CN106399983A - Non-cyanide electroless gold plating bath and electroless gold plating method - Google Patents
Non-cyanide electroless gold plating bath and electroless gold plating method Download PDFInfo
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- CN106399983A CN106399983A CN201610584745.6A CN201610584745A CN106399983A CN 106399983 A CN106399983 A CN 106399983A CN 201610584745 A CN201610584745 A CN 201610584745A CN 106399983 A CN106399983 A CN 106399983A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The invention provides a gold plating bath which can be used in gold plating of an ENIG procedure and an ENEPIG procedure. The non-cyanide electroless gold plating bath includes gold salt with water solubility, a reducing agent and a complexing agent. The gold plating bath without cyanide is characterized in that the reducing agent includes formic acid or salt thereof, and hydrazine.
Description
Technical field
The present invention relates to a kind of non-cyanide electroless gold bath and electroless gold-plating method.
Background technology
In the past, in the installation procedure of printed circuit board (PCB) or electronic unit, it is surface-treated as final, has in chemical nickel plating
The gold-plated ENIG of upper formation displaced type (Electroless Nickel Immersion Gold, chemical nickel plating leaching gold) operation.Should
Operation can use in welding.Additionally, pass through to implement after this ENIG operation thick gold-plated it is also possible to make in wire bonding
With.
On the other hand, by chemical palladium-plating in based chemistry nickel plating and form gold-plated ENEPIG (Electroless
Nickel Electroless Palladium Immersion Gold, chemical nickel plating plating palladium leaching gold) operation be also adopted by above-mentioned
Final surface treatment.This operation is particularly well-suited in pb-free solder.In addition it is also applied in wire bonding.
Above-mentioned ENIG operation and ENEPIG operation, can be selected according to the purposes of plated body, and both are finally real
Plating gold.When but except for the difference that, in formation, this is gold-plated, with respect to the former with ionization tendency big (oxidation-reduction potential is low)
Nickel is substrate, and the latter is with the palladium of ionization tendency little (oxidation-reduction potential is high) as substrate.Thus, up to now, use respectively
Adapt to the gold plating bath of various operations.
Additionally, as above-mentioned gold plating bath, the conventional cyanogen gold plating bath that has is widely used, it is contemplated that the toxicity of cyanogen, need
Find non-cyaniding type gold plating bath.
For example, as cyaniding type gold plating bath non-used in above-mentioned ENEPIG operation, Patent Document 1 discloses, in print
On the conductor part of printed circuit board, when sequentially forming chemical nickel plating film, chemical palladium-plating film and chemical plating golden film, form described chemistry
The gold plating liquid that gold-plated film is used is made up of the aqueous solution containing water-soluble gold compound, reducing agent and chelating agent, this reducing agent
It is at least one in formaldehyde sulfurous acid hydrogen species, rongalite and hydrazine.Additionally, Patent Document 2 discloses, as can
The chemical gold plating liquid of golden film is directly separated out with autocatalysis reduction reaction on chemical palladium-plating film, non-cyanogen is contained with normal concentration
Sulfurous acid gold salt, sulphite, thiosulfate, water-soluble poly amino carboxylic acid, benzotriazole cpd, the amino acidifying of sulfur-bearing
Compound and the plating solution of hydroquinone.
But, according to the purposes of plated body, prepare the plating bath of each operation and replacing plating bath can spend process number and expense,
Impracticable from the viewpoint of operability and economy.Thus need ENIG operation and ENEPIG operation formed gold-plated in
The gold plating bath using.
Further, above-mentioned non-cyaniding type gold plating bath, compared with having cyanogen gold plating bath, exist be susceptible to plating bath stability and
The tendency that plating reactivity reduces.Thus, non-cyaniding type gold plating bath expects to have both the preferred of plating bath stability and plating reactivity
Characteristic.
Prior art literature
Patent documentation
Patent documentation 1：No. 5526440 publications of Japanese Patent No.
Patent documentation 2：JP 2010-180467 publication
Content of the invention
Currently invention addresses above-mentioned technical problem, it is intended that realize one kind in ENIG operation and ENEPIG operation
In can use non-cyanide electroless gold bath, and using this chemical gilding bath electroless gold-plating method.
The non-cyanide electroless gold solving the present invention of above-mentioned technical problem is bathed and is, containing water solublity gold salt, reducing agent and
Chelating agent, and the chemical gilding not containing cyanogen is bathed it is characterised in that described reducing agent contains formic acid or its salt, and hydrazine.
Described non-cyanide electroless gold bath, further preferably has the compound of nitro.
Present invention additionally comprises a kind of electroless gold-plating method is it is characterised in that bathed using above-mentioned non-cyanide electroless gold, in quilt
Implement chemical gilding on the surface of plating thing.This electroless gold-plating method, the surface of described plated body is nickel or nickel alloy, i.e. permissible
For ENIG operation, or, the surface of described plated body is palladium or palldium alloy, i.e. can also be ENEPIG operation.
In accordance with the invention it is possible to provide the no cyanogen that can use in any one in ENIG operation and ENEPIG operation
Chemical gilding is bathed.Specifically, in ENIG operation, when forming gold-plated in nickel plating, the corrosion of nickel plating is suppressed.In addition in ENIG
In any one in operation and ENEPIG operation, the evolution reaction of gold improves, and is capable of gold-plated thick-film.For example
In ENIG operation, with more than 0.07 μm of precipitation can be obtained within about 20 minutes in nickel plating, in ENEPIG operation on plating palladium
With more than 0.05 μm of precipitation can be obtained within about 30 minutes.
Brief description
Fig. 1 and Fig. 2 is SEM (the Scanning Electron representing the presence or absence of corrosion of nickel plating surface in embodiment
Microscope) observe photo.
Specific embodiment
The present inventor, in order to solve described technical problem, has made intensive studies.It is it was found that for conduct
When reducing agent contains the non-cyanide electroless gold bath of the displacement reduced form of formic acid or its salt and hydrazine, substrate can not be occurred to plate
The excessive corrosion of nickel etc., improves the evolution reaction of gold, can ENIG operation and ENEPIG operation both in use, thus
Complete the present invention.Hereinafter, also the non-cyanide electroless gold bath of the present invention is referred to as " chemical gilding bath " or " gold plating bath ".Following
In, contained each compound in the non-cyanide electroless gold bath of the present invention is illustrated
(A) hydrazine
Hydrazine is particularly useful the compound improving the coating precipitation property on palladium, promotes on plating palladium in ENEPIG operation
Gold-plated formation.Additionally, hydrazine also contributes to keep good Deposit appearance, its result contributes to guarantee good weldability
With wire bonding zygosity (W/B zygosity).On the other hand, in ENIG operation, necessity is promoted in nickel plating hydrazine with Shangdi
The carrying out of displacement reaction, can lead to the excessive corrosion of nickel plating.But as be described hereinafter, by and with formic acid or its salt, can be suppressed this
The excessive corrosion of nickel plating.
As described hydrazine, it is possible to use hydrazine, the hydrazine hydrate of hydrazine hydrate etc., carbonic acid hydrazine, Hydrazinium sulfate, dihydrazine sulfate, salt
The hydrazonium salt of sour hydrazine etc., organic derivative of hydrazine of pyrazoleses, triazole type, hydrazides class etc. etc..As described pyrazoleses, except pyrazoles
Outward, it is possible to use the pyrazole derivatives of 3，5-dimethylpyrazole, 3- methyl -5- pyrazolone etc..As described triazole type, permissible
Using 4- amino -1,2,4- triazole, 1,2,3- triazole etc..As hydrazides class, it is possible to use adipic dihydrazide, maleic acid acyl
Hydrazine, carbohydrazide etc..It is preferably hydrazine hydrate, the Hydrazinium sulfate of a hydrazine hydrate etc..These compounds can individually or two or more merging makes
With.
Total concentration of above-mentioned hydrazine, preferably 0.1-5g/L.More preferably 0.3-3g/L.
(B) formic acid or its salt
Formic acid or its salt, have the effect of the excess displacement reaction suppressing above-mentioned hydrazine to lead to.Hereinafter, also will " formic acid or
Its salt " is generically and collectively referred to as formic acid class.Especially, during gold-plated in ENIG operation, the excessive corruption of the Ni film as substrate can be suppressed
Erosion.On the other hand, not with above-mentioned hydrazine and with and only using formic acid class in the case of, particularly in ENEPIG operation, easily
The evolution reaction that gold occurs reduces.Specifically, golden evolution reaction difference on the plating palladium as substrate is it is difficult to guarantee gold-plated
Thickness.Thus it is necessary to being used in combination with above-mentioned hydrazine.By and with hydrazine and formic acid class, the excessive corrosion of above-mentioned nickel plating is pressed down
System, and also contribute to weldability and W/B zygosity.
As the salt of described formic acid, for example, can enumerate the alkali metal salt of the formic acid of potassium formate, sodium formate etc.；Magnesium formate, first
The alkali salt of the formic acid of sour calcium etc.；The ammonium salt of formic acid, quarternary ammonium salt, comprise amine salt of one-level～tertiary amine etc..The present invention
In, formic acid or its salt can individually or two or more merges and uses.
Total concentration of above-mentioned formic acid class is preferably to contain in the range of 1-100g/L.In order that the effect above is fully sent out
Wave, preferably more than 1g/L, more preferably more than 5g/L, more preferably more than 10g/L.On the other hand, excessively contain sometimes
Plating bath easily becomes unstable, below 100g/L preferably described above.
That is, in the present invention, pass through and use hydrazine and formic acid class as reducing agent, in the gold-plated process of ENIG operation
In, the nickel corrosivity (displacement reaction) that hydrazine leads to are suppressed by formic acid class, can suppress the corrosion of the nickel plating as gold-plated substrate.
On the other hand, in the gold-plated process of ENEPIG operation, due to high response on plating palladium for the hydrazine, compare what formic acid was used alone
Situation promotes gold-plated formation, so that gold-plated thick-film is possibly realized.This is the result due to promoting reduction reaction.
The gold plating bath of the present invention, in addition to above-mentioned hydrazine and formic acid class it is necessary to containing water solublity gold salt and chelating agent and
Do not contain cyanogen.In addition such as following, it is possible to use the reducing agent beyond hydrazine and formic acid class.Hereinafter, from above-mentioned water solublity gold salt
Start to illustrate successively.
The chemical gilding of the present invention first is bathed, and contains water solublity gold salt as Jin Yuan.Water solublity gold salt described above is non-
Cyanogen, specifically, can enumerate gold sulphite, thiosulfate, rhodanate, sulfate, nitrate, mesylate, four
Ammino-complex, chloride, bromide, iodide, hydroxide, oxide etc..These compounds can individually or two or more conjunction
And use.Total concentration of the water solublity gold salt in plating bath is preferably calculated as 0.3-5g/L with golden (Au) concentration, particularly preferably
0.5-4g/L.During less than 0.3g/L, there is the slack-off situation of speed of separating out.When on the other hand, more than 5g/L, existence and stability drops
Low situation, even if incrementss effect is also not changed in substantially, expense also can uprise in addition.
The chemical gilding bath of the present invention, as reducing agent, in addition to above-mentioned hydrazine and formic acid class, can also contain following
Reducing agent.That is, ascorbic acid or its salt (sodium salt, potassium salt, the ammonium of ascorbic acid, arabo-ascorbic acid (erythorbic acid) etc. can be enumerated
Salt etc.)；Hydroquinone of hydroquinone, methyl hydroquinone etc. or derivatives thereof；Pyrogallol, pyrogallol monomethyl ether, neighbour
Pyrogallol of benzenetriol -4- formic acid, pyrogallol -4,6- dioctyl phthalate, gallic acid etc. or derivatives thereof etc..These compounds
Can individually or two or more merge use.In the present invention, as reducing agent, above-mentioned hydrazine and formic acid class and with being necessary,
For example, show in embodiment No.10 described later, even if the reducing agent as beyond above-mentioned hydrazine and formic acid class is anti-bad
Hematic acid is used in combination with formic acid class, and it also cannot obtain desired characteristic.
Hydrazine in gold plating bath and the above-mentioned reducing agent beyond formic acid class add up to concentration to be preferably 0.5-50g/L, especially excellent
Elect 1-10g/L as.
The chemical gilding bath of the present invention contains chelating agent.It is that there is dissolution metal (such as nickel, palladium etc.) as chelating agent
The chelating agent of complexing, it is however preferred to have the chelating agent of the complexing of gold.As preferably described, there is dissolution metal
The chelating agent of complexing, can enumerate hydroxyacetic acid, diglycolic acid, lactic acid, malic acid, citric acid, gluconic acid, glucoheptonic acid
The hydroxy carboxylic acid of (acid of ヘ プ ト グ Le U Application) etc. or its salt (sodium salt, potassium salt, ammonium salt etc.)；Glycine, diamino dicarboxylic acid, amino
The amino carboxylic acid of triacetic acid, EDTA, hydroxyethylethylene diamine tri-acetic acid, diethylene triamine pentacetic acid (DTPA), polyaminocarboxylic acid etc. or its salt
(sodium salt, potassium salt, ammonium salt, hydrochlorate, sulfate etc.)；HEDP (hydroxyl ethane -1,1- di 2 ethylhexyl phosphonic acid), amino trimethyl sulfonic acid, second
The phosphorous acid system chelating agen of diamidogen tetramethyl sulfonic acid etc. or its salt (sodium salt, potassium salt, ammonium salt, hydrochlorate, sulfate etc.)；Second two
The amine system chelating agen of amine, diethylenetriamines, trien etc. and its salt (hydrochlorate, sulfate etc.) etc..These chemical combination
Thing can individually or two or more merge use.
Additionally, as the chelating agent of the complexing preferably with gold, sodium sulfite, potassium sulfite, sulfurous can be enumerated
Sour ammonium, sodium sulfite, Potassium acid sulfite, ammonium bisulfite, sodium pyrosulfite, potassium metabisulfite, ammonium pyrosulfite, thio sulfur
Sour sodium, Potassium hyposulfite., Ammonium hyposulfite., hydantoin compound, imide compound etc..These compounds can individually or
Two or more merges use.More preferably using sodium sulfite, ammonium sulfite etc..
In gold plating bath, the network of the chelating agent of the described complexing with dissolution metal and the described complexing with gold
Total concentration of mixture is preferably 1-200g/L, particularly preferably 10-150g/L.
The chemical gilding bath of the present invention, preferably also contains the compound with nitro.By having the change of nitro containing this
Compound, even if not containing cyanogen, to plating reactivity, that is, the evolution reaction of gold is also harmless, can substantially ensure that plating bath is stable
Property.As this mechanism of action it is believed that nitro captures stabilizing it of gold.In contrast, do not contain for example adjacent benzene two of nitro
The effect of stability is not shown in phenol or benzoic acid.
As the above-mentioned compound with nitro, for example, can enumerate the aromatic compound with nitro.Have as this
The aromatic compound of nitro, for example, can enumerate Nitrobenzol；Nitrophenol, 4- Nitrocatechol etc. have the virtue of nitro and hydroxyl
Fragrant compounds of group；The aromatic compound with nitro and alkyl of Methylnitrobenzene, nitroxylene, nitrostyrolene etc.；Nitre
The aromatic compound with nitro and amido of base aniline, 4- nitro -1,2- phenylenediamine etc.；Nitro thiophenol, 2,4- dinitro
The aromatic compound with nitro and sulfur-containing group of the nitrobenzene-sulfonic acid of base benzenesulfonic acid etc. etc..Further, as having
Nitro and the nitrobenzoic acid of carboxyl, for example, can enumerate 2- nitrobenzoic acid, 3,5- dinitrobenzoic acid, 3,4- dinitro benzene first
Acid, there is 5- amino -2- nitrobenzoic acid of amino etc. further.Additionally, while can enumerating with nitro, there is halogen radical
The aromatic compound of group, ester group, ether, carbonyl, aldehyde radical etc..In addition as the aromatic compound above with nitro
Salt, can use ammonium salt, sodium salt, potassium salt etc..
For example in the case of above-mentioned nitrobenzoic acid, when nitro is located on the ortho position of carboxyl, the effect of stability improves institute
To preferably use.That is, the size order of the effect of stability is 2- nitrobenzoic acid ＞ 3- nitrobenzoic acid ＞ 4- nitrobenzoyl
Acid.
As the above-mentioned compound with nitro, in addition to the above-mentioned aromatic compound with nitro, can also make
With having the aliphatic compound of nitro.
More preferably there is the compound of nitro and electron-donating group simultaneously, especially while having nitro and electron-donating group
The aromatic compound of group.When having electron-donating group, the effect of the stability of nitro improves.Nitro is two adjacent nitros
In the case of, two nitros are formed as clip shape (ト ラ ッ プ The Ru shape), are improved by the effect of this stability.As described power supply
Subbase group, for example, can enumerate hydroxyl, alkyl, amino, sulfur-containing group, carboxyl, ester group, halogen group, ether etc..Preferably have
Of the above more than one.
Independent for above-mentioned various compounds or two or more merging can be used by the above-mentioned compound with nitro.Above-mentioned tool
There is total concentration of the compound of nitro, preferably in the range of such as 0.0010-5g/L.Above-mentioned total concentration is 0.0010g/
During below L, hardly result in the effect above.Above-mentioned total concentration be more preferably more than 0.005g/L, more preferably 0.010g/L with
On.On the other hand, during the excessive concentration of the above-mentioned compound with nitro, the surface as the nickel plating of substrate becomes easy corruption
Erosion.Thus above-mentioned total concentration, preferably as above-mentioned below 5g/L, more preferably below 4g/L, more preferably 3g/L with
Under.
The pH of the chemical gilding bath of the present invention is preferably 5-10.During less than this scope, the speed of separating out of gold is easily reduced, separately
On the one hand, when exceeding above range, plating bath easily becomes unstable.Above-mentioned pH is more preferably 6-9.
The chemical gilding bath of the present invention, is not affecting in the range of the purpose of the present invention, can suitably contain known pH
Regulator, pH buffer and other additive.As above-mentioned pH adjusting agent, for example, can enumerate hydrochloric acid, sulphuric acid, nitre as acid
Acid, phosphoric acid, carboxylic acid etc., can enumerate sodium hydroxide, potassium hydroxide, ammonia etc. as alkali.Additionally, as above-mentioned pH buffer, can
Enumerate the carboxylic acid of citric acid, tartaric acid, malic acid, phthalic acid etc.；The phosphorus of orthophosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid etc.
Acid, or they potassium salt, sodium salt, the phosphate of ammonium salt etc.；Boric acid, tetraboric acid etc..Additionally, as metal cation screening agent,
The azole of benzotriazole, methylbenzotrazole etc., phenanthrolene, bipyridyl, salicylate etc. can be enumerated.In addition as auxiliary
Chelating agent, can enumerate the amino carboxylic acid of EDTA, EDTMP etc., ammonium salt, chloride etc..In addition as stabilizer, for example, can enumerate and contain
Sulfurheterocyclic compound (2-mercaptobenzothiazole, 2- mercaptobenzoxazole etc.), nitrogen-containing heterocycle compound (benzotriazole, N- hydroxyl
Benzotriazole etc.) etc..
The chemical gilding bath of the present invention, it is possible to further add in thallium compound, arsenic compound and lead compound
More than kind.These compounds have the gold-plated speed of raising and the effect as crystallization modifier.As this compound, specifically may be used
Enumerate and constitute the carbonate of metal (arsenic, thallium, lead) of compound, acetate, nitrate, sulfate, hydrochlorate etc..In gold plating bath
Above-mentioned crystallization modifier concentration, for example preferably add up to 0.1-100mg/L in terms of metal concentration, more preferably add up to 0.2-
50mg/L, further preferably adds up to 0.2-20mg/L.
The present invention also specify the method carrying out chemical gilding using the bath of above-mentioned non-cyanide electroless gold.Implement gold-plated plated
Thing, can enumerate its surface is nickel or nickel alloy.In above-mentioned ENIG operation, the surface that can enumerate plated body is chemical nickel plating or change
Learn the situation of nickel plating alloy (hereinafter referred to as " chemical nickel plating system ").As described nickel alloy, nickel-phosphor alloy can be enumerated, nickel-boron is closed
Gold etc..
Implement gold-plated plated body, its surface can also be palladium or palldium alloy.In above-mentioned ENEPIG operation, can enumerate by
The surface of plating thing is the situation of chemical palladium-plating or chemical palladium-plating alloy (hereinafter referred to as " chemical palladium-plating system ").Close as described palladium
Gold, can enumerate Pd-P alloys etc..
In ENIG operation, for example, form chemical nickel plating system in Al the or Al based alloy, Cu or Cu based alloy of composition electrode,
Then it is formed on chemical gilding, in ENEPIG operation, for example, constituting Al or Al based alloy, Cu the or Cu based alloy of electrode
Upper formation chemical nickel plating system, is subsequently formed chemical palladium-plating system, is then formed on chemical gilding, above-mentioned chemical nickel plating system or change
Learn the formation of plating palladium system, the method generally carrying out can be adopted.
In any one in above-mentioned ENIG operation and ENEPIG operation, the formation of chemical gilding, except using the present invention
Non-cyanide electroless gold bath outside, can be using the condition that generally carries out.For example can enumerate in the chemical gilding of the present invention is bathed
About contact 3-20 minute.As this contact, it is possible to use the known method of impregnating.Using of chemical gilding bath is warm
Degree, preferably 40-90 DEG C.During not enough above range, there is the possibility that speed of separating out reduces, on the other hand, when exceeding above range,
There is the possibility that plating bath is unstable.Above-mentioned use temperature is preferably 50-80 DEG C.
The chemical gilding bath of the present invention and the electroless gold-plating method using the bath of this chemical gilding, are suitable for printing electricity
The wired circuit mounting portion of the electronic unit of base board, ceramic substrate, semiconductor substrate, IC package etc. or terminal part are carried out
The situation of gold-plated process.It is particularly suitable for, to the Al electrode on chip or Cu electrode, engaging with wire bonding (W/B) to weld
For the purpose of UBM (Under Barrier Metal) formation technology in.By using the gold plating bath of the present invention, can stablize into
Row forms the formation of the chemical gilding of a part of technology as UBM, and its result can be achieved on stable membrane property.
Based on the application advocates Japanese invention patent application filed in 28 days July in 2015 the 2015-148523rd
Priority.The full content of the description of Japanese invention patent application filed in 28 days July in 2015 the 2015-148523rd is made
It is that reference is incorporated into the application.
Embodiment
Next, being specifically described to the present invention by enumerating embodiment, the present invention is not limited by following embodiments,
Suitable change can be carried out in the teachings adapting to context to implement, these are all contained in the technical scope of the present invention.
[confirmation that has or not of corrosion for gold-plated film thickness measuring, nickel plating and the making of the sample of gold-plated visual inspection]
(sample of ENIG operation)
The sample of the ENIG operation of the uses such as above-mentioned gold-plated film thickness measuring, is obtained with following method.That is, prepare conduct
The TEG chip that the Al-Cu of the Al based alloy of electrode is formed, on this electrode, using electroless nickel bath (C. Uyemura ＆ Co Ltd
NPR-18 processed), form the nickel plating of 5.0 μ m thick by electroless plating method, next, using chemical gilding bath as shown in table 1, real
Apply chemical gilding.Hereinafter this sample is referred to as " the sample I of ENIG operation ".
(sample of ENEPIG operation)
The sample of the ENEPIG operation of the uses such as above-mentioned gold-plated film thickness measuring, is obtained with following method.That is, prepare to make
The TEG chip being formed for the Al-Cu of the Al based alloy of electrode, on this electrode, using electroless nickel bath (upper village industry strain formula meeting
Society NPR-18), form the nickel plating of 5.0 μ m thick by electroless plating method, next in this nickel plating, bathed using chemical palladium-plating
(C. Uyemura ＆ Co Ltd TFP-30), forms the plating palladium of 0.05 μ m thick, further, using such as table by electroless plating method
Chemical gilding bath shown in 1, implements chemical gilding.Hereinafter this sample is referred to as " the sample I of ENEPIG operation ".
The further condition of the chemical gilding that each sample of above-mentioned ENIG operation and ENEPIG operation is carried out in making is as follows
Described.That is, in chemical gilding bath, use gold sodium sulfide solution (Au concentration=100g/L) as Jin Yuan, shown in aftermentioned table 1
Au concentration in chemical gilding bath.Additionally, using thallium carbonate as thallium (Tl) compound, in aftermentioned table 1, show chemical plating
Tl concentration in gold bath.The temperature of described chemical gilding bath is 75 DEG C, the dipping in the bath of described chemical gilding, ENIG operation
Carry out in the case of sample I 20 minutes, carry out in the case of the sample I of ENEPIG operation 30 minutes, formed gold-plated.And, after
In the sample I of the ENEPIG operation of the No.1 of table 1,2,4 and 6 stated, due to gold-plated thickness can be guaranteed in advance, therefore impregnate
Time is 20 minutes.
[gold-plated film thickness measuring in ENIG operation or ENEPIG operation]
The gold-plated thickness fluorescent X-ray film that the sample I of the sample I of above-mentioned ENIG operation and ENEPIG operation is formed
Thick instrument measures.And, the situation evaluation particularly, the gold-plated thickness on the plating palladium in ENEPIG operation being more than 0.05 μm
For being applicable to the gold plating bath of ENEPIG operation.
[the presence or absence of nickel plating corrosion is observed by SEM]
For by the gold-plated nickel plating surface being removed and being exposed with the golden liquid of stripping of the sample I of ENIG operation, with SEM in multiplying power
Observe under 5000 times, confirm the presence or absence of corrosion trace.Then will confirm that the sample of corrosion trace is evaluated as nickel plating corrosivity " having ", will
The sample not confirming corrosion trace is evaluated as nickel plating corrosivity "None".Shine as showing in reference Fig. 1 and Fig. 2 that SEM observes
Piece.Fig. 1 is the photo of the embodiment of the present invention of corrosion trace not confirming nickel plating, and Fig. 2 is the corrosion trace confirming nickel plating
The photo of comparative example.
[gold-plated visual inspection]
The gold-plated surface of the sample I of above-mentioned ENIG operation and the sample I of ENEPIG operation is detected by an unaided eye.Then, it is in
Now the sample of uniformly golden Deposit appearance is evaluated as " good ", is not that Deposit appearance that is golden but being changed into redness is evaluated as
" bad ".
[making of weldability and wire bonding (W/B) property sample for evaluation]
(sample of ENIG operation)
Used in weldability and W/B evaluation, the sample of ENIG operation, prepares C. Uyemura ＆ Co Ltd's BGA substrate
(pad diameter), on the substrate, identically with the sample I of above-mentioned ENIG operation, using electroless nickel bath (upper village
Industrial Co., Ltd NPR-18), form the nickel plating of 5.0 μ m thick by electroless plating method, next, using as shown in table 1
Chemical gilding is bathed, and implements chemical gilding.Hereinafter this sample is referred to as " the sample II of ENIG operation ".
(sample of ENEPIG operation)
Used in weldability and W/B evaluation, the sample of ENEPIG operation, prepares C. Uyemura ＆ Co Ltd's BGA substrate
(pad diameter φ 0.5mm), on the substrate, identically with the sample I of above-mentioned ENEPIG operation, using electroless nickel bath (on
Industrial Co., Ltd of village NPR-18), form the nickel plating of 5.0 μ m thick by electroless plating method, next in this nickel plating, use
Chemical palladium-plating bathes (C. Uyemura ＆ Co Ltd TFP-30), forms the plating palladium of 0.05 μ m thick by electroless plating method, further
Ground, using chemical gilding bath as shown in table 1, implements chemical gilding.Hereinafter this sample is referred to as the " sample of ENEPIG operation
II”.
[evaluation of weldability]
Using the sample II of the above-mentioned ENIG operation and sample II of ENEPIG operation, using Dage society Bondtester
Each condition evaluating of SERIES 4000 is 20 points.Specifically, total 4 conditions below sequentially determining in each No. of table 1 ×
The weld strength that 20=80 divides,
Using the sample II of ENIG operation, following reflow's cycles are the situation of 1 time；
Using the sample II of ENEPIG operation, following reflow's cycles are the situation of 1 time；
Using the sample II of ENIG operation, following reflow's cycles are the situation of 5 times；And
Using the sample II of ENEPIG operation, following reflow's cycles are the situation of 5 times.
As this weld strength, obtain the welding breaking rate of fracture mode.Welding forms the condition determination with weld strength
As follows.In the present embodiment, the situation that welding breaking rate is more than 85% is evaluated as weldability " good ", welding breaking rate is not
The situation of foot 85% is evaluated as weldability " bad ".
(condition that solder is formed and weld strength measures)
Mensuration mode：Soldered ball pull-out test
Soldered ball：Thousand live in metal φ 0.6mm Sn-3.0Ag-0.5Cu
Reflux：Field village makes made TMR-15-22LH
Counterflow conditions：Top 240℃
Backflow environment：Air
Reflow's cycle：1 time or 5 times
Flask：Thousand live in metal 529D-1 (RMA type)
Test speed：5000 μm/second
Aging (half field マ ウ Application ト Hou エ ジ Application グ) after weldering installation：1 hour
[evaluation of wire bonding (W/B) property]
Using the sample II of the above-mentioned ENIG operation and sample II of ENEPIG operation, by TPT society Semi-automatic lead key
Clutch HB16 carries out wire bonding, is 20 points by each condition evaluating of Dage society Bondtester SERIES 4000.Tool
Body ground, the sample in the case of the sample II using ENIG operation with using ENEPIG operation for the sequentially determining in each No. of table 1
In the case of II, the Wire bonding strength (W/B intensity) that total 2 condition × 20=40 divide, the W/B calculating its meansigma methods is average
Intensity and standard deviation.Further, obtain the coefficient of variation (=standard deviation ÷ meansigma methodss × 100) on the basis of it.Wire bonding
The condition of formation condition and wire bonding evaluation is as follows.And be more than 8gf by W/B mean intensity, and the coefficient of variation
Situation for less than 15% is evaluated as wire bonding " good ", by least one in above-mentioned W/B mean intensity and the coefficient of variation
Situation outside above range is evaluated as wire bonding " bad ".
(condition that wire bonding is formed and wire bonding is evaluated)
Capillary tube：B1014-51-18-12(PECO)
Lead：1Mil-Gold
Phase temperature：150℃
Ultrasound wave (mW)：250 (1st), 250 (2nd)
Bonding time (millisecond)：200 (1st), 50 (2nd)
Pulling force (gf)：25 (1st), 50 (2nd)
Step-length (the first to the second length)：0.700mm
Mensuration mode：Bracing wire is tested
Test speed：170 μm/second
And, in the present embodiment, above-mentioned weldability and above-mentioned wire bonding are the situation of " good ", evaluate welding
Property and W/B " good ", above-mentioned weldability and above-mentioned wire bonding are had a situation of " bad ", evaluate weldability and W/
B " bad ".
[evaluation of plating bath stability]
The chemical gilding bath of each plating bath composition shown in table 1 is placed one month at a temperature of 70 DEG C, evaluates plating bath
Stability.Place one month also the bath of Undec chemical gilding be evaluated as " stablize ", without the chemical plating of a just decomposition in month
Gold bath is evaluated as " unstable ".
The merging of its result is recorded in table 1.
Table 1
Following situation as shown in Table 1.In No.1-6, using by the formic acid class of regulation and hydrazine and with gold plating bath plated
Gold, gold-plated thickness also can fully ensure that in the case of ENEPIG operation, and in ENIG operation, the corrosion of nickel plating also obtains
Suppression, obtains good plating outward appearance.Additionally, these embodiments all can carry out welding well and wire bonding engages.And,
Be can be seen that from the viewpoint of guaranteeing sufficient plating bath stability by the contrast of No.1-3 and No.4, preferably also contain tool
There is the gold plating bath of the compound of nitro.Additionally, by the contrast of No.3 and No.5 as can be seen that the content of preferably formic acid class is to push away
Below the upper limit recommended (below 100g/L).
In contrast, No.7-10 does not contain any one in the formic acid class and hydrazine of regulation, there is defect.Specifically,
Due to not containing formic acid class, there is the corrosion of nickel plating in No.7 and No.8.Its result is weldability and W/B is deteriorated.In addition No.9
For not containing the example of hydrazine.In this example, the gold-plated thickness in ENEPIG operation is thinning.In addition No.10 is to use Vitamin C
Acid replaces hydrazine as reducing agent, the example with formic acid class.In this embodiment, the gold-plated thickness in ENEPIG operation becomes
Thin.In addition in No.9 and 10, gold-plated outward appearance is changed into red.It is such that to be changed into red be weldability and W/B the reason produce bad
Property be deteriorated.
Claims (5)
1. a kind of non-cyanide electroless gold bath, it is containing water solublity gold salt, reducing agent and chelating agent that this non-cyanide electroless gold is bathed, and does not contain
The chemical gilding having cyanogen is bathed it is characterised in that described reducing agent contains formic acid or its salt, and hydrazine.
2. non-cyanide electroless gold bath according to claim 1, wherein, this non-cyanide electroless gold bathes also to contain has nitro
Compound.
3. a kind of electroless gold-plating method is it is characterised in that usage right requires the non-cyanide electroless gold bath described in 1 or 2, plated
Chemical gilding is implemented on the surface of thing.
4. electroless gold-plating method according to claim 3, wherein, the surface of described plated body is nickel or nickel alloy.
5. electroless gold-plating method according to claim 3, wherein, the surface of described plated body is palladium or palldium alloy.
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| JP2015148523A JP6594077B2 (en) | 2015-07-28 | 2015-07-28 | Non-cyanide electroless gold plating bath and electroless gold plating method |
| JP2015-148523 | 2015-07-28 |
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| Country | Link |
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| JP (1) | JP6594077B2 (en) |
| KR (1) | KR102502530B1 (en) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111663123A (en) * | 2019-03-06 | 2020-09-15 | 上村工业株式会社 | Electroless gold plating bath |
| CN111763934A (en) * | 2020-06-01 | 2020-10-13 | 东莞市斯坦得电子材料有限公司 | Cyanide-free chemical thick gold plating process for printed circuit board |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200121333A (en) | 2018-02-20 | 2020-10-23 | 우에무라 고교 가부시키가이샤 | Electroless palladium plating solution and palladium film |
| JP6945050B1 (en) * | 2020-12-01 | 2021-10-06 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Non-cyanide replacement gold plating solution and replacement gold plating method |
| JP2023058312A (en) * | 2021-10-13 | 2023-04-25 | 上村工業株式会社 | Electroless gold plating bath |
| CN114737060B (en) * | 2022-05-02 | 2024-01-12 | 湖南金瑞新能源科技有限公司 | Recycling method of waste lithium battery anode material |
| CN115558912A (en) * | 2022-11-08 | 2023-01-03 | 深圳创智芯联科技股份有限公司 | Environment-friendly chemical reduction gold liquid and process thereof |
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| CN101634021A (en) * | 2008-07-24 | 2010-01-27 | 罗门哈斯电子材料有限公司 | Electroless gold plating solution |
| CN104736739A (en) * | 2012-07-13 | 2015-06-24 | 学校法人关东学院 | Non-cyanide gold plating bath and method for preparing non-cyanide gold plating bath |
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| BE793128A (en) | 1971-12-24 | 1973-04-16 | Kraftwerk Union Ag | PROCESS AND DEVICE FOR RELIEF, DEGAZATION AND DEACTIVATION OF CONDENSATES IN STEAM PLANTS, ESPECIALLY IN NUCLEAR PLANTS |
| JP4932542B2 (en) * | 2007-03-05 | 2012-05-16 | ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． | Electroless gold plating solution |
| JP5371465B2 (en) | 2009-02-09 | 2013-12-18 | メタローテクノロジーズジャパン株式会社 | Non-cyan electroless gold plating solution and conductor pattern plating method |
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2015
- 2015-07-28 JP JP2015148523A patent/JP6594077B2/en active Active
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2016
- 2016-06-20 TW TW105119314A patent/TWI688672B/en active
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101634021A (en) * | 2008-07-24 | 2010-01-27 | 罗门哈斯电子材料有限公司 | Electroless gold plating solution |
| CN104736739A (en) * | 2012-07-13 | 2015-06-24 | 学校法人关东学院 | Non-cyanide gold plating bath and method for preparing non-cyanide gold plating bath |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111663123A (en) * | 2019-03-06 | 2020-09-15 | 上村工业株式会社 | Electroless gold plating bath |
| CN111763934A (en) * | 2020-06-01 | 2020-10-13 | 东莞市斯坦得电子材料有限公司 | Cyanide-free chemical thick gold plating process for printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106399983B (en) | 2020-07-21 |
| KR20170013814A (en) | 2017-02-07 |
| TWI688672B (en) | 2020-03-21 |
| KR102502530B1 (en) | 2023-02-21 |
| JP2017025399A (en) | 2017-02-02 |
| TW201715081A (en) | 2017-05-01 |
| JP6594077B2 (en) | 2019-10-23 |
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