Repone K or sodium-chlor are such, picture ammonium sulfate, the vitriol that vitriolate of tartar or sodium sulfate are such, picture ammonium phosphate, the phosphoric acid salt that potassiumphosphate or sodium phosphate are such, the picture ammonium oxalate, the oxalate that potassium oxalate or sodium oxalate are such, the picture ammonium tartrate, the tartrate that soluble tartrate or sodium tartrate are such, picture ammonium hydroxide, the oxyhydroxide that potassium hydroxide or sodium hydroxide are such, the picture ammonium borate, the borate that potassium borate or Sodium Tetraborate are such is as volatile salt, the carbonate that salt of wormwood or yellow soda ash are such etc.
These salt may be used alone, two or more kinds can also be used.
In the present invention, conductive compound better cooperates 0.1～500g/L in plating bath, better cooperate 20～400g/L, fits best 40～200g/L.
Other any composition
Plating bath of the present invention can also contain other any composition as required.As other so any compositions, for example can enumerate pH and adjust agent, buffer reagent, tensio-active agent, surface conditioner, coordination agent, dispersion agent etc.
In according to palladium electroplating liquid of the present invention, be purpose with the pH that adjusts this liquid, can also contain pH and adjust agent.When the adjustment of plating bath and in which of electroplating processes process, can suitably add pH and adjust agent.The pH of palladium electroplating liquid of the present invention is normally in 6～9 the scope, preferably is adjusted in 6.5～8 the scope.
In the present invention, pH adjusts agent if can adjust the adjustment agent of the pH of plating bath, just has no particular limits, and for example adjusts agent as suitable pH, can use ammoniacal liquor, dilute sulphuric acid, dilute hydrochloric acid, rare nitric acid etc.
In addition, in plating bath of the present invention,, can also contain buffer reagent for the pH that makes plating bath maintains certain scope.As such buffer reagent, as long as palladium salt, sulfamate, and then other compositions such as conductive compound are not impacted containing in the electroplate liquid, just have no particular limits, can suitably select the buffer reagent of habitually practising and use.
Can also contain tensio-active agent according to plating bath of the present invention.As such tensio-active agent, can enumerate known nonionogenic tenside and cats product.
As surface conditioner, for example can enumerate the alcohols as ethanol, butyleneglycol, glycerol, glycol-ether, as having glucose, sucrose, starch, being the organic compound the isomerized sugar of mixture of glucose and fructose with OH base, organic compound as acetaldehyde, formaldehyde with CHO base, organic compound as acetone, Pinacolone, methyl ether, methyl phenyl ketone, pimelinketone with CO base, and the organic compound with N base as amines such as methylamine, trolamine, pyridine, bipyridine etc.
Electroplating processes
Using palladium electroplating liquid of the present invention to carry out under the situation of electroplating processes, as mentioned above, typically the pH of plating bath is being adjusted in 6～9 the scope, preferably be adjusted in 6.5～8 the scope.And, the temperature of plating bath typically is adjusted to 30～70 ℃, preferably be adjusted in 45～65 ℃ the scope and electroplate to good.
And then the cathode current density when electroplating processes is typically 0.2～20A/dm
2, 1～10A/dm preferably
2
In addition, the thickness of formed plating palladium layer has no particular limits, but can change aptly by employed current density and electroplating time etc.
Utilize the electroplating processes of palladium electroplating liquid of the present invention, as required, can use habitual electroplating processes method to implement.Therefore, for example in the process of electroplating processes, can suitably stir electroplate liquid, and meanwhile carry out electroplating processes, in addition, as required and electroplating processes the time or before and after it, carry out the filtration treatment of plating bath.And then, follow the carrying out of electroplating processes, the occasion that the palladium concentration in plating bath reduces is only added the soluble palladium salt component in this plating bath, also can proceed electroplating processes.
As utilizing palladium electroplating liquid of the present invention to implement galvanized ground, for example can enumerate materials of lead frame, connector with ground etc., but be typically materials of lead frame.
At this, the material of so-called materials of lead frame if the material that uses just has no particular limits, for example can be enumerated copper alloy, iron nickel alloy, recombiner etc. in semiconductor element.In addition, electroplate, comprise the outer lead of materials of lead frame and any of internal lead are implemented to electroplate said on materials of lead frame, enforcement.As the connector ground, the connector that for example can enumerate the copper that uses or copper alloy system in the semi-conductor correlated product is with ground etc. at this, but especially is not limited to these.
The method of plating palladium is provided in another embodiment of the invention, and this method comprises: use above-mentioned palladium electroplating liquid to prepare plating bath, in this plating bath, make the temperature of this plating bath reach 30～70 ℃, make cathode current density reach 0.2～20A/dm
2,, be formed on the plating face that has needle crystal shape surface on this ground by ground is carried out electroplating processes.
In addition, in other embodiments of the present invention, also provide, ground is electroplated, and form the goods that plate palladium by using above-mentioned palladium electroplating liquid.These goods preferably utilize above-mentioned electro-plating method to form.
And then, also providing electro-plating method according to other preferred forms of the present invention, this method is the manufacture method of the goods of plating palladium, it comprises uses above-mentioned palladium electroplating liquid to prepare plating bath, in this plating bath, make this plating bath temperature reach 30～70 ℃, make cathode current density reach 0.2～20A/dm
2, by ground is carried out electroplating processes, be formed on the plating face that has needle crystal shape surface on this ground, then cover the surface of its needle crystal shape with sealing resin.
At this,, for example can enumerate Resins, epoxy (for example line style phenol aldehyde type), silicone resin etc. as the sealing resin that can use.
At this, the customary means that can use those skilled in the art to know is suitably carried out the operation with sealing resin covering plating face.
The stickiness of the plate surface of these resins and needle crystal shape is good, the use of these resins, also can expect to improve and plating face between the anchoring effect of associativity, be favourable therefore providing on the plated item of excellent in stability.
Embodiment
Below, specifically describe the present invention according to embodiment, but these embodiment not delimit the scope of the invention.
Example 1
Modulation has the palladium electroplating liquid 1 of following composition.The temperature of this plating bath is 55 ℃.
Palladium electroplating liquid 1:
Dichloro four ammino palladium 2g/L (converting) as the Pd amount
Thionamic acid sodium 100g/L is adjusted to pH7 with ammonium hydroxide or dilute sulphuric acid
As test substrate, use Ha Le セ Le copper coin (can buy) from Yamamoto Gold Plating Tester Co., Ltd., adopt habitual means to implement the matt nickel plating (Ni) of 1 μ m in advance.Then, to the ground that obtains, in the bath of above-mentioned palladium electroplating liquid, while stir plating bath, at current density 3.5A/dm
2Condition under, carry out 10 seconds electroplating processes, obtain electrolytic coating, with this as electroplated sample 1.
Example 2
Be modulated into palladium electroplating liquid 2 with following composition.The temperature of this plating bath is 55 ℃.
Palladium electroplating liquid 2:
Dinitrobenzene four ammino palladium 20g/L (converting) as the Pd amount
Ammonium sulfamate 50g/L
Be adjusted to pH7 then with ammonium hydroxide or dilute sulphuric acid, use this plating bath and example 1 to carry out electroplating processes in the same manner, obtain electroplated sample 2.Example 3 is modulated into the palladium electroplating liquid 3 with following composition.The temperature of this plating bath is 55 ℃.
Palladium electroplating liquid 3:
Dichloro four ammino palladium 2g/L (converting) as the Pd amount
Thionamic acid sodium 100g/L
SODIUMNITRATE 400g/L
Be adjusted to pH7 then with ammonium hydroxide or dilute sulphuric acid, use this plating bath and example 1 to carry out electroplating processes in the same manner, obtain electroplated sample 3.Example 4 is modulated into the palladium electroplating liquid 4 with following composition.The temperature of this plating bath is 55 ℃.
Palladium electroplating liquid 4:
Dinitrobenzene four ammino palladium 20g/L (converting) as the Pd amount
Ammonium sulfamate 50g/L
Ammonium sulfate 100g/L
Be adjusted to pH7 then with ammonium hydroxide or dilute sulphuric acid, use this plating bath and example 1 to carry out electroplating processes in the same manner, obtain electroplated sample 4.Example 5 (comparative example) is modulated into the palladium electroplating liquid 5 with following composition.The temperature of this plating bath is 55 ℃.
Palladium electroplating liquid 5:
Dichloro four ammino palladium 2g/L (converting) as the Pd amount
Thionamic acid sodium 100g/L
Pyridine-3-sulphonic acid 10g/L
Be adjusted to pH7 then with ammonium hydroxide or dilute sulphuric acid, use this plating bath and example 1 to carry out electroplating processes in the same manner, obtain electroplated sample 5.Example 6 (comparative example) is modulated into the palladium electroplating liquid 6 with following composition.The temperature of this plating bath is 55 ℃.
Palladium electroplating liquid 6:
Dinitrobenzene four ammino palladium 20g/L (converting) as the Pd amount
Ammonium sulfamate 50g/L
Ammonium sulfate 100g/L
Potassium sulfite 20g/L
Be adjusted to pH7 then with ammonium hydroxide or dilute sulphuric acid, use this plating bath and example 1 to carry out electroplating processes in the same manner, obtain electroplated sample 6.Example 7 (comparative example)
With the lead frame degreasing, after implementing to utilize the cleanup acid treatment (that is, the acid corrosion operation) of 100g/L ammonium persulphate, with the thickness formation plated nickel film of 0.8 μ m.Thickness with 0.1 μ m forms palladium plated film again on this plated nickel film, obtains electroplated sample 7.
Evaluation test
Resulting palladium electroplating liquid 1～6 and electroplated sample 1～7 are looked like following evaluation test 1～4.
Evaluation test 1: current efficiency
At 55 ℃ of liquid temperature, current density 3.5A/dm
2, under 1 minute the condition of electroplating time, form the plating palladium layer of thickness 0.9 μ m.At this moment, be determined at the changes in weight of the sample in the electroplating processes front and back, obtain plating palladium amount.Resulting plating palladium amount is removed with the theory plating amount of the palladium in the above-mentioned condition, obtained current efficiency (percentage), it is estimated according to following benchmark.
Estimate A: current efficiency is the occasion more than 90%
Estimate B: current efficiency is the occasion less than 90%
Evaluation test 2: electroplate outward appearance
Electroplate optimum current density test method (for example, reference " ELECTORDEPOSITION ", 217-220 page or leaf, NOYES PUBLICATIONS) according to what is called,, the glossy state of plate surface is estimated with the plate surface of each electroplated sample of visual observation.At this, not see glossy as " tarnish ", can see that than " tarnish " glossy is as " semi-gloss " at the plate surface of sample.
Evaluation test 3: the state of plate surface
With scanning electronic microscope (SEM) (Jeol Ltd.'s system: JSM-5600LV) observe the plate surface (condition determination: 10000 times) of each electroplated sample, estimate the state of plate surface.With the surface that forms the needle crystal shape at plate surface as " needle crystal ", represent as " laminated crystalline " to form lamellated crystallization.About sample 7, do not form crystalline state at plate surface, the surface is concavo-convex.
Evaluation test 4: electroplate liquid life-span
Each palladium electroplating liquid that is modulated into is prepared a certain amount of (1 liter) respectively as the test plating bath, use this test plating bath to carry out electroplating processes, the palladium completely consumed that in the unit volume of plating bath, contains.At this moment, electroplating processes being begun sequence of operations that the palladium to the plating bath disappears can be regarded as 1 and takes turns.
One take turns end after, in used plating bath, only add the palladium composition immediately again.At this moment, except adding the palladium composition, do not carry out the plating bath revisal.Then, carry out electroplating processes once more, 1 electroplating processes of taking turns is down implemented in the palladium completely consumed in plating bath.
These programs are proceeded, until since the variation of the rerum natura of plating bath etc. make electroplating processes be difficult to continue, may the galvanized number of taking turns with regard to each electroplate liquid investigation.
Take turns several data based on relevant each electroplate liquid is resulting, according to the liquid life-span of the following benchmark evaluation plating bath of picture.This means that the many more plating baths of wheel number are difficult to cause the liquid deterioration when long-time the use more.
Estimate A: electroplate possible wheel number and be 10 take turns above
Estimate B: electroplate possible wheel number and take turns less than 10
Evaluation result
The evaluation result of above-mentioned test is as shown in table 1.
In the observation of plate surface,, confirmed needle crystal at plate surface for using according to electroplate liquid of the present invention.At this moment, forming the electrolytic coating of needle crystal, also is good with regard to resin sticking power.
Table 1
| Example | Electroplate outward appearance | Current efficiency | The state of plate surface | The liquid life-span |
| ?1 | Matt | ????A | Needle crystal | ????A |
| ?2 | Matt | ????A | Needle crystal | ????A |
| ?3 | Matt | ????A | Needle crystal | ????A |
| ?4 | Matt | ????A | Needle crystal | ????A |
| 5 (comparative examples) | Semi-gloss | ????A | Laminated crystalline | ????B |
| 6 (comparative examples) | Semi-gloss | ????A | Laminated crystalline | ????A |
| 7 (comparative examples) | Matt | ????A | Concavo-convex (noncrystalline shape) | ????- |
Claims (10)
1. palladium electroplating liquid, it is soluble palladium salt and the thionamic acid of 0.1～300g/L or the palladium electroplating liquid of its salt that contains 1～60g/L (converting as the palladium amount) at least, does not contain gloss-imparting agent in fact.
2. the palladium electroplating liquid of claim 1 record, wherein, soluble palladium salt is to select from the group that the muriate of the ammino complex salt of palladium, bromide, iodide, nitrite, nitrate and vitriol are formed.
3. the palladium electroplating liquids of claim 1 or 2 records, wherein, the salt of thionamic acid is to select the group formed of the ammonium salt of the alkaline earth salt of an alkali metal salt, thionamic acid from thionamic acid and thionamic acid.
4. the palladium electroplating liquid of each record in the claim 1～3 wherein, also contains conductive compound.
5. the palladium electroplating liquid of claim 4 record, wherein, conductive compound is to select from the group that nitrate, muriate, vitriol, phosphoric acid salt, oxalate, oxyhydroxide, boric acid, borate, tartrate and carbonate are formed.
6. the palladium electroplating liquid of claim 4 or 5 records wherein, contains the conductive compound of 0.1～500g/L.
7. one kind is plated the palladium method, and this method comprises: the palladium electroplating liquid with each record in the claim 1～6 is prepared plating bath; Then, in this plating bath, make bath temperature reach 30～70 ℃, cathode current density and reach 0.2～20A/dm
2,, on this ground, form the plating face on surface with needle crystal shape by ground is carried out electroplating processes.
8. the method for claim 7 record, wherein, above-mentioned ground is a materials of lead frame.
9. goods that plate palladium, it is to use the palladium electroplating liquid of each record in the claim 1～6, and ground is carried out the plating palladium goods that electroplating processes forms.
10. manufacture method of plating the palladium goods, this manufacture method comprises: the palladium electroplating liquid with each record in the claim 1～6 is prepared plating bath; Then, in this plating bath, make bath temperature reach 30～70 ℃, cathode current density and reach 0.2～20A/dm
2,, on this ground, form plating face with needle crystal shape surface by ground is carried out electroplating processes; And the plating face that covers surface with sealing resin with this needle crystal shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01130247 CN1289716C (en) | 2001-11-30 | 2001-11-30 | Palladium electroplating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01130247 CN1289716C (en) | 2001-11-30 | 2001-11-30 | Palladium electroplating liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1421546A true CN1421546A (en) | 2003-06-04 |
| CN1289716C CN1289716C (en) | 2006-12-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 01130247 Expired - Fee Related CN1289716C (en) | 2001-11-30 | 2001-11-30 | Palladium electroplating liquid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102312228A (en) * | 2010-07-06 | 2012-01-11 | 上海德门电子科技有限公司 | Method for generating electric function material on surface of non-conductive base material |
| CN102586830A (en) * | 2011-01-10 | 2012-07-18 | 深圳市奥美特科技有限公司 | Equipment and method for plating gold or plating palladium on surface of metal wire |
| CN102037162B (en) * | 2008-05-07 | 2013-03-27 | 尤米科尔电镀技术有限公司 | Pd and Pd-Ni electrolyte baths |
| CN105401182A (en) * | 2015-10-14 | 2016-03-16 | 佛山科学技术学院 | Plating solution formula and electroplating method for electroplating thick palladium on stainless steel |
| CN105420773A (en) * | 2015-11-20 | 2016-03-23 | 无锡市嘉邦电力管道厂 | Palladium electroplating liquid containing tetraphenylantimony bromide and electroplating method of palladium electroplating liquid |
| CN106521576A (en) * | 2016-11-29 | 2017-03-22 | 江苏澳光电子有限公司 | Plating solution for copper alloy surface palladium plating and application of plating solution |
| CN108004573A (en) * | 2017-12-12 | 2018-05-08 | 安徽启东热能科技有限公司 | A kind of process of surface treatment of gas-liquid separation disk disk body |
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2001
- 2001-11-30 CN CN 01130247 patent/CN1289716C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102037162B (en) * | 2008-05-07 | 2013-03-27 | 尤米科尔电镀技术有限公司 | Pd and Pd-Ni electrolyte baths |
| CN102312228A (en) * | 2010-07-06 | 2012-01-11 | 上海德门电子科技有限公司 | Method for generating electric function material on surface of non-conductive base material |
| CN102586830A (en) * | 2011-01-10 | 2012-07-18 | 深圳市奥美特科技有限公司 | Equipment and method for plating gold or plating palladium on surface of metal wire |
| CN102586830B (en) * | 2011-01-10 | 2015-12-09 | 深圳市奥美特科技有限公司 | Wire surface gold-plated or plating palladium Apparatus and method for |
| CN105401182A (en) * | 2015-10-14 | 2016-03-16 | 佛山科学技术学院 | Plating solution formula and electroplating method for electroplating thick palladium on stainless steel |
| CN105420773A (en) * | 2015-11-20 | 2016-03-23 | 无锡市嘉邦电力管道厂 | Palladium electroplating liquid containing tetraphenylantimony bromide and electroplating method of palladium electroplating liquid |
| CN106521576A (en) * | 2016-11-29 | 2017-03-22 | 江苏澳光电子有限公司 | Plating solution for copper alloy surface palladium plating and application of plating solution |
| CN108004573A (en) * | 2017-12-12 | 2018-05-08 | 安徽启东热能科技有限公司 | A kind of process of surface treatment of gas-liquid separation disk disk body |
| CN108004573B (en) * | 2017-12-12 | 2020-10-16 | 安徽启东热能科技有限公司 | Surface treatment process for gas-liquid separation disc body |
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