CN1425800A - Coating composition - Google Patents
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- CN1425800A CN1425800A CN 02146348 CN02146348A CN1425800A CN 1425800 A CN1425800 A CN 1425800A CN 02146348 CN02146348 CN 02146348 CN 02146348 A CN02146348 A CN 02146348A CN 1425800 A CN1425800 A CN 1425800A
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Abstract
Disclosed are compositions suitable for electroless gold plating including one or more water soluble gold compounds, one or more gold complexing agents, one or more organic stabilizer compounds, and one or more carboxylic acid uniformity enhancers. Methods of plating and methods of manufacturing electronic devices using these compositions are also provided.
Description
Technical field
The present invention relates to the field of electroless metal.Particularly, the present invention relates to the field of Electroless plating.
Background technology
Dipping or displacement plating are the electroless process, but are that it is divided into different kinds in this field.In the dipping plating, sedimentation is from substrate substitutional element metal by the metal ion in the coating solution.In electroless, be sedimentation to take place at the beginning by solution metal ionic autocatalytically reduction reaction.This kind electroless need carry out under the condition of going back the original reagent existence.
The dipping plating does not need to use impressed current, but it still is the electrochemical displacement reaction, and this electrochemical displacement reaction system is driven by the substrate position with respect to the series of potentials of the sedimentary metal of desire in this solution.Metal ion in being dissolved in the plating bath is via contacting with this plating bath and the metal of activity bigger (inertia is less) when replacing, plating promptly taking place.
When making printed-wiring board (PWB), form the coating (solderable finishes) that can weld typically on the substrate of the printed-wiring board (PWB) with weld pad and/or through hole, this weld pad and/or through hole system see through cover curtain (as, scolding tin mask) and expose to the open air out.Since electroless also can be on the surface of cover curtain metal refining (this is not desired situation), so plant the coating that can weld usually system form by the dipping plating.Because dipping plating reaction system is driven by electrochemical potential difference, so plating only takes place in the zone of the metal through exposing to the open air.For example, United States Patent (USP) the 5th, 143, No. 544 (Iantosca) promptly discloses a kind of solution that can be used for flooding the plating tin-lead alloy, and this tin-lead alloy is suitably used as the coating that welds on the substrate of printed-wiring board (PWB).Yet, when making printed-wiring board (PWB) with regard to the employed lead, still continue to increase for the demand of the selection that more can accept for environment.Therefore, in electronic component, use lead and lead alloy being faced with uncertain future.Referring to, for example, United States Patent (USP) the 5th, 536, No. 908 (Etchells et al.).
For plumbous, silver is the another kind of selection that more can accept for environment, and existing suggestion is used as the coating that can weld with silver.As mentioned above, deposit the preferred approach system of the coating that this kind can weld by the dipping plating.For example, United States Patent (USP) the 5th, 955, No. 141 (Souter et al.) disclose certain and flood silver-colored plating bath, and this plating bath is suitable for depositing silver layer on printed-wiring board (PWB).Yet silver still has many shortcomings, and for example the sedimental sticking power of dipping silver is not good, and silver easily has dark and gloomy tendency; Therefore, need to use anti--dark and gloomy coating.
Because gold utensil has low-resistivity and its erosion for corrosives to have inertia, life-time service is golden as the metal that is connected with surface electrical behavior in electronic industry.This kind deposition of gold typically is to use not have electricity or flood golden plating bath to carry out plating.Particularly, the life-time service gold formation coating that can weld on nickel priming paint.Typically, this nickel priming paint system forms with electroless, and gold system forms with immersion deposition.This kind processing procedure system is called electroless-nickel-dipping-Jin, or is called " ENIG ".
A kind of type system of bath of known Electroless plating is based on thiosulphate, and makes it stable with sulfite ion.When this kind bath lie in the pH value be 6 or below when operating, because this bath can discharge sulfurous gas under the condition of this kind pH value, so this bath is unsettled.Known this kind thiosulfate ion can decompose generting element sulphur and sulfite ion in acidic solution.About 4 to 5 the time through being adjusted into when the pH of sodium thiosulfate solution value system, because forming element sulphur, this solution will become muddiness.Yet, if S-WAT also is added in the above-mentioned solution, will be not can forming element sulphur, and this solution will comparatively be stablized and limpid.Therefore, in the field of known metal deposition solution, be to use S-WAT and Sulfothiorine to stablize this solution.Yet the problem that the supporter uses S-WAT to produce is, this kind S-WAT ion is unsettled in slightly acidic solution, and sulfurous gas is formed lentamente and discharges from this solution.The acidity of this solution is big more, and the speed of the capable one-tenth of this sulfurous gas is then big more.This causes the consumption increase of S-WAT and the unstable of the metal thiosulfuric acid salt composite in the acidic solution to improve.
United States Patent (USP) the 5th, 302, No. 278 (Nobel et al.) discloses a kind of Metal plating solution that comprises golden electroplating solution, and this solution contains thiosulphate and makes it stable with organic-sulfinate.Do not disclose electroless and dipping coating solution in this patent.
The bath of Electroless plating is to contain to go back original reagent.Typically going back original reagent is sulphur and alkyl sulfide derivative; The compound that contains enol, for example xitix (referring to United States Patent (USP) the 4th, 481, No. 035 (Andrascek et al.)); The compound that contains boron, for example boranes and hydroborate class.These known baths still have some shortcoming.For example, contain sulphur as the bath of going back original reagent must be heated to about 80 ℃ to 90 ℃ so that it has acceptable sedimentation rate.This temperature is too high for employed some electronic package material.And this coating solution becomes unstable under this temperature, and forms trickle gold grain naturally in whole solution, but not only produces deposition of gold on required substrate.The compound that use contains boron is when going back original reagent, and this kind compound is increased with temperature by the speed system of hydrolysis reaction and this hydrolysis reaction at first earlier.Many original reagents of going back that contain boron consume in the side reaction of this non-expectation, and make the control of its concentration become quite difficult.
International application WO 99/18254 (Scheel et al.) discloses a kind of solution that is used for Electroless plating, and this solution can contain some goes back original reagent, for example oxalic acid.This patent does not disclose uses-sulfinic acid or-sulfinate as stablizer.
Flood gold-plated bath and can avoid many above-mentioned reduction reagent place deutero-shortcoming.Yet this kind dipping plating bath typically needs high plating temperature (for example, 70 ℃ or more than) in order to operation.Usually, this kind high temperature system is unfavorable for some electronic package material.
Therefore, still need a kind of stable, and can be in the Electroless plating solution of lower temperature operation compared to known coating solution.
Summary of the invention
On the one hand, the invention provides a kind of composition of Electroless plating, said composition comprises: a) gold compound of one or more water solubles; B) one or more golden complexing agents; C) one or more are suc as formula R-SO
2Organic stabilizer compounds shown in the-Y, wherein, R is (C
1-C
18) alkyl, aryl or heteroaryl, and Y is hydrogen or univalent positively charged ion; And d) one or more even promotors.
On the other hand, the invention provides a kind of on substrate the method for electroless deposition gold, this method comprises the step that substrate is contacted with above-mentioned composition.
The present invention further provide again a kind of positive polarity less than the metal of gold on the method for deposited gold, this method comprises to make and contains positive polarity and contact with above-mentioned composition less than the substrate of the metal of gold.
Again on the other hand, the present invention provides a kind of manufacturing to comprise the method for the electronic installation of deposited gold layer again, this method comprises makes the electronic installation substrate contact one section step that is enough to deposit the required golden layer time with composition, and said composition comprises: a) gold compound of one or more water solubles; B) one or more golden complexing agents; C) one or more are suc as formula R-SO
2Organic stabilizer compounds shown in the-Y, wherein, R is (C
1-C
18) alkyl, aryl or heteroaryl, and Y is hydrogen or univalent positively charged ion; And d) one or more even promotors.
In this specification sheets, point out that following meaning is promptly represented in following abbreviation unless have clearly in addition: ℃=centigradetemperature; °F=Fahrenheit temperature; The g=gram; The L=litre; MN=milli newton; The mm=millimeter; During μ in=microinch; And μ m=micron." deposition " and " plating " can be used alternatingly in this specification sheets." alkyl " means straight chain, branch and cyclic alkyl." halogen " means fluorine, chlorine, bromine and iodine.Similarly, " halogen " means fluorine-based, chloro, bromo and iodo.Except as otherwise noted, have two or more substituent aromatics, comprise ortho position, a position and para-orientation.Except as otherwise noted, all proportions is all weight ratio.All digital scopes be all comprise and can any sequential combination, unless these digital scopes systems are limited in below 100% significantly.
The invention provides a kind of composition of Electroless plating, said composition comprises: a) gold compound of one or more water solubles; B) one or more golden complexing agents; C) one or more are suc as formula R-SO
2Organic stabilizer compound shown in the-Y, wherein, R is (C
1-C
18) alkyl, aryl, (C
1-C
18) alkaryl or heteroaryl, and Y is hydrogen or univalent positively charged ion; And d) one or more even promotors.
Any gold compound of the water soluble of gold (I) that can provide in said composition all can be used for the present invention.The gold compound that is fit to comprises, but is not limited to: basic metal gold thiosulfuric acid salt compound, for example golden thiosulfuric acid trisodium and golden thiosulfuric acid tripotassium.This gold compound system is preferable with golden thiosulfuric acid trisodium.Will be appreciated that multiple other the gold compound of water soluble also can be used for composition of the present invention, basic metal gold sulphite for example is as golden S-WAT and golden potassium sulfite, golden ammonium sulphite; The halogenide of gold is as gold trichloride; The basic metal gold cyanide is as golden sodium cyanide and golden potassium cyanide and golden ammonium cyanide.Yet cyanide ion and sulfite ion are not contained in fact in the preferable system of the present invention." do not contain in fact " and mean this kind ion that contains in the composition of the present invention below the 0.05 gram/litre.Better person does not contain cyanide ion and sulfite ion fully in the composition of the present invention.
The total amount of the gold compound of these one or more water solubles is typically from 0.1 to 60 gram/litre.The preferably, the content of this gold compound is from 0.5 to 15 gram/litre, and better person 0.5 to 5 gram/litre.The gold compound of this kind water soluble generally can be buied by a plurality of suppliers, or can be made by known method in this field.
Multiple golden complexing agent also can be used for the present invention.The golden complexing agent that is fit to comprises, but is not limited to: thiosulfuric acid; Thiosulphate, for example sodium thiosulfate, Potassium Thiosulphate and ammonium thiosulfate; Ethylenediamine tetraacetic acid (EDTA) and salt thereof; Nitrogen base nitrilotriacetic etc.Preferable with thiosulfuric acid and thiosulphate.Better person is a sodium thiosulfate.
When using this kind thiosulphate, can provide with any form that dissolves in solution, for example alkali metal thiosulfate (as, Sulfothiorine or Potassium Thiosulphate) or ammonium thiosulfate, and be most economical and obtain easily with the Sulfothiorine pentahydrate.
These one or more complexing agents, typically the total amount with 0.1 to 150 gram/litre exists, and preferable from 1 to 100 gram/litre.Better person, this kind complexing agent exists with the amount of 5 to 75 gram/litres, and better again person is from 10 to 60 gram/litres.These one or more complexing agents generally are commercially available getting, or can be made by method as known in the art.
Be used for one or more organic stabilizer compounds of the present invention, have suc as formula R-SO
2Structure shown in the-Y, wherein, R is (C
1-C
18) alkyl, aryl or heteroaryl, and Y is hydrogen or univalent positively charged ion.With regard to Y, the monovalent cation that is fit to is a basic metal, for example sodium and potassium.Y is that hydrogen also is the preferably.With regard to R, the example of alkyl group comprises, but is not limited to: methyl, ethyl, just-propyl group, different-propyl group, just-butyl, the 3rd-butyl, different-butyl, just-amyl group, new-amyl group, hexyl, octyl group and decyl.Typical aromatic yl group is the group that has 5 to 14 carbon atoms in those aromatic nucleus.The aromatic yl group that is fit to comprises, but is not limited to: phenyl; (C
1-C
6) alkaryl, for example tolyl and xylyl; Naphthyl; And dihydroxyphenyl propane.The heteroaryl groups that is fit to comprises, but is not limited to: furyl, pyridyl, thiophenyl etc.Preferably, R are aromatic yl group, and better person is a phenyl.
Have the knack of this operator and should be appreciated that, (the C of replacement
1-C
18) alkyl, aryl or heteroaryl also be contained in the just " (C of replacement of category 1 of the present invention
1-C
18) alkyl, aryl or heteroaryl ", be meant this (C
1-C
18) one or more hydrogen on alkyl, aryl or the heteroaryl groups, be to replace with one or more substituting group group.The substituting group group that is fit to comprises, but is not limited to: halogen, hydroxyl, (C
1-C
6) alkoxyl group, carbonyl (C
1-C
6) alkoxyl group, nitro, sulfenyl, (C
1-C
6) alkylthio etc.
Generally speaking, the consumption of this one or more organic stabilizer compounds is at least 0.5 gram/litre, is preferably at least 1 gram/litre.The actual upper bound of the consumption of this one or more organic stabilizer compounds is to reach capacity in said composition with this kind compound to exceed.The preferably, the consumption of this one or more organic stabilizer compounds be from 2 gram/litres to 25 gram/litres, and better person is from 3 to 15 gram/litres.Organically the consumption of stablizer with from 3 to 10 gram/litres for suitable especially.The organic stabilizer compounds of this kind generally is commercially available getting, or can be made by known method in this field.
Do not desire to be subject to down theoretical, believe that the organic stabilizer compounds of this kind can make the composition of this Electroless plating more stable, when particularly under the condition of little acid, using thiosulfate ion, make this solution can be in short-duration failure, and can not discharge sulfurous gas to any survey amount.
One or more even promotors can be added in the composition of the present invention.The even promotor of this kind typically is the organic carboxyl acid that sequestering action can be provided.Do not desiring to be subject under the theory, the even promotor of this kind also can be used as gentle reductive agent in addition.Found the deposition of gold that the even promotor of this kind is provided, compared to not containing the deposition of gold that this kind compound compositions is provided, more even.The even promotor that is fit to comprises poly carboxylic acid, for example two-and the tri-carboxylic acids compound; The carboxylic acid chemical combination that replaces through hydroxyl etc.This even promotor is preferable with two-carboxylic acid.The example of this even promotor comprises, but is not limited to: oxalic acid, xitix, citric acid, oxysuccinic acid, oxyacetic acid, propanedioic acid, lactic acid, oxalacetic acid, and tartrate.Other even promotor that is fit to comprises phthalic acid, hexanodioic acid, Succinic Acid and pentanedioic acid.The preferably, this even promotor is oxalic acid, propanedioic acid, xitix and citric acid.Better person, this even promotor is an oxalic acid.
Generally speaking, the consumption of this one or more even promotor system is from 0.1 to 50 gram/litre, and preferable system is from 1 to 15 gram/litre.The particularly suitable consumption of this even promotor is from 2 to 8 gram/litres.
The useful especially composition of the present invention comprises: a) one or more basic metal gold thiosulfuric acid salt compounds of 0.5 to 15 gram/litre; B) one or more of 1 to 100 gram/litre are selected from the golden complexing agent that thiosulfuric acid or alkali metal thiosulfate constitute; C) 2 gram/litres to one or more of 25 gram/litres suc as formula R-SO
2Organic stabilizer compound shown in the-Y, wherein, R is (C
1-C
18) alkyl, aryl or heteroaryl, and Y is hydrogen or univalent positively charged ion; And d) oxalic acid of 1 to 15 gram/litre.
Also can further comprise the compound of regulating the pH value in the composition of the present invention.The compound of any pH of adjusting value all can use, as long as this compound can not cause adverse influence to the stability and the usefulness of said composition.The pH value that is fit to is regulated compound and is comprised phosphoric acid salt, for example Kdp monohydrate, Rhodiaphos DKP, Tripotassium phosphate; Boric acid etc.PH value that the consumption system that this kind pH value is regulated compound desires to keep according to institute and selected specific pH value adjusting compound and decide.For example, Kdp typically consumption is 1 to 50 gram/litre, and is preferably 5 to 25 gram/litres.Generally speaking, the pH value of composition of the present invention system maintains between 3 to 9, be preferably 4 to 8, and preferable system is from 5 to 7.5.
In the said composition, generally comprise water.The water of any grade all can use, and is preferable with deionized water.
Gold-plated composition of the present invention also can optionally contain one or more other additive, for example interfacial agent.Negatively charged ion and non-ionic surfactant are preferable interfacial agent, and better person is a teepol.The teepol that is fit to comprises phosphoric acid ester, the phosphoric acid ester of aliphatics alcohols (phosphoric acid ester that comprises glyceride type) for example, and the preferably is the phosphoric acid ester of long-chain fat family alcohols.The phosphoric acid ester teepol that is fit to comprise those respectively by Rhodia and Crompton Corporation with trade(brand)name R
HODAFACAnd E
MPHOSThe person of selling.This kind interfacial agent typically is to use with the amount of 0.1 to 2 gram/litre.
Composition of the present invention can be complied with any order, by preparing in conjunction with mentioned component.When using gold trichloride, preferable this gold complexing agent, the organic stabilizer compounds and after evenly promotor is added into said composition of lying in is added into this gold trichloride in the said composition again.Add in the process of this gold trichloride, the pH value of said composition system with maintain 〉=5 preferable.Keep this pH value can by, for example, add oxyhydroxide (as potassium hydroxide).
Generally speaking, gold-plated bath of the present invention is to use when heating, typically is from 25 ℃ to 65 ℃.From 30 ℃ to 60 ℃, and better person system is from 45 ℃ to 60 ℃ through heating for preferably, bath of the present invention system.Also can use when temperature is higher than about 65 ℃, only, an advantage of the present composition, be said composition compared to known Electroless plating process, its when low temperature the institute a sedimentary gold can be more even.Be subject under the theory not desiring, believe composition of the present invention can be by the processing procedure that mixes electroless deposited gold.Owing to do not need electric current when using composition of the present invention gold-plated, so it also can be described as the electroless process.Yet, composition of the present invention can't be on goldleaf plated with gold, so composition of the present invention is not autocatalytic, therefore believe that it is not " real " electroless processing procedure.Yet compared to known steeping process, composition of the present invention provides a kind of thicker deposition of gold.For example, after composition of the present invention contacted 1 hour, the gold in the time of can on ni substrate, depositing a bed thickness and reach 175 microinch.Therefore, believe that plating process of the present invention is " mixing " plating process.
By the time length that control basal plate contacts with coating composition of the present invention, can on this substrate, control required deposition of gold thickness.The advantage of composition of the present invention ties up in said composition can provide sticking power good deposition of gold.Composition of the present invention is particularly suitable for deposited gold on multiple substrate, particularly on the metal of positive polarity less than gold, that is, and dipping plating method traditionally.Positive polarity comprises less than the typical metal of gold, but is not limited to: nickel, copper, palladium and iron.Can use the metal of more than one its positive polarities less than gold.For example, according to the present invention, the palladium layer on nickel dam is a kind of substrate that is suitable for deposited gold.Therefore, the present invention further provide again a kind of positive polarity less than the metal of gold on the method for deposited gold, this method comprises to make and contains positive polarity and contact with this above-mentioned composition less than the substrate of the metal of gold.
Composition of the present invention also is fit to use " real " electroless process clad deposit gold on substrate.With regard to real electroless deposition, typically be that the known original reagent of going back is added in the composition of the present invention.Can suitably use the multiple known original reagent of going back.Yet composition of the present invention is not contain thiocarbamide; Thiourea derivative is as methylthiourea, dimethyl thiourea, ethyl thiourea, N-methylthiourea etc.; Resorcinol; Catechols etc. are preferable.This kind electroless deposition system is by the substrate of desiring with golden plating being contacted with this above-mentioned composition and reaching.
Combination system of the present invention is particularly suitable for making electronic installation, for example printed-wiring board (PWB), unicircuit and ic package.For example, when manufacturing comprises the electronic installation of a gold medal layer, this gold layer can be by method deposition, and this method comprises makes the electronic installation substrate contact one section step that is enough to deposit golden layer required time with composition, and said composition comprises: a) gold compound of one or more water solubles; B) one or more golden complexing agents; C) one or more are suc as formula R-SO
2Organic stabilizer compounds shown in the-Y, wherein, R is (C
1-C
18) alkyl, aryl or heteroaryl, and Y is hydrogen or univalent positively charged ion; And d) one or more even promotors.The metal (positive polarity is less than the metal of gold) that is fit to is as above-mentioned those disclosed herein, and the preferably is the palladium on nickel and the nickel dam.This kind nickel and palladium layer are formed by electroless deposition.Particularly suitable ic package comprises, but is not limited to: weld pad on lead frame, the wafer and ceramic package etc.The present invention also is adapted at providing on the substrate gold plate that can weld (finish), or on unicircuit deposited gold.
Following embodiment system is in order to further specifying a plurality of viewpoint of the present invention, but is not to limit to category of the present invention anyways
Embodiment
Embodiment 1
By gold (Au with metallic state
0) be dissolved in the mixture of hot hydrochloric acid and nitric acid, with the preparation gold plating solution.After the gold of metallic state dissolves fully, this solution is heated to drying regime.Then,, and heat once more till in this solution, no longer recording nitrate, generate HAuCl with the left salt of the deionized water wash of heat
4
With above-mentioned prepared HAuCl
4Be added into Na at leisure
2O
3S
2In the saturated solution, till can't entering in the solution again, and produce milky solution down in this state.Virahol is added wherein, be clarification and begin to form white precipitate up to this solution.This solution left standstill is spent the night with complete reaction.Suppose that all gold are reduced to aurous state by the state of gold.Filter this solution, and place baking oven dry throw out, to form AuNa
3O
6S
4 Embodiment 2
Gold-plated bath system by with the composition in the table 1 and the amount shown in complying with in conjunction with and prepare.
Table 1
Become component (gram/litre)
AuNa
3O
6S
4The gold 1 of form
Sulfothiorine 50
-sulfinic acid benzene 10
Kdp 15
Oxalic acid 5
Water adds to 1 liter
The pH value of this bath is 5.5.The temperature maintenance of this bath is at 120 °F (about 49 ℃).Desire to impregnated in this bath 5 minutes with a plurality of by the substrate (the FR-4 substrate that contains nickel dam) of dipping plated with gold.After this substrate removed in this bath, wash this substrate and make its drying; Analyze the deposition of gold of gained, when finding that its thickness is 4 to 7 microinch.
Embodiment 3
Use the nickel product (EVERON of the commercially available electroless that gets
TMThe nickel of BP electroless, available from Shipley Company, Marlboroug Massachusetts), is positioned at aluminium pad on the wafer with the nickel plating.Use standardized plating condition (190), during with 12 microinch/minute deposited at rates nickel.Behind the electroless nickel plating, wash this nickel coating.
After the washing, this aluminium base through the nickel plating is contacted with the gold-plated bath of embodiment 2.With near 2 microinch the time/minute speed, make deposition of gold on this nickel dam.After gold-plated, this substrate is removed in this plating bath, wash this substrate and make its drying.
Embodiment 4
Pad on this wafer is that the bath of copper and this electroless nickel plating lies under 185 the temperature the operation, repeats the program of embodiment 3.During with 10 microinch/minute deposited at rates nickel.
Embodiment 5
According to the gold-plated bath of embodiment 2 preparations, only, the amount of each composition is as shown in 2.
Table 2
Composition
Amount (gram/litre)
AuNa
3O
6S
4The gold 1 of form
Sulfothiorine 55
-sulfinic acid benzene 10
Kdp 20
Oxalic acid 5
Water adds to 1 liter
The pH value of this bath is 7.The temperature maintenance of this bath is at 120 °F (about 49 ℃).
Embodiment 6
The plating bath that uses embodiment 5 with golden plating in 16 RF-4 test products (about 1 * 12 inch) that contain the nickel dam of electroless deposition.Use X-ray fluorescent (" XRF ") spectral measurement to be deposited on the thickness of the gold of each test product.Measure twice in each test product.Most of test product the thickness of sedimentary gold when being 7 to 8 microinch, when its mean value is 7.06 microinch.
Embodiment 7
A RF-4 test product (about 1 * 12 inch) that contains the nickel dam of electroless deposition is contacted with the plating bath of embodiment 5.After 30 minutes, this test product is removed in this bath, the thickness of sedimentary gold when being 78 microinch by the XRF spectral measurement.
Embodiment 8
A RF-4 test product (about 1 * 12 inch) that contains the nickel dam of electroless deposition is contacted with the plating bath of embodiment 5.After 60 minutes, this test product is removed in this bath, the thickness of sedimentary gold when being 173 microinch by the XRF spectral measurement.
Embodiment 9
Assess these nickel dams that contain electroless deposition and according to the lead joint capacity of the RF-4 test product (about 1 * 12 inch) of the sedimentary gold layer of 2 of embodiment (during 7 to 9 microinch).Use K﹠amp; S pattern 4523 aluminum steel joiners are engaged to gold layer on several test products with aluminum steel (1 Mill) with ultrasound.Use K﹠amp; S pattern 4524 gold thread joiners are engaged to gold layer on several test products with gold thread (1.3 Mill) with hot sound (thermosonically).The test product of aluminum steel and gold thread be engaged to to(for) part are pullled.The part test product lay under 150 ℃ the condition baking 1 hour before pullling.Part test product system engages aluminum steel or gold thread then earlier through baking (1 hour, 150 ℃), is pullling.With the gram is that the unit record makes the required strength of this thread breakage.It the results are shown in table 3.
Table 3
Wire rod Engage and pull (gram) Engage, toast and pull (gram) Toast, engage and pull (gram)Aluminium 8.5 to 8.6 8.5 to 8.6 8 to 8.1 gold medals 11.5 to 12 13 to 13.5 11 to 11.5
Embodiment 10
Except this test product system contain electroless deposition nickel dam, be covered in the palladium of this nickel dam with electroless deposition, and be covered in beyond the gold on this palladium layer, repeat the program of embodiment 9.Obtain acceptable aluminum steel and gold thread and engage the result.
Embodiment 11
Assess ten nickel dams that contain electroless deposition and according on the RF-4 test product (about 1 * 12 inch) of 2 sedimentary gold layers of embodiment (during 7 to 9 microinch) the Weldability of sedimentary gold.Use M
ENISCOST-50 wet balanced (wetting balance) assessment Weldability.Five test products lie in to be tested after gold-plated, and baking was tested in 16 hours again under the condition of other five test products system prior to 150 ℃.Lead-free scolder lies under 245 ℃ the condition and uses.Employed solubility promoter (flux) is K
ESTERThe non-purification type of 422-CX (no clean type).At each test product, the wetting power (wetting force) (is unit with the milli Newton/millimeter) when measuring for zero string time (zero cross time) (is unit with the second) and 2 seconds.Measure twice in each test product, and write down its mean value.It the results are shown in table 4.
Table 4
Test product Zero string time (second) Wetting power in the time of 2 seconds (milli Newton/millimeter)0.15 0.26 baking back 0.25 0.28 behind the plating
Claims (10)
1. the coating composition of an Electroless plating, said composition comprises:
A) gold compound of one or more water solubles;
B) one or more golden complexing agents;
C) one or more are suc as formula R-SO
2Organic stabilizer compound shown in the-Y, wherein, R is (C
1-C
18) alkyl, aryl or heteroaryl, and Y is hydrogen or univalent positively charged ion; And
D) one or more even promotors.
2. composition as claimed in claim 1, wherein, this gold compound is a basic metal gold thiosulfuric acid salt compound.
3. as the composition of claim 1 or 2, wherein, R is phenyl, tolyl, xylyl, naphthyl or dihydroxyphenyl propane.
4. as each composition of claim 1 to 3, wherein, the content of these one or more organic stabilizer compounds is at least 2 gram/litres.
5. as each composition of claim 1 to 4, wherein, these one or more even promotor is selected from oxalic acid, xitix, citric acid, oxysuccinic acid, oxyacetic acid, propanedioic acid, lactic acid, oxalacetic acid, tartrate, phthalic acid, hexanodioic acid, Succinic Acid and pentanedioic acid.
6. as each composition of claim 1 to 5, wherein, said composition is substantially free of cyanide ion and sulfite ion.
7. the method for an electroless deposition gold on substrate, this method comprise the step that substrate and claim 1 to 6 composition in each is contacted.
One kind positive polarity less than the metal of gold on the method for deposited gold, this method comprises making and contains positive polarity and contact less than the substrate and claim 1 to 6 of the metal of the gold composition in each.
9. a manufacturing comprises the method for the electronic installation of deposited gold layer, and this method comprises the step that electronic installation substrate and claim 1 to 6 composition in each is contacted.
10. method as claimed in claim 9, wherein, this electronic installation substrate is selected from weld pad and the ceramic package on the substrate, unicircuit, lead frame, wafer of printed-wiring board (PWB).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US35008401P | 2001-10-25 | 2001-10-25 | |
| US60/350,084 | 2001-10-25 | ||
| US60/339,659 | 2001-12-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1425800A true CN1425800A (en) | 2003-06-25 |
| CN1250768C CN1250768C (en) | 2006-04-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02146348 Expired - Fee Related CN1250768C (en) | 2001-10-25 | 2002-10-24 | Coating composition |
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| Country | Link |
|---|---|
| CN (1) | CN1250768C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI408252B (en) * | 2006-03-20 | 2013-09-11 | Shinko Electric Ind Co | Non-cyanide electroless gold plating solution and process for electroless gold plating |
| CN107250076A (en) * | 2015-02-23 | 2017-10-13 | 麦克德米德乐思公司 | Inhibitor combination during Chrome-free etchant for hanger is used in plastics coating method |
-
2002
- 2002-10-24 CN CN 02146348 patent/CN1250768C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI408252B (en) * | 2006-03-20 | 2013-09-11 | Shinko Electric Ind Co | Non-cyanide electroless gold plating solution and process for electroless gold plating |
| CN107250076A (en) * | 2015-02-23 | 2017-10-13 | 麦克德米德乐思公司 | Inhibitor combination during Chrome-free etchant for hanger is used in plastics coating method |
| CN107250076B (en) * | 2015-02-23 | 2021-06-29 | 麦克德米德乐思公司 | Inhibitor composition for hangers when using chromium-free etchants in plastic plating processes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1250768C (en) | 2006-04-12 |
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