CN102304733A - High-temperature-resistant bright tin-plating stabilizing agent - Google Patents
High-temperature-resistant bright tin-plating stabilizing agent Download PDFInfo
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- CN102304733A CN102304733A CN201110241599A CN201110241599A CN102304733A CN 102304733 A CN102304733 A CN 102304733A CN 201110241599 A CN201110241599 A CN 201110241599A CN 201110241599 A CN201110241599 A CN 201110241599A CN 102304733 A CN102304733 A CN 102304733A
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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
Technical field
The present invention relates to a kind of electroplating additive, specifically a kind of high temperature resistant bright tin plating stablizer.
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, no 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 a vitriol---sulfuric acid liquid technology.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 basically.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, deposition, Sn
4+Very easily produce, and produce the coating outward 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 many more more in the solution; After arriving certain concentration, will cause cathodic current to imitate to descend, solution dispersibility is poor, coating is coarse and have tin must generation etc. problems.Use the sulfuric acid of higher concentration in the technology so be everlasting, in the hope of 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 bigger hidden danger again, and can not suppress stannic generation effectively again.
In view of the foregoing, the present invention has studied and has been adapted at broad, higher temperature range light plates the Sn stablizer.
Summary of the invention
The object of the invention is exactly the defective to existing bright tin plating technology, and a kind of high temperature resistant bright tin plating stablizer 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+Be reduced to Sn effectively
2+
This is bright through following technical scheme realization: it is to do by structural formula
A material, structural formula do
The mixing solutions formed of B material, sodium wolframate and potassium aluminium sulfate, R in the A material wherein
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's technical scheme preferably 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 on the Pt electrode, records shows: stablizer is to restraining Sn
2+Oxidation, stable plating bath has very obvious effects.Actual correlated result under the condition of same period, same temperature shows there is not the solution of stablizer with same basic solution, leaves standstill and puts 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 plating bath secular stable, transparent.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+Be reduced to Sn effectively
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 done and to further describe:
Embodiment 1
To prepare 1000 milliliters is example, and 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 7.5 gram xitix again and join in the above-mentioned solution, stir dissolving; Add water and be supplemented to 1000 milliliters.
Embodiment 2
To prepare 1000 milliliters is example, and 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 6 gram glucose again and join in the above-mentioned solution, stir dissolving; Add water and be supplemented to 1000 milliliters.
Embodiment 3
To prepare 1000 milliliters is example, and 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 15 gram saccharans again and join in the above-mentioned solution, stir dissolving; Add water and be supplemented to 1000 milliliters.
Embodiment 4
To prepare 1000 milliliters is example, and 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 5 gram saccharans again and join in the above-mentioned solution, stir dissolving; Add water and be supplemented to 1000 milliliters.
Claims (4)
1. high temperature resistant bright tin plating stablizer, it is to do by structural formula
A material, structural formula do
The mixing solutions formed of B material, sodium wolframate and potassium aluminium sulfate, R in the A material wherein
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.
2. a kind of high temperature resistant bright tin plating stablizer according to claim 1 is characterized in that: described A material is polyvinyl alcohol 1000, polyvinyl alcohol 1200 or polyvinyl alcohol 20000.
3. a kind of high temperature resistant bright tin plating stablizer according to claim 1, it is characterized in that: described B material is xitix, glucose or saccharan.
4. a kind of high temperature resistant bright tin plating stablizer according to claim 1 is characterized in that: 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110241599 CN102304733B (en) | 2011-08-22 | 2011-08-22 | High-temperature-resistant bright tin-plating stabilizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110241599 CN102304733B (en) | 2011-08-22 | 2011-08-22 | High-temperature-resistant bright tin-plating stabilizing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102304733A true CN102304733A (en) | 2012-01-04 |
| CN102304733B CN102304733B (en) | 2013-04-17 |
Family
ID=45378644
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110241599 Expired - Fee Related CN102304733B (en) | 2011-08-22 | 2011-08-22 | High-temperature-resistant bright tin-plating stabilizing agent |
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Citations (4)
| 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 |
-
2011
- 2011-08-22 CN CN 201110241599 patent/CN102304733B/en not_active Expired - Fee Related
Patent Citations (4)
| 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 (1)
| Title |
|---|
| 尹国光 等: "硫酸盐电镀锡添加剂的探讨", 《材料保护》 * |
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| Publication number | Publication date |
|---|---|
| CN102304733B (en) | 2013-04-17 |
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| C14 | Grant of patent or utility model | ||
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Granted publication date: 20130417 Termination date: 20210822 |