CN105316722A - Palladium electroplating solution containing tetraphenylarsonium bromide and electroplating method of palladium electroplating solution - Google Patents
Palladium electroplating solution containing tetraphenylarsonium bromide and electroplating method of palladium electroplating solution Download PDFInfo
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- CN105316722A CN105316722A CN201510812642.6A CN201510812642A CN105316722A CN 105316722 A CN105316722 A CN 105316722A CN 201510812642 A CN201510812642 A CN 201510812642A CN 105316722 A CN105316722 A CN 105316722A
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- palladium
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Abstract
The invention discloses a palladium electroplating solution containing tetraphenylarsonium bromide and an electroplating method of the palladium electroplating solution. The palladium electroplating solution comprises 5-20 g/L of trans-diamido-palladous bromide in terms of palladium, 60-90 g/L of ammonium bromide, 70-100 g/L of diammonium hydrogen phosphate, 2-5 g/L of 3-pyridine sulphonic acid and 1-4 mg/L of the tetraphenylarsonium bromide. According to the palladium electroplating solution, the trans-diamido-palladous bromide serves as main palladium salt, the tetraphenylarsonium bromide serves as antioxidants, and the dipicolinic acid serves as brightening agent salt, so that the obtained electroplating solution is high in dispersion force and deep-plating capacity, the efficiency of cathode currents is high, and the performance of the electroplating solution is excellent. By the adoption of the electroplating solution, the porosity of a coating obtained through electroplating under the alkaline condition is low, the brightness is high, and the quality of the coating is good.
Description
Technical field
The present invention relates to palladium plating technical field, particularly relate to a kind of palladium electroplating liquid containing tetraphenylphosphonibromide bromide arsenic and electro-plating method thereof.
Background technology
Palladium is the precious metal material of the stable chemical nature being similar to gold.Coating is had the characteristics such as excellent solidity to corrosion, wear resistance and electrical property, palladium is more cheap than gold, therefore coating oneself through being applied in the electronic unit such as appliance contact, junctor, IC lead frame and printed board replacing gold.The problem run in coating application is had: (1) palladium thickness of coating is difficult to control, internal stress trends towards increasing along with the increase of thickness of coating, is difficult to obtain sufficient ductility.(2) the line cohesiveness that palladium coating heat treated is later and solder wettability decline.Along with high performance and the miniaturization of all kinds of e-machine, be all vital characteristic the weldability etc. of coating for electronic unit.
Chinese patent CN101839680A discloses a kind of palladium plating technique, and this technique adopts the brightening agents such as propiolic alcohol.Although this technique technique is comparatively simple, the current efficiency of this plating solution is lower, the poor-performing of plating solution, and the quality of coating is not good yet.
Summary of the invention
In view of this, one aspect of the present invention provides the palladium electroplating liquid containing tetraphenylphosphonibromide bromide arsenic, and the plating solution performance of this electroplate liquid is better, and the quality of coating using this plating solution to obtain is higher.
Containing a palladium electroplating liquid for tetraphenylphosphonibromide bromide arsenic, comprise in palladium 5 ~ 20g/L trans diamino dibrominated palladium, 60 ~ 90g/L brometo de amonio, 70 ~ 100g/L Secondary ammonium phosphate, 0.6 ~ 2.4g/L3-pyridine-sulfonic acid and 1 ~ 4mg/L tetraphenylphosphonibromide bromide arsenic.
Aforementioned preferred formula is, in palladium 10g/L trans diamino dibrominated palladium, 70g/L brometo de amonio, 80g/L Secondary ammonium phosphate, 1.6g/L3-pyridine-sulfonic acid and 3mg/L tetraphenylphosphonibromide bromide arsenic.
In the present invention, tetraphenylphosphonibromide bromide arsenic because of containing As atom, its under the hot conditions of air comparatively palladium be more easily oxidized, to play antioxidant effect preferably to palladium electrolytic coating, thus improve the solder wettability of palladium electrolytic coating.
In the present invention, 3-pyridine-sulfonic acid can significantly improve the bright property of palladium coating.
Dawn known to those skilled in the art, brometo de amonio plays conducting salt.
Take phosphoric acid salt as brightening agent.Phosphoric acid salt can obtain smooth, that glossiness is high, bonding force is good coating.
Aforementioned, trans diamino dibrominated palladium is as the main salt of palladium.Trans diamino dibrominated palladium is flush type molecular structure, and two ammonia lay respectively at the both sides of palladium central atom as part.Compared to Palladous chloride, the former is the divalent palladium existed with complex form, due to the space steric effect of two ammonia, make its not easily in water hydroxide radical is combined and produces palladium hydroxide precipitation, reduction divalent palladium ion and the electrodeposition efficiency of negative electrode.
Except mentioned component, the present invention also can select suitable amounts other in this area the additive commonly used, the such as conven-tional adjuvants such as coordination agent, tensio-active agent, these all can not damage the characteristic of coating.
The present invention provides a kind of electro-plating method, the better performances of the electroplate liquid that the method adopts on the other hand, higher according to quality of coating prepared by the method.
Use an above-mentioned electroplate liquid electric plating method, comprise the following steps:
(1) electroplate liquid is prepared: in water, dissolve each feed composition form electroplate liquid, described often liter of electroplate liquid contains in palladium 5 ~ 20g trans diamino dibrominated palladium, 60 ~ 90g brometo de amonio, 70 ~ 100g Secondary ammonium phosphate, 0.6 ~ 2.4g3-pyridine-sulfonic acid and 1 ~ 4mg tetraphenylphosphonibromide bromide arsenic;
(2) insert in described electroplate liquid with the base material of electroplated and pass into electric current, apply ultrasonic wave simultaneously and electroplate.
Wherein, described electric current is monopulse rectangular wave current; The pulsewidth of described monopulse rectangular wave current is 2 ~ 5ms, and dutycycle is 5 ~ 30%, and average current density is 2 ~ 4A/dm
2.
Wherein, in described step (2), the pH of electroplate liquid is 7.5 ~ 8.5.
Wherein, in described step (2), the temperature of electroplate liquid is 45 ~ 55 DEG C.
Wherein, in described step (2), the time of plating is 3 ~ 9min.
Wherein, in described step (2), the anode of plating and the area ratio of negative electrode are (1 ~ 4): 1.
Wherein, in described step (2), described base material is copper or stainless steel.
Carry out under being plated on Ultrasonic Conditions in the present invention.Hyperacoustic applying mode can adopt ultrasonic generator.The present invention without particular requirement, can adopt commercially available to the concrete model of ultrasonic generator and structure.The hyperacoustic actual conditions of ultrasonic generator, such as ultrasonic power, frequency etc., also have no special requirements, and specifically can select according to practical situation.
Monopulse rectangular wave current is defined as at t
1passing into current density in time is J
pelectric current, at t
2without passing into electric current in time, it is a kind of intermittent pulse current.Dutycycle is defined as t
1/ (t
1+ t
2), frequency is 1/ (t
1+ t
2), mean current is defined as J
pt
1/ (t
1+ t
2).Compare with DC electrodeposition, thickness and the ion concentration distribution of electrostatic double layer all change; While adding electrochemical polarization, reduce concentration polarization, the direct effect of generation is, the coating that pulse plating obtains than DC electrodeposition coating evenly, crystallization is finer and closely woven.Moreover, pulse plating also has: hardness and the wear resistance of (1) coating are all high; (2) solution dispersibility and covering power good; (3) decrease the super plating of part edge, coating distributing homogeneity is good, can save plating solution usage quantity.
The present invention does not add restriction to the process of plating piece after the treatment process of the base material of electroplated before plating and plating, can take conventional pretreatment process, such as cleaning before copper plating, polishing etc.The selection of the electrode of plating also can adopt conventional method to carry out.
The present invention is with trans diamino dibrominated palladium for the main salt of palladium, and using tetraphenylphosphonibromide bromide arsenic as antioxidant, using pyridine dicarboxylic acid as brightening agent salt, make the plating solution of acquisition have good dispersion force and covering power thus, cathode efficiency is high, and plating solution performance is excellent.The porosity that employing electroplates the coating of acquisition in the basic conditions at plating solution is low, and luminance brightness is high, and quality of coating is good.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 2ms, and dutycycle is 30%, and average current density is 2A/dm
2; PH is 7.5, and temperature is 45 DEG C, and electroplating time is 9min.
Embodiment 2
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.6ms, and dutycycle is 25%, and average current density is 2.5A/dm
2; PH is 7.5, and temperature is 45 DEG C, and electroplating time is 5min.
Embodiment 3
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.8ms, and dutycycle is 20%, and average current density is 3A/dm
2; PH is 8.5, and temperature is 55 DEG C, and electroplating time is 6min.
Embodiment 4
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 1ms, and dutycycle is 15%, and average current density is 3.5A/dm
2; PH is 8.5, and temperature is 55 DEG C, and electroplating time is 7min.
Embodiment 5
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.9ms, and dutycycle is 5%, and average current density is 4A/dm
2; PH is 8, and temperature is 50 DEG C, and electroplating time is 6min.
Embodiment 6
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.7ms, and dutycycle is 10%, and average current density is 3.5A/dm
2; PH is 8, and temperature is 50 DEG C, and electroplating time is 5min.
With reference to following methods, dispersive ability test is carried out to the plating solution of embodiment 1 ~ 6:
The dispersive ability of plating solution adopts far and near cathode method (Haring-Blue method) to measure.Measure the Hull groove that groove adopts the HullCell267ml model of Kocour company of the U.S., interior dimensions is 150mm × 50mm × 70mm.Negative electrode selects thickness to be the copper sheet of 0.5mm, and working face is of a size of 50mm × 50mm; Anode is plating nickel plate with holes; Plating electric current 1A, electroplating time 30min.
The dispersive ability calculation formula of plating solution is:
Dispersive ability=[K-(the Δ M of plating solution
1/ Δ M
2)]/(K-1) (result represents with percentage);
In formula, K is negative electrode far away to the distance of anode and nearly negative electrode to the ratio of distances constant of anode, and in this test, K gets 2; Δ M
1for the increment (g) after plating on nearly negative electrode; Δ M
2for the increment (g) after plating on negative electrode far away.
With reference to following methods, covering power test is carried out to the plating solution of embodiment 1 ~ 6:
Endoporus method is adopted to measure.Negative electrode selects internal diameter l10mm, and pipe range is the copper pipe of 50mm, and one end is closed.During test, the distance of the mouth of pipe and anode is fixed on 80mm, test current 0.2A, electroplating time 30min.According to following formulae discovery:
Covering power=endoporus coating length/pipe range (result represents with percentage).
With reference to following methods, current efficiency test is carried out to the plating solution of embodiment 1 ~ 6:
Copper voltameter method is adopted to measure.Negative electrode to be tested and copper voltameter cleaned and dry up rear electronic scale weighing, then insert in electrodeposit groove by two negative electrodes simultaneously, be energized 10 ~ 30min, take out and clean dry up after use electronic scale weighing.According to following formulae discovery:
Current efficiency=(1.186 × cathode quality to be measured)/(electrochemical equivalent of copper voltameter quality × cathodic deposition metal to be measured) × 100%.Here, electrochemical equivalent=molar mass ÷ (depositing ions valency × 26.8), unit is g.A
-1.h
-1.In this test, divalent palladium electrochemical equivalent is 1.985g.A
-1.h
-1.
Speed test is plated with reference to the plating solution of following methods to embodiment 1 ~ 6:
Mass method is adopted to measure sedimentation rate.Be 10 with sensitivity
-4electronic balance weighing sample plating before and after quality.By the acquisition sedimentation rate of poor quality of unit time, unit surface, press formulae discovery below:
Plating speed=(after plating before sample mass-plating sample mass)/(specimen surface to be plated long-pending × plating time).Each Data duplication is measured three times and is got its mean value.
Test with reference to the bonding force of following methods to the coating of embodiment 1 ~ 6:
The method adopting line to draw lattice measures the bonding force of coating, is specially: being 30 degree with one cutting edge by electrodeposition cladding, converted steel draws parallel lines or the 1mm that 2mm of being separated by drawn by cutter
2square lattice.Whether the coating observing line tilts or peels off.Should master the dynamics during line, a cutter just can scratch coating, arrives matrix metal.Adopt quench to measure the bonding force of coating, be specially: the test piece of having plated is placed in retort furnace quenching in the cold water being heated to 300 DEG C of insulation 30min taking-up immersion 10 DEG C immediately, observe coating and whether occur bubble and decortication phenomenon.
With reference to following methods, toughness test is carried out to the coating of embodiment 1 ~ 6:
Coating is stripped down, is bent to 180 °, and extrudes knee, observe coating and whether occur fracture.
With reference to following methods, porosity test is carried out to the coating of embodiment 1 ~ 6:
The large young pathbreaker of porosity is directly connected to the corrosion resisting property of coating, adopts paster method to press GB5935-86 standard detection.The etchant solution that the potassium ferricyanide solution of 10g/L and the sodium chloride solution of 20g/L are tested as porosity.Operation steps is: after wiped clean of being deoiled by coating surface, is close to coating surface with the filter paper soaking into etchant solution, and the two can not have gap.Buy the fully wetting filter paper of etchant solution solution by glass stick or degreasing swab stick, supplement a solution at interval of lmin, taken off by filter paper after 5min, dry after clean with distilled water flushing, record hole is counted.Be placed on cleaned glass plate and dry, the number of number Bluepoint.Substitute into formulae discovery voidage below:
Number/tested area (individual/the cm of porosity=spot
2);
When calculating number of apertures, do following calculating by spot diameter size: hot spot diameter is less than lmm, and with a porosimeter at often; Be greater than lmm and be less than 3mm often o'clock with three porosimeters; Be greater than 3mm and be less than 5mm, often with ten porosimeters.
With reference to following methods, Surface flat test is carried out to the coating of embodiment 1 ~ 6:
By the Hull groove of the HullCell267ml model with the Kocour company of the test piece U.S. after 200 order sand paperings evenly at 3A/dm
2dC current density carries out plating 10min at 25 DEG C of temperature, and whether then observe test piece has scratch.
To expose aptitude tests with reference to the coating of following methods to embodiment 1 ~ 6:
Adopt the Hull groove of the HullCell267ml model of Kocour company of the U.S. at 3A/dm
2after DC current density carries out plating 10min at 25 DEG C of temperature, observe the surface luminous intensity of coating.
The test result of the coating of embodiment 1 ~ 6 and comparative example and the performance of plating solution is as follows:
As can be seen from the above table, in embodiment 1 ~ 6, consider from the integration test effect of plating solution and coating, the dispersive ability of the formula plating solution of embodiment 6, covering power, current efficiency and plating speed, the porosity of coating and bonding force will be got well compared with other embodiment.Thus, this formula is screening formulation of the present invention, and the preferred plating conditions of its correspondence is the pulsewidth of monopulse rectangular wave current is 0.7ms, and dutycycle is 10%, and average current density is 3.5A/dm2; PH is 8, and temperature is 50 DEG C, and electroplating time is 5min, and male and femal face is long-pending than being 3:1.
It should be noted that and understand, when not departing from the spirit and scope of accompanying claim the present invention for required protection, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Below know-why of the present invention is described in conjunction with specific embodiments.These describe just in order to explain principle of the present invention, and can not be interpreted as limiting the scope of the invention by any way.Based on explanation herein, those skilled in the art does not need to pay performing creative labour can associate other embodiment of the present invention, and these modes all will fall within protection scope of the present invention.
Claims (9)
1. the palladium electroplating liquid containing tetraphenylphosphonibromide bromide arsenic, it is characterized in that, comprise in palladium 5 ~ 20g/L trans diamino dibrominated palladium, 60 ~ 90g/L brometo de amonio, 70 ~ 100g/L Secondary ammonium phosphate, 0.6 ~ 2.4g/L3-pyridine-sulfonic acid and 1 ~ 4mg/L tetraphenylphosphonibromide bromide arsenic.
2. electroplate liquid according to claim 1, is characterized in that, comprises in palladium 10g/L trans diamino dibrominated palladium, 70g/L brometo de amonio, 80g/L Secondary ammonium phosphate, 1.6g/L3-pyridine-sulfonic acid and 3mg/L tetraphenylphosphonibromide bromide arsenic.
3. an electric plating method, is characterized in that, comprises the following steps:
(1) electroplate liquid is prepared: in water, dissolve each feed composition form electroplate liquid, described often liter of electroplate liquid contains in palladium 5 ~ 20g trans diamino dibrominated palladium, 60 ~ 90g brometo de amonio, 70 ~ 100g Secondary ammonium phosphate, 0.6 ~ 2.4g3-pyridine-sulfonic acid and 1 ~ 4mg tetraphenylphosphonibromide bromide arsenic;
(2) insert in described electroplate liquid with the base material of electroplated and pass into electric current, apply ultrasonic wave simultaneously and electroplate.
4. method according to claim 4, is characterized in that, described electric current is monopulse rectangular wave current; The pulsewidth of described monopulse rectangular wave current is 2 ~ 5ms, and dutycycle is 5 ~ 30%, and average current density is 2 ~ 4A/dm
2.
5. method according to claim 4, is characterized in that, in described step (2), the pH of electroplate liquid is 7.5 ~ 8.5.
6. method according to claim 4, is characterized in that, in described step (2), the temperature of electroplate liquid is 45 ~ 55 DEG C.
7. method according to claim 4, is characterized in that, in described step (2), the time of plating is 3 ~ 9min.
8. method according to claim 4, is characterized in that, in described step (2), the anode of plating and the area ratio of negative electrode are (1 ~ 4): 1.
9. method according to claim 4, is characterized in that, in described step (2), described base material is copper or stainless steel.
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|---|---|---|---|
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| CN201510812642.6A CN105316722A (en) | 2015-11-20 | 2015-11-20 | Palladium electroplating solution containing tetraphenylarsonium bromide and electroplating method of palladium electroplating solution |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60243296A (en) * | 1983-12-29 | 1985-12-03 | イノヴアン−シユトレ−ベ・ゲ−・エム・ベ−・ハ−・ウント・コンパニ−・コマンデイ−トゲゼルシヤフト | High speed electrodeposition bath for crack-free pore-free glossy high ductility palladium layer |
| US4750977A (en) * | 1986-12-17 | 1988-06-14 | Bacharach, Inc. | Electrochemical plating of platinum black utilizing ultrasonic agitation |
| JPH0711476A (en) * | 1993-06-23 | 1995-01-13 | Kojima Kagaku Yakuhin Kk | Palladium plating solution |
| TW524896B (en) * | 1997-05-30 | 2003-03-21 | Matsushita Electric Ind Co Ltd | Palladium plating solution, palladium plating film formed using the solution and lead frame for semiconductor apparatuses having the palladium plating film |
| CN1420947A (en) * | 1999-10-27 | 2003-05-28 | 小岛化学药品株式会社 | Palladium plating solution |
-
2015
- 2015-11-20 CN CN201510812642.6A patent/CN105316722A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60243296A (en) * | 1983-12-29 | 1985-12-03 | イノヴアン−シユトレ−ベ・ゲ−・エム・ベ−・ハ−・ウント・コンパニ−・コマンデイ−トゲゼルシヤフト | High speed electrodeposition bath for crack-free pore-free glossy high ductility palladium layer |
| US4750977A (en) * | 1986-12-17 | 1988-06-14 | Bacharach, Inc. | Electrochemical plating of platinum black utilizing ultrasonic agitation |
| JPH0711476A (en) * | 1993-06-23 | 1995-01-13 | Kojima Kagaku Yakuhin Kk | Palladium plating solution |
| TW524896B (en) * | 1997-05-30 | 2003-03-21 | Matsushita Electric Ind Co Ltd | Palladium plating solution, palladium plating film formed using the solution and lead frame for semiconductor apparatuses having the palladium plating film |
| CN1420947A (en) * | 1999-10-27 | 2003-05-28 | 小岛化学药品株式会社 | Palladium plating solution |
Non-Patent Citations (1)
| Title |
|---|
| 王丽丽: "电镀钯电解液", 《电镀与精饰》 * |
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Application publication date: 20160210 |