CN102304733B - High-temperature-resistant bright tin-plating stabilizing agent - Google Patents

High-temperature-resistant bright tin-plating stabilizing agent Download PDF

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Publication number
CN102304733B
CN102304733B CN 201110241599 CN201110241599A CN102304733B CN 102304733 B CN102304733 B CN 102304733B CN 201110241599 CN201110241599 CN 201110241599 CN 201110241599 A CN201110241599 A CN 201110241599A CN 102304733 B CN102304733 B CN 102304733B
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grams
temperature
substance
plating
stabilizing agent
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CN102304733A (en
Inventor
宋文超
左正忠
胡哲
周自强
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WUHAN JADECHEM CHEMICALS CO Ltd
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WUHAN JADECHEM CHEMICALS CO Ltd
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Abstract

The invention relates to a plating additive, in particular to a high-temperature-resistant bright tin-plating stabilizing agent. The high-temperature-resistant bright tin-plating stabilizing agent is a mixed solution consisting of a substance A of a structural formula shown in the specification, a substance B of a structural formula shown in the specification, sodium tungstate and aluminium potassium sulfate, wherein in the substance A, R1 and R2 are H, -OH or -CH2OH, n is 10 to 15, and R1 and R2 are the same or different; in the substance B, R1 is O, R2 is -CnH2nOh and n is an integer; and 1,000 milliliters of the mixed solution comprises 10 to 30 grams of the aluminium potassium sulfate, 5 to 20 grams of the sodium tungstate, 3.0 to 10 grams of the substance A and 5 to 15 grams of the substance B. The high-temperature-resistant bright tin-plating stabilizing agent can inhibit oxidation of Sn<2+>, has good stabilizing effect on the Sn<2+>, has strong reducing effect on Sn<4+>, can effectively reduce the Sn<4+> existing in the solution into the Sn<2+>, has the coagulation sedimentation function on suspended substances in the solution, and guarantees long-term transparency of the solution.

Description

High-temperature-resistant bright tin-plating stabilizing agent
Technical field
The present invention relates to a kind of electroplating additive, specifically a kind of high-temperature-resistant bright tin-plating stabilizing agent.
Background technology
In electronic industry, very strict to the requirement of bright tin plating, should satisfy not only that conventional bonding force is good, outside careful smooth, the many requirements such as fragility is low, solderability is good of crystallization, also require coating Wuxi palpus, without leak source, pin hole, pit; Plating bath also answer sedimentation velocity fast, can adapt under the higher temperature condition and work.
Present bright tin plating mainly is vitriol---sulfuric acid liquid technique.Its feature is that composition is simple, and sedimentation velocity is fast, and is easy to operate, with low cost, and the coating of gained can satisfy above-mentioned requirements substantially.But weak point is that the temperature that plating bath adapts to is lower, generally can only between 15-25 ℃, surpass 30 ℃ of then easy muddiness of solution, precipitation, Sn 4+Very easily produce, and produce Deposit appearance thereupon and present vaporific, greyness and pin hole, pit are arranged, even have whisker to produce.This will bring great harm to microelectronic circuits.
In vitriol or the zinc-plated process of muriatic Bivalent Tin, since raw material bring into and anode on electrochemical anodic oxidation, cause that the tetravalent tin ion accumulates more and more in the solution, after arriving certain concentration, will cause that the cathodic current effect descends, solution dispersibility is poor, coating is coarse and have tin must generation etc. problems.Use the sulfuric acid of higher concentration in the technique therefore be everlasting, to alleviating this phenomenon.Yet sulfuric acid concentration is too high, causes plating bath very easily to heat up, and secondly safety in production is brought again larger hidden danger, and can not effectively suppress stannic generation again.
In view of the foregoing, the present invention has studied and has been adapted at wider, higher temperature range light plating Sn stablizer.
Summary of the invention
Purpose of the present invention is exactly the defective for existing bright tin plating technique, and a kind of high-temperature-resistant bright tin-plating stabilizing agent is provided.The present invention can not only suppress Sn 2+Oxidation, to Sn 2+The satisfactory stability effect is arranged, also to Sn 4+Stronger reductive action is arranged, can be with already present Sn in the solution 4+Effectively be reduced to Sn 2+
This bright being achieved through the following technical solutions: it is to be by structural formula A material, structural formula be
Figure BDA0000085197410000021
B material, sodium wolframate and the mixing solutions that forms of potassium aluminium sulfate, wherein R in the A material 1, R 2For H ,-OH or-CH 2OH, n=10~15, R 1, R 2Identical or different; R in the B material wherein 1Be O, R 2For-C nH 2nOH, the n integer; Sulfur acid aluminium potassium 10~30 grams, sodium wolframate 5~20 grams, A material 3.0-10 gram, B material 5-15 gram in 1000 milliliters of mixing solutionss.
The present invention preferably technical scheme is: described A material is polyvinyl alcohol 1000, polyvinyl alcohol 1200 or polyvinyl alcohol 20000.Described B material is xitix, glucose or saccharan.
The better technical scheme of the present invention is: sulfur acid aluminium potassium 15~25 grams, sodium wolframate 10~15 grams, A material 3.0-5.0 gram, B material 7.5-10 gram in 1000 milliliters of mixing solutionss.More preferably potassium aluminium sulfate 20 sodium wolframates 15 grams, A material 4, B material 6.Under this conditions of mixture ratios, the stabilising effect of stablizer is better.
The present invention uses the electrochemistry survey technology, and the electrochemistry cyclic voltammetric behavior that records at the Pt electrode shows: stablizer is to restraining Sn 2+Oxidation, stable plating bath has very significantly effect.The result of same basic solution actual contrast under the condition of same period, same temperature is shown there is not the solution of stablizer, leave standstill and put 5-7 days, turbid phenomenon just occurs; The solution that has added stablizer then just occurs muddy after 3-4 week.When actually operating is produced, only need in time add stablizer, more can keep long-term stable, transparent of plating bath.It can not only suppress Sn 2+Oxidation, to Sn 2+The satisfactory stability effect is arranged, also to Sn 4+Stronger reductive action is arranged, can be with already present Sn in the solution 4+Effectively be reduced to Sn 2+And can the coagulative precipitation function be arranged to the floating outstanding thing in the solution, guaranteed the transparent for a long time of solution.
Embodiment
Below in conjunction with embodiment the present invention is described further:
Embodiment 1
To prepare 1000 milliliters as example, preparation method of the present invention is:
1, take by weighing 15 gram potassium aluminium sulfates, 10 gram sodium wolframates, insert in 600 milliliters the water, heating for dissolving obtains potassium aluminium sulfate and sodium wolframate mixing solutions;
2, take by weighing 3.0 gram polyvinyl alcohol 1200 and join in the above-mentioned mixing solutions stirring and dissolving;
3, add again 7.5 gram xitix and join in the mentioned solution, stir dissolving; Add water and be supplemented to 1000 milliliters.
Embodiment 2
To prepare 1000 milliliters as example, preparation method of the present invention is:
1, take by weighing 20 gram potassium aluminium sulfates, 15 gram sodium wolframates, insert in 600 milliliters the water, heating for dissolving obtains potassium aluminium sulfate and sodium wolframate mixing solutions;
2, take by weighing 4 gram polyvinyl alcohol 1200 and join in the above-mentioned mixing solutions stirring and dissolving;
3, add again 6 gram glucose and join in the mentioned solution, stir dissolving; Add water and be supplemented to 1000 milliliters.
Embodiment 3
To prepare 1000 milliliters as example, preparation method of the present invention is:
1, take by weighing 30 gram potassium aluminium sulfates, 20 gram sodium wolframates, insert in 600 milliliters the water, heating for dissolving obtains potassium aluminium sulfate and sodium wolframate mixing solutions;
2, take by weighing 10 gram polyvinyl alcohol 20000 and join in the above-mentioned mixing solutions stirring and dissolving;
3, add again 15 gram saccharans and join in the mentioned solution, stir dissolving; Add water and be supplemented to 1000 milliliters.
Embodiment 4
To prepare 1000 milliliters as example, preparation method of the present invention is:
1, take by weighing 15 gram potassium aluminium sulfates, 15 gram sodium wolframates, insert in 600 milliliters the water, heating for dissolving obtains potassium aluminium sulfate and sodium wolframate mixing solutions;
2, take by weighing 5 gram polyvinyl alcohol 20000 and join in the above-mentioned mixing solutions stirring and dissolving;
3, add again 5 gram saccharans and join in the mentioned solution, stir dissolving; Add water and be supplemented to 1000 milliliters.

Claims (2)

1. high-temperature-resistant bright tin-plating stabilizing agent, the mixing solutions that it is comprised of polyvinyl alcohol, antioxidant, sodium wolframate and potassium aluminium sulfate, sulfur acid aluminium potassium 10 ~ 30 grams, sodium wolframate 5 ~ 20 grams, polyvinyl alcohol 3.0-10 gram, antioxidant 5-15 gram in 1000 milliliters of mixing solutionss, described polyvinyl alcohol is polyvinyl alcohol 1000, polyvinyl alcohol 1200 or polyvinyl alcohol 20000, and described antioxidant is xitix, glucose or saccharan.
2. a kind of high-temperature-resistant bright tin-plating stabilizing agent according to claim 1 is characterized in that: sulfur acid aluminium potassium 15 ~ 25 grams, sodium wolframate 10 ~ 15 grams, polyvinyl alcohol 3.0-5.0 gram, antioxidant 7.5-10 gram in 1000 milliliters of mixing solutionss.
CN 201110241599 2011-08-22 2011-08-22 High-temperature-resistant bright tin-plating stabilizing agent Expired - Fee Related CN102304733B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1385556A (en) * 2002-01-23 2002-12-18 武汉大学 Stabilizer for plating tin-bismuth alloy and preparation method thereof
US20090236232A1 (en) * 2008-03-24 2009-09-24 Fujitsu Limited Electrolytic plating solution, electrolytic plating method, and method for manufacturing semiconductor device
CN101922026A (en) * 2010-08-18 2010-12-22 济南德锡科技有限公司 Methanesulfonic acid-based matte pure tin electroplating solution and additive thereof
CN101962790A (en) * 2010-08-20 2011-02-02 河南科技大学 Electrolyte composition for half bright acid tinning

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1385556A (en) * 2002-01-23 2002-12-18 武汉大学 Stabilizer for plating tin-bismuth alloy and preparation method thereof
US20090236232A1 (en) * 2008-03-24 2009-09-24 Fujitsu Limited Electrolytic plating solution, electrolytic plating method, and method for manufacturing semiconductor device
CN101922026A (en) * 2010-08-18 2010-12-22 济南德锡科技有限公司 Methanesulfonic acid-based matte pure tin electroplating solution and additive thereof
CN101962790A (en) * 2010-08-20 2011-02-02 河南科技大学 Electrolyte composition for half bright acid tinning

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
尹国光 等.硫酸盐电镀锡添加剂的探讨.《材料保护》.2011,第44卷(第6期),1-4.
硫酸盐电镀锡添加剂的探讨;尹国光 等;《材料保护》;20110630;第44卷(第6期);1-4 *

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