CN100402700C - Methyl free copper plating method and used solution thereof - Google Patents
Methyl free copper plating method and used solution thereof Download PDFInfo
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- CN100402700C CN100402700C CNB02151397XA CN02151397A CN100402700C CN 100402700 C CN100402700 C CN 100402700C CN B02151397X A CNB02151397X A CN B02151397XA CN 02151397 A CN02151397 A CN 02151397A CN 100402700 C CN100402700 C CN 100402700C
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Abstract
The present invention provides a chemical copper plating method without using formaldehyde and chemical copper plating solutions used in the method, and therefore, the present invention discloses a chemical copper plating method. The method comprises the steps: a platinum catalyst or a platinum-tin catalyst is deposited on resin base materials; the resin base materials of the catalyst deposited on the resin base materials are processed by a non-formaldehyde chemical copper plating solution containing copper ions and reducing agents; the rapid processing of the catalyst is not needed after the deposits of the catalyst are processed. Even if the rapid processing of the catalyst is not carried out by a single process, a copper thin layer is formed on the resin base materials in short time by the method. The method obviously enhances the productivity of copper-resin composite materials.
Description
[technical field of the present invention]
The present invention relates to the electroless copper plating method that a kind of use contains the formaldehydeless chemical copper plating solution of cupric ion and reductive agent.
The invention still further relates to chemical copper plating solution that is used for aforesaid method and the copper-resin composite materials that obtains by this method.
[background of invention]
When the preparation printed circuit board (PCB), use a kind of chemical plating method that utilizes chemical copper plating solution, in the through hole of non-conductive plastic basis material so that the copper layer of conduction to be provided.Re-plating copper on the conductive copper layer in through hole then.
[problem that the present invention solves]
Art methods institute major issue of inherent is to use formaldehyde in chemical copper plating solution.Formaldehyde relates to teratogenecity, mutagenicity and carinogenicity.Therefore, some formaldehydeless chemical copper plating solutions have been developed.
In addition, the problem that electroless copper plating method ran into that the use of prior art contains the chemical plating solution of formaldehyde is, unless the use catalyzer, the deposition of copper needs for a long time.And the formaldehydeless chemical copper plating solution of most conventional is because their hyperergy has poor stability, and very fast decomposition when using.Therefore need exploitation to have the formaldehydeless chemical copper plating solution of high bath stability, and use it can finish the electroless copper process rapidly.
A target of the present invention provides the electroless copper plating method that does not need to use formaldehyde, thereby has got rid of and the environmental effect of using this compound to interrelate.Formaldehyde involves teratogenecity, mutagenicity and carinogenicity.Another target of the present invention provides the formaldehydeless chemical copper plating solution of deposited copper rapidly; The present invention also has a target to provide chemical copper plating solution formaldehydeless, that react rapidly, and this solution shows high bath stability.
[method of dealing with problems]
The invention provides a kind of formaldehydeless electroless copper plating method, may further comprise the steps:
1) palladium or palladium-tin catalyst are deposited on the resin base material; And
2) handle base material with formaldehydeless chemical copper plating solution, this solution contains cupric ion and reductive agent.
The invention still further relates to the formaldehydeless chemical copper plating solution that is used for described method, reach matrix material according to this method preparation.
The invention further relates in the copper coating that powers on of the described matrix material according to present method preparation, and according to the matrix material of this method preparation.
[embodiment preferred]
In the present invention, " electroless copper " is meant a kind of chemical process, forms the copper layer of conduction on resin base material by this method.This be deposited on subsequently plating such as the copper sulfate electroplating processes before finish.Among the present invention, the copper lamina of high conduction has from the teeth outwards on the resin base material of palladium or palladium-tin catalyst and forms rapidly.The invention provides the formaldehyde-free aqueous electroless copper plating bath that is used for aforesaid method.This plating bath contains cupric ion and reductive agent, can have from the teeth outwards to form thin copper layer on the resin base material of palladium or palladium-tin catalyst, and wherein catalyzer does not stand accelerate process.In the present invention, " chemical copper plating solution " is meant and can wherein has palladium or palladium-tin catalyst without accelerate process on the surface of base material by contact the plating bath that forms thin copper layer on base material with base material.
Use this catalyzer to remove the demand of accelerate process from the substrate surface.
The cupric ion that exists in the solution can derive from any suitable source.For example, can use the copper compound that when dissolving in plating bath, can produce cupric ion.Perhaps, can with compound dissolution in water, form the solution that contains cupric ion, supply in the plating bath then.The copper compound that can be used as the copper source comprises water miscible, that contain cupric ion and normally used in the art those compounds.Preferably, such compound will comprise: copper sulfate, cupric nitrate, cupric chloride, copper hydroxide, thionamic acid copper, cuprous carbonate, cupric oxide etc.More preferably use copper sulfate and cupric chloride.Suitable copper compound both can use separately, also can be used in combination.
The concentration of cupric ion is pressed metallic copper calculating in the solution, normally 0.5-5g/L, preferably 1-2g/L.Yet when chemical copper plating solution of the present invention comprises complexing agent and complexing agent concentration when high, copper ion concentration can be 2g/L or bigger.For example copper ion concentration can be up to 10g/L or bigger.
The reductive agent that uses in the chemical copper plating solution of the present invention is water miscible and can makes cupric ion be reduced into metallic copper and deposit to those reductive agents on the resin base material.Except that formaldehyde, any reductive agent all can use.Preferred reductive agent example includes but not limited to: the derivative of sodium borohydride, POTASSIUM BOROHYDRIDE, dimethylamino borine, front three amino borane, hydrazine and these compounds.What more preferably be used as reductive agent is the derivative of sodium borohydride, POTASSIUM BOROHYDRIDE, dimethylamino borine, front three amino borane, hydrazine and these compounds.What more more preferably be used as reductive agent is sodium borohydride and POTASSIUM BOROHYDRIDE, most preferably sodium borohydride.Above-mentioned reductive agent can use separately, also can be used in combination.
The concentration of reductive agent in chemical copper plating solution of the present invention is generally 0.1～10g/L, preferred 0.5～2g/L.When concentration surpassed 10g/L, it is unstable that plating bath becomes, and this reductive agent often becomes inoperative.
Randomly, chemical copper plating solution of the present invention can comprise complexing agent.Used complexing agent must complex copper ion.The example of complexing agent includes but not limited to: polyamines and salt thereof, aminocarboxylic acid and salt thereof, hydroxycarboxylic acid and salt thereof, alkanolamine and salt thereof etc.Can use single complexing agent among the present invention, or these combination of agents.
Polyamines and salt thereof comprises as quadrol, diethylenetriamine, diethylene tetramine, Triethylenetetramine (TETA) etc., with and hydrochloride, vitriol etc., but be not limited to these.
The polyamines that uses in the chemical copper plating solution and the concentration of salt thereof are generally 1～100g/L, preferred 5～50g/L.
Aminocarboxylic acid and salt thereof include but not limited to: iminodiethanoic acid and sodium salt thereof; Nitrilotriacetic acid(NTA) and sodium salt thereof; Reach hydroxyethylethylene diamine tri-acetic acid, THED tetrahydroxy ethylene diamine acetate, dihydroxymethyl ethylenediamine-N,N'-diacetic acid(EDDA), ethylenediamine tetraacetic acid (EDTA), 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetrapropionic acid(EDTP), N, N, N ', N '-four-(2-hydroxypropyl) quadrol etc., and their sodium salt and sylvite.
These compound concentrations of using in chemical copper plating solution are generally 1～100g/L, preferred 5～50g/L.
Chain triacontanol amine compound preferably includes: single-, two-and three-thanomin, but be not limited to these compounds.The concentration of the chain triacontanol amine compound that uses in chemical copper plating solution is generally 5～200ml/L, preferred 50～100g/L.
The example of hydroxycarboxylic acid comprises: tartrate, citric acid and glyconic acid.Hydroxycarboxylate's example comprises sodium tartrate, soluble tartrate, sodium-potassium tartrate, Trisodium Citrate, Tripotassium Citrate, ammonium citrate, gluconic acid sodium salt and potassium gluconate, but is not limited to these compounds.The concentration that common above-claimed cpd uses in chemical copper plating solution of the present invention is 1～100g/L, preferred 5～50g/L.
Chemical copper plating solution of the present invention can be chosen wantonly and comprise: water-soluble thallium compound, water-soluble cerium compound and/or water-soluble sulfide.Comprise water-soluble thallium compound, water-soluble cerium compound and/or water-soluble sulfide in the chemical copper plating solution, can improve the stability of plating bath significantly.Most preferably water-soluble thallium compound and/or water-soluble cerium compound.
Can use any water miscible thallium or cerium compound in the chemical copper plating solution of the present invention.As for water-soluble sulfide, can use any dissolve in solution comprise the compound of element sulphur with sulphided form.Water-soluble thallium compound, cerium compound or sulfide can comprise: the compound that contains in the elementary sulfur of elemental cerium, element thallium or sulphided form any one; Perhaps contain compound multiple in the elementary sulfur of elemental cerium, element thallium or sulphided form.In addition, these compounds can use separately or be used in combination.
Described water-soluble thallium compound, described water-soluble cerium compound and/or described water-soluble sulfide can directly be dissolved in the chemical copper plating solution, or can be dissolved in earlier in the water, then the solution that is generated are added in the plating bath.
Can be used for water-soluble cerium compound of the present invention and comprise for example salt,, but be not limited to these compounds as cerous acetate, cerous nitrate, cerous sulfate, comprise cerium bromide, cerous carbonate, Cerium II Chloride, cerium fluoride, Sedemesis and their hydrate.Can be used for water-soluble thallium compound of the present invention and comprise salt, as thallium chloride, formic acid thallium, thallium trinitrate (TTN), thallium oxide, thallic sulfate and thallium acetate, or their hydrate, but be not limited to these compounds.Can be used for the sulfide that sulfide of the present invention comprises basic metal or alkaline-earth metal, but be not limited to these compounds.Preferred water-soluble sulfide comprises sodium sulphite, Sodium sulfhydrate, potassium sulphide, potassium bisulfide, barium sulphide, barium hydrosulfide, magnesium sulfide, sulphur magnesium hydride etc.Preferred water-soluble sulfide comprises sodium sulphite, Sodium sulfhydrate, potassium sulphide and potassium bisulfide.
The quantity of the water-soluble thallium compound that comprises in the chemical copper plating solution, water-soluble cerium compound and/or water-soluble sulfide should be enough to stablize chemical copper plating solution.The quantity of water-soluble cerium compound is 1mg/L～1000mg/L normally, preferred 5mg/L～30mg/L; The quantity of water-soluble thallium compound is 1mg/L～1000mg/L normally, preferred 5mg/L～30mg/L; The quantity of water-soluble sulfide is 1mg/L～1000mg/L normally, preferred 5mg/L～20mg/L.
Randomly, chemical copper plating solution of the present invention can comprise iodine and/or water-soluble iodine compound.Preferred chemical copper plating solution of the present invention comprises iodine and/or water-soluble iodine compound.If chemical copper plating solution comprises iodine or water-soluble iodine compound, can improve the stability of electroless copper plating bath and the sedimentation velocity of raising copper.The two all increases to contain benefit that iodine element obtains in the chemical copper plating solution and be the stability of electroless copper plating bath and copper sedimentation velocity.Under the general condition of the inventive method, just can reach this effect.
If chemical copper plating solution comprises iodine or water-soluble iodine compound, another benefit that obtains is to make become fine and close and resulting copper layer of sedimentary copper have the tone of gloss and metallic copper.In electroless copper plating method of the present invention, if chemical copper plating solution does not contain iodide ion, sedimentary copper layer is lackluster on the contrary mutually with the outward appearance of metal.In the electroless copper field, the outward appearance of institute's copper layer is considered to very important, therefore, wishes that especially the copper layer has the glossy metallic surface appearance.
Anyly in its molecule, contain iodine and dissolve in compound in the chemical copper plating solution, all can be used as water-soluble iodine compound of the present invention and use, but be not limited to these compounds especially.Iodine in the water-soluble iodine compound can exist in any form, for example with the form of iodide ion salt, as potassiumiodide, ammonium iodide, sodium iodide, thallium iodide; Or with the form of iodine and organism covalent linkage as 1,3-two chloro-4-phenyl-iodides, 8-hydroxyl-7-iodo-5-quinoline sulfonic acid and iodobenzoic acid.The water-soluble iodine compound that the present invention includes can use separately, and use maybe can mutually combine.
Water-soluble iodine compound can comprise other useful components of the present invention simultaneously, as thallium iodide.
Equally, iodine and/or described water-soluble iodine compound can directly be dissolved in the chemical copper plating solution, or can be dissolved in earlier in the water, then the solution that is generated are added in the plating bath.
In chemical copper plating solution of the present invention, iodine element can exist with the form of iodide ion, or exists with the part of molecule, as above-mentioned iodine to be covalently bound to the compound in the organism.Preferred chemical copper plating solution of the present invention comprises iodine compound.
Can infer that iodine quickens the deposition reaction of copper in the electroless copper treating processes, its mechanism is that iodine is adsorbed on the palladium catalyst or palladium-tin catalyst without accelerate process.Can also imagine that this works iodine element, because iodine all has above-mentioned effect with the ionic form or with the state that is covalently bound in the compound on palladium catalyst or palladium-tin catalyst.
If the iodine that comprises in the chemical copper plating solution of the present invention and/or the usage quantity of water-soluble iodine compound are too little, then can not demonstrate the effect of quickening deposited copper; If but used excessively, they could cause palladium catalyst or palladium-tin catalyst inerting.Therefore, the amount of iodine and/or water-soluble cpds is calculated with the weight of iodine, is generally 1mg/L～1000mg/L, preferred 5mg/L～30mg/L, more preferably 10mg/L～20mg/L.
Chemical copper plating solution of the present invention can randomly comprise the derivative of glycolylurea and/or glycolylurea.When chemical copper plating solution comprised glycolylurea and/or hydantoin derivatives, the sedimentation velocity of copper was accelerated.Preferred chemical copper plating solution of the present invention contains the derivative of glycolylurea.
In one embodiment of the invention, can use any compound, as the hydantoin derivatives that contains in the chemical copper plating solution of the present invention with glycolylurea structure.Another embodiment of the invention comprises by disconnection having resulting those compounds of glycolylurea ring in the compound of glycolylurea structure, as Ureidoacetic acid.These hydantoin derivatives can comprise any this compounds that dissolves in chemical copper plating solution, but are not limited to these compounds.These glycolylurea and/or hydantoin derivatives can use separately or be used in combination.
Be used for glycolylurea of the present invention and/or hydantoin derivatives and comprise glycolylurea, Ureidoacetic acid, 1-methyl glycolylurea, 5,5-diphenyl hydantoin, 5,5-T10,1,5,5-trimethylammonium glycolylurea and their derivative, but be not limited to these compounds.Preferred 5,5-T10 and 5,5-diphenyl hydantoin.The normally used concentration of glycolylurea and/or hydantoin derivatives is 1～100g/L in the chemical copper plating solution of the present invention, preferred 5～50g/L.
If desired, chemical copper plating solution of the present invention can contain various additives.These additives comprise for example pH regulator agent, coating improving agent, but are not limited to these.
The pH regulator agent remains on preferred value with the pH value of chemical copper plating solution of the present invention, and quickens cupric ion is deposited as the reduction reaction of copper.These pH regulator agent comprise mineral acid such as sulfuric acid, hydrochloric acid, phosphoric acid etc., and oxyhydroxide such as sodium hydroxide, potassium hydroxide etc., but are not limited to these compounds.The pH regulator agent can add with the amount of the pH that is enough to regulate chemical copper plating solution.The pH value that is preferred for the chemical copper plating solution of electroless copper plating method of the present invention is more than 10 or 10, and more preferably more than 13 or 13.
The purpose that adds the coating improving agent is the character for the copper lamina that improves the inventive method generation, as ductility, tensile strength, hardness, internal stress etc.; Perhaps its objective is the copper particulate that is deposited for refining.These coating improving agents for example comprise: sulfocompound such as thio-compounds, 2, and 2 '-dipyridyl, 1, the 1-phenanthroline, yellow prussiate of potash, ethylene oxide tensio-active agent, polyoxyethylene glycol etc., but be not limited to these compounds.These additives can use separately or be used in combination.
The quantity that adds these additives in the chemical copper plating solution of the present invention is set at the quantity that each additive shows required effect easily.For example, the concentration of thio-compounds is generally 1～100mg/L, preferred 5～10mg/L; The concentration of Bipyridine compound is generally 1～50mg/L, preferred 5～15mg/L; Surfactant concentrations is generally 1～500mg/L, preferred 10～20mg/L.
Resin base material of the present invention can use any base material, needs only them and has the character that is suitable for application purpose, for example intensity and erosion resistance; And they can be any forms and without any special restriction.The spendable resin base material of the present invention has no particular limits the moulding of resin, but can be to comprise strongthener as inserting the matrix material of the glass fibre in the resin; Or the matrix material of resin layer arranged on the ground of various materials as pottery, glass, metal etc.
Can use any resin to make resin base material, for example, polyolefin resin such as polyvinyl resin are as high density polyethylene(HDPE), medium-density polyethylene, side chain new LDPE (film grade), linear low density polyethylene, ultrahigh molecular weight polyethylene(UHMWPE); Acrylic resin; Polybutadiene; Poly-(1-butylene) resin; Polybutene resin; Polystyrene resin etc.Also can use halogen-containing resin such as polyvinyl chloride, polyvinylidene dichloride, polyvinylidene dichloride-vinyl chloride copolymer resin, chlorinatedpolyethylene, Chlorinated Polypropylene III, tetrafluoroethylene etc.In addition, can use the AS resin; ABS resin; The MBS resin; Polyvinyl alcohol resin; Polyacrylate resin such as polymethyl acrylate; Polymethacrylate resin such as polymethylmethacrylate; The copolymer of methyl methacrylatestyrene resin; The maleic anhydride-styrene copolymers resin; Vinylite; Celluosic resin such as cellulose propionate resin, rhodia resin; Resins, epoxy; Polyimide resin; Polyamide resin such as nylon; Polyamide-imide resin; The poly-allylat resin; Polyethers-imide resin; Polyether-ether-ketone resin; Polyethylene oxide resin; Various vibrin such as PET resin; Polycarbonate resin; Polysulfone resin; The polyvinyl ether resin; Polyvinyl butyral acetal; Poly (phenylene ether) resin such as polyphenylene oxide; Polyphenylene sulfide; The polybutylene terephthalate resin; The polymethylpentene resin; Polyacetal resin; The vinyl chloride vinyl acetate copolymer resin; Vinyl-vinyl acetate copolymer; Ethylene-vinyl chloride copolymer; And thermoplastic resin such as their multipolymer and their blend; Thermosetting resin such as Resins, epoxy; Xylene resin; Guanamine resin; Diallyl phthalate resin; Vinylester resin; Phenol resins; Unsaturated polyester resin; Furane resin; Polyimide resin; Urethane resin; Maleic acid resin; Melamine resin; Urea resin etc., and their blend, but be not limited to these compounds.Preferred resin comprises Resins, epoxy, polyimide resin, Vinylite, phenol resins, nylon resin, poly (phenylene ether) resin, acrylic resin, fluorinated resin and ABS resin.Preferred resin comprises Resins, epoxy, polyimide resin, poly (phenylene ether) resin, fluorinated resin and ABS resin.More more preferably Resins, epoxy and polyimide resin.Resin base material can be formed or be made up of various kinds of resin by single resin.Also can use resin is coated with the matrix material of spreading or being laminated on other grounds.
Can use conventional commercially available palladium or palladium-tin catalyst as the palladium among the present invention or palladium-tin catalyst.Employed catalyzer is the catalyzer of liquid form, and wherein palladium or palladium tin catalyst are present in the medium as colloid.For example can use the dilute aqueous solution of Crimson Activator-5300, it is a kind of palladium-tin catalyst that derives from Shipley company; And ConductronDP-H activator enriched material, it is a kind of palladium-tin catalyst that derives from LeaRonal Japan Inc.; But be not limited to these kinds.If use palladium-tin catalyst, the ratio of palladium and tin is a palladium: tin=1: 1～1: 100, more preferably 1: 1～1: 10.
In the electroless copper plating method of the present invention, at first palladium or palladium-tin catalyst are deposited on the resin base material.Anyly catalyst deposit all can be can be used to deposited catalyst to the method on the resin base material, for example resin base material is immersed in the catalyst solution, or catalyst solution is sprayed onto on the resin base material, but be not limited to these methods.In addition if desired, with before resin base material contacts, resin base material can stand burin-in process and etch is handled, and for example resin base material is immersed in catalyst solution at catalyzer, or catalyst solution is sprayed onto on the resin base material, so that palladium or palladium-tin catalyst are deposited on the resin base material easily.
With the densitometer of palladium, the catalyst concn in the catalyst solution that the present invention uses is 30mg/L～500mg/L, preferred 70mg/L～200mg/L.If the concentration of palladium is too low, can not from the copper solutions that comprises reductive agent, obtain the deposition of enough copper.If the concentration of palladium is too high, the palladium catalyst of absorption is excessive, and therefore the adhesion property of catalyzer reduces, and cost can increase.
As mentioned above, by resin base material being immersed in the catalyst solution or, implementing the depositing treatment of catalyzer on resin base material by catalyst solution is sprayed onto on the resin base material.When vertical the processing, deposit normally 3～10 minutes required treatment time, preferred 5～8 minutes; Normally 25～50 ℃ of the temperature of depositing treatment, preferred 35～45 ℃.When horizontal processing, deposit 15 second～3 minute normally of required treatment time, preferred 30 second～2 minute; Normally 25～50 ℃ of the temperature of depositing treatment are preferably 35～45 ℃.
Then, in electroless copper plating method of the present invention, the resin base material of catalyzer is arranged on the surface that obtains by above-mentioned processing, need not carry out any accelerate process, can be handled by chemical copper plating solution of the present invention, and will carry out accelerate process in the routine techniques.In the electroless copper plating method of conventional use formaldehyde, in the accelerating step of after supported catalyst, carrying out, tin is removed from palladium-tin catalyst.This is because catalyzer stands that palladium does not come out before the accelerate process, and the palladium PARA FORMALDEHYDE PRILLS(91,95) has high catalytic activity.Therefore the situation that stands accelerate process with catalyzer relatively needs the very long time induce the electroless copper reaction.If use the catalyzer that does not stand accelerate process, the impurity that is derived from the catalystic material of decomposition can enter in the liquor, makes the chemical copper plating solution instability, thereby has improved the danger of decomposing.
Phrase among the present invention " does not carry out the accelerate process of catalyzer " and is meant the processing that does not improve catalyst activity; Otherwise it will carry out between the step that deposits the step of disactivation catalyzer on the resin and handled with chemical copper plating solution afterwards as independent step.When described chemical copper plating solution contained the hyperergy reductive agent, in the process of handling with chemical copper plating solution of the present invention, this catalyzer was activated in chemical copper plating solution, finished the electroless copper reaction simultaneously.This moment, activity of such catalysts was enhanced.But this activation is not finished in single independent process.Therefore even realized the raising of catalyst activity by the processing of chemical copper plating solution, this raising is included in the description scope that this specification sheets " do not carry out the accelerate process of catalyzer ".
Because chemical copper plating solution of the present invention contains cupric ion and reductive agent, chemical copper plating solution forms the thin layer of copper on resin base material, thereby generates copper-resin composite materials.In electroless copper plating method of the present invention,, in the copper lamina of described copper-resin composite materials, there be the palladium or the palladium-Xi of metallic forms because resin base material is just to be handled by chemical copper plating solution behind resin base material at catalyst deposit.
In the present invention, the surface has the base material of catalyst deposit to contact with chemical copper plating solution of the present invention is firm, and copper just begins deposition rapidly, has spread whole catalyst surfaces when copper is coated with, and reaction has just been finished.Although can be when changing various conditions and regulate deposition reaction and finish the thickness of copper lamina, thickness is 0.01～0.2 μ m usually, preferred 0.03～0.1 μ m.Under any circumstance, the thickness of this copper lamina is less than 0.2～0.5 μ m, the chemical copper plating solution that this is to use identical catalyzer and resin base material and contains formaldehyde is by comprising the method for carrying out accelerate process step and electroless copper step, the general thickness of resulting copper lamina.
The sedimentation velocity of copper layer among the present invention is defined as chemical copper plating solution of the present invention contacts copper layer after 1 minute with base material thickness.If being deposited within a minute of copper layer finished, just Measuring Time suitably is set at and finishes the required time of copper layer deposition.
If use the chemical copper plating solution that contains formaldehyde, because the phenomenon of finishing as copper layer deposition among the present invention can not appear in the autocatalysis function of deposited copper.Even in this case, copper layer sedimentation velocity still is defined as chemical copper plating solution contacts copper layer after a minute with resin thickness.If do not observe the deposition of copper after chemical copper plating solution contacts one minute with base material, sedimentation velocity was with expression in 0 μ m/ minute.
In electroless copper plating method of the present invention, sedimentation velocity is preferably more than 0.02 μ m/ minute or 0.02 μ m/ minute, more preferably more than 0.05 μ m/ minute or 0.05 μ m/ minute.
Be sprayed onto on the resin base material by resin base material is immersed in the chemical copper plating solution or with chemical copper plating solution, finish the processing of chemical copper plating solution of the present invention.During vertical the processing, normally 1～5 minute plating bath treatment time, preferred 1～2 minute; And normally 30～70 ℃ of the temperature that plating bath is handled, preferred 50～60 ℃.During horizontal processing, the plating bath treatment time is 15 second～2 minute normally, preferred 30 second～1 minute; And normally 30～70 ℃ of the temperature that plating bath is handled, preferred 50～60 ℃.In a preferred embodiment of the invention, contain the chemical copper plating solution of formaldehyde with use and use same catalyst and routine techniques that resin base material carries out electroless copper relatively, depositing time has shortened, and the required treatment time of whole system has also shortened.
Copper-resin composite materials that electroless copper plating method of the present invention obtains can further impose electroless copper and handle, to form other layer of copper layer on the copper lamina of matrix material.As above-mentioned electroless copper plating method, can use any electroless copper plating method known in the art, as copper sulfate plating, cupric cyanide plating and cupric pyrophosphate plating.The preferred copper sulfate that uses plates.
Embodiment
In the following example, the whole bag of tricks of each embodiment and comparative example is under normal condition, uses and carries out at the normally used commercially available chemical reagent of these methods, except as otherwise noted.
The time of using chemical copper plating solution to handle in the following method is to finish the required time cycle of copper deposition substantially.The sedimentation velocity of copper layer is contact with base material afterwards by measuring chemical copper plating solution of the present invention that sedimentary copper coating thickness calculates in one minute the deposition process.Finish if be deposited within one minute, measure the sedimentation velocity of the suitable point before deposition is finished substantially.
It is as follows to measure the employed method of copper layer sedimentation velocity: the weight of 1) measuring the glass-epoxy base material of thorough drying with a precision balance; 2) on described base material, carry out electroless copper; 3) by the weight after measuring processed base material oven dry on the balance, gravimetric increase; 4) calculate deposit thickness by the increase of weight and the surface-area of base material.
Embodiment 1～8 and comparative example 1
Relatively copper-the resin composite materials that obtains by electroless copper plating method of the present invention and Electrocoppering method and those copper-resin composite materials that obtain by the conventional chemical copper electroplating method.
Resin base material adopts the copper-clad four of the thick 1.6mm of sheet to press material (Hitachi chemistry company limited makes) layer by layer, and it comprises glass fibre and bisphenol A type epoxy resin (FR-4).Embodiment 1～6,10 with 11 and comparative example 1 use vertical processing.Embodiment 7,8 and embodiment 9 application level are handled.Embodiment 8 has measured copper layer deposit thickness over time.
Embodiment 1
[table 1]
Table 1
| Step | Treatment temp | Treatment time |
| The aging formaldehydeless chemical copper plating solution * of etch load P d-Sn catalyzer copper electroplating | 60℃ 25℃ 43℃ 60℃ 25 |
5 minutes 1 |
*: formaldehydeless chemical copper plating solution
| Copper sulfate pentahydrate EDTA sodium borohydride 2,2 '-dipyridyl pH | 15g/L 45g/L 1g/L 10mg/L 12.5 |
When handling, finish electroless copper to handle the required time be 16 minutes from beginning to handle with aforesaid method; And it is 5 minutes that electroless copper is handled the required time.Obtain thickness and be 0.05 micron copper layer.Copper layer sedimentation velocity is 0.01 micron/minute.Observe 100 holes that diameter is 0.3mm, show that the space incidence of copper electroplating layer is 26%, wherein the space is meant and does not form the copper layer.Decompose immediately after the prepared chemical copper plating solution test.
Embodiment 2
[table 2]
Table 2
| Step | Treatment temp | Treatment time |
| The aging formaldehydeless chemical copper plating solution * of etch load P d-Sn catalyzer copper electroplating | 60℃ 25℃ 43℃ 60℃ 25 |
5 minutes 1 |
*: formaldehydeless chemical copper plating solution
| Copper sulfate pentahydrate EDTA sodium borohydride 2,2 '-dipyridyl thallic sulfate pH | 15g/L 45g/L 1g/L 10mg/L 14mg/L 12.5 |
When handling, finish electroless copper to handle the required time be 16 minutes from beginning to handle with aforesaid method; And it is 5 minutes that electroless copper is handled the required time.Obtain thickness and be 0.05 micron copper layer.Copper layer sedimentation velocity is 0.01 micron/minute.
In performance evaluation, four of observation copper-clad is pressed 100 holes that diameter is 0.3mm on the material layer by layer, shows that the space incidence of copper electroplating layer is 16%.Yet do not observe the decomposition of chemical copper plating solution.
Comparing embodiment 1 and embodiment 2, though the treatment time of electroless copper is identical, the space incidence of embodiment 2 is lower, and has improved coating performance.Result thus, obviously the deposition properties of copper layer has improved among the embodiment 2.Proved in addition in copper electroplating solution to add thallium, suppressed the decomposition of chemical copper plating solution.
Embodiment 3
[table 3]
Table 3
| Step | Treatment temp | Treatment time |
| The aging formaldehydeless chemical copper plating solution * of etch load P d-Sn catalyzer copper electroplating | 60℃ 25℃ 43℃ 60℃ 25 |
5 minutes 1 |
*: formaldehydeless chemical copper plating solution
| Copper sulfate pentahydrate T10 sodium borohydride 2,2 '-dipyridyl thallic sulfate pH | 15g/L 30g/L 0.5g/L 10mg/L 14mg/L 13.0 |
When handling, finish electroless copper to handle the required time be 13 minutes from beginning to handle with aforesaid method; And it is 2 minutes that electroless copper is handled the required time.The copper layer thickness that obtains is 0.08 micron.Copper layer sedimentation velocity is 0.04 micron/minute.
In performance test,, there be not coming off of binding substances between internal layer Copper Foil and copper sulfate coating even under the situation of the thermal test that comprises 100 circulations (260 ℃ of oil/10 seconds, 25 ℃ of methyl alcohol/10 seconds).Observe 100 holes that diameter is 0.3mm, show the copper electroplating layer tight, show that the result is good.In addition, do not observe the decomposition of chemical copper plating solution.
Embodiment 4
[table 4]
Table 4
| Step | Treatment temp | Treatment time |
| The aging formaldehydeless chemical copper plating solution * of etch load P d-Sn catalyzer copper electroplating | 60℃ 25℃ 43℃ 60℃ 25 |
5 minutes 1 |
*: formaldehydeless chemical copper plating solution
| Copper sulfate pentahydrate T10 sodium borohydride 1,10-phenanthroline thallic sulfate pH | 15g/L 30g/L 0.5g/L 10mg/L 14mg/L 13.0 |
When handling, finish electroless copper to handle the required time be 13 minutes from beginning to handle with aforesaid method; And it is 2 minutes that electroless copper is handled the required time.The copper layer thickness that obtains is 0.08 micron.Copper layer sedimentation velocity is 0.04 micron/minute.
In performance test,, there be not coming off of binding substances between internal layer Copper Foil and copper sulfate coating even comprising under 100 circulations oven test situation in (260 ℃ of oil/10 seconds, 25 ℃ of methyl alcohol/10 seconds).Observe 100 holes that diameter is 0.3mm, show the copper electroplating layer tight, show that the result is good.In addition, do not observe the decomposition of chemical copper plating solution.
By found that of embodiment 2 and 3, no matter the type of employed coating improving agent how, has all obtained effect of the present invention.
[table 5]
Table 5
| Step | Treatment temp | Treatment time |
| The aging formaldehydeless chemical copper plating solution * of etch load P d-Sn catalyzer copper electroplating | 60℃ 25℃ 43℃ 60℃ 25 |
5 minutes 1 |
*: formaldehydeless chemical copper plating solution
| Copper sulfate pentahydrate T10 sodium borohydride 2,2 '-dipyridyl cerous acetate potassiumiodide pH | 4g/L 30g/L 0.5g/L 10mg/L 15mg/L 10mg/L 12.5 |
When handling, finish electroless copper to handle the required time be 12 minutes from beginning to handle with aforesaid method; And it is 1 minute that electroless copper is handled the required time.The copper layer thickness that obtains is 0.06 micron.Copper layer sedimentation velocity is 0.06 micron/minute.
In performance test,, there be not coming off of binding substances between internal layer Copper Foil and copper sulfate coating even under the situation of the thermal test that comprises 100 circulations (260 ℃ of oil/10 seconds, 25 ℃ of methyl alcohol/10 seconds).Observe 100 holes that diameter is 0.3mm, show the copper electroplating layer tight, show that the result is good.In addition, do not observe the decomposition of chemical copper plating solution.
Embodiment 6
[table 6]
Table 6
| Step | Treatment temp | Treatment time |
| The aging formaldehydeless chemical copper plating solution * of etch load P d-Sn catalyzer copper electroplating | 60℃ 25℃ 43℃ 60℃ 25 |
5 minutes 1 |
*: formaldehydeless chemical copper plating solution
| Copper sulfate pentahydrate T10 sodium borohydride yellow prussiate of potash cerous acetate potassiumiodide pH | 4g/L 30g/L 0.5g/L 10mg/L 15mg/L 10mg/L 12.5 |
When handling, finish electroless copper to handle the required time be 12 minutes from beginning to handle with aforesaid method; And it is 1 minute that electroless copper is handled the required time.The copper layer thickness that obtains is 0.06 micron.Copper layer sedimentation velocity is 0.06 micron/minute.
In performance test,, there be not coming off of binding substances between internal layer Copper Foil and copper sulfate coating even under the situation of the thermal test that comprises 100 circulations (260 ℃ of oil/10 seconds, 25 ℃ of methyl alcohol/10 seconds).Observe 100 holes that diameter is 0.3mm, show the copper electroplating layer tight, show that the result is good.In addition, do not observe the decomposition of chemical copper plating solution.
By found that of embodiment 5 and 6, no matter the type of employed coating improving agent how, has all realized effect of the present invention.
Comparing embodiment 2～6, the time of finishing the electroless copper processing is 5 minutes in embodiment 2, is 2 minutes in embodiment 3 and 4, is 1 minute in embodiment 5 and 6.In embodiment 3 and 4, use T10, in embodiment 5 and 6, used T10 and potassiumiodide.Find thus that in electroless copper plating method of the present invention hydantoin compound and iodine element improve the sedimentation velocity of copper.
Embodiment 7
[table 7]
Table 7
| Step | Treatment temp | Treatment time |
| The aging formaldehydeless chemical copper plating solution * of etch load P d-Sn catalyzer copper electroplating | 60℃ 25℃ 43℃ 60℃ 25℃ | 30 40 minutes 30 seconds of second of 15 seconds, 15 seconds |
*: formaldehydeless chemical copper plating solution
| Copper sulfate pentahydrate T10 sodium borohydride trolamine 2,2 '-dipyridyl cerous acetate 8-hydroxyl-7-iodo-5-quinoline sulfonic acid pH | 4g/L 30g/L 0.5g/L 4g/L 10mg/L 15mg/L 10mg/L 13.0 |
When handling, finish electroless copper to handle the required time be 1 minute 30 second from beginning to handle with aforesaid method; And it was 30 seconds that electroless copper is handled the required time.The copper layer thickness that obtains is 0.05 micron.Copper layer sedimentation velocity is 0.1 micron/minute.
In performance test,, there be not coming off of binding substances between internal layer Copper Foil and copper sulfate coating even under the situation of the thermal test that comprises 100 circulations (260 ℃ of oil/10 seconds, 25 ℃ of methyl alcohol/10 seconds).Observe 100 holes that diameter is 0.3mm, show the copper electroplating layer tight, show that the result is good.In addition, do not observe the decomposition of chemical copper plating solution.
By found that of embodiment 7, the adding of iodine element has improved the sedimentation velocity of copper, even iodine exists with the form of iodine compound.
Embodiment 8
[table 8]
Table 8
| Step | Treatment temp | Treatment time |
| The aging formaldehydeless chemical copper plating solution * of etch load P d-Sn catalyzer copper electroplating | 60℃ 25℃ 43℃ 60℃ 25℃ | 30 40 minutes 30 seconds of second of 15 seconds, 15 seconds |
*: formaldehydeless chemical copper plating solution
| Copper sulfate pentahydrate T10 sodium borohydride trolamine sodium sulfate cerous acetate 8-hydroxyl-7-iodo-5-quinoline sulfonic acid pH | 4g/L 30g/L 0.5g/L 4g/L 10mg/L 15mg/L 10mg/L 13.0 |
When handling, finish electroless copper to handle the required time be 1 minute 30 seconds from beginning to handle with aforesaid method; And it is 30 seconds that electroless copper is handled the required time.The copper layer thickness that obtains is 0.05 micron.Copper layer sedimentation velocity is 0.1 micron/minute.
In performance test,, there be not coming off of binding substances between internal layer Copper Foil and copper sulfate coating even under the situation of the thermal test that comprises 100 circulations (260 ℃ of oil/10 seconds, 25 ℃ of methyl alcohol/10 seconds).Observe 100 holes that diameter is 0.3mm, show the copper electroplating layer tight, show that the result is good.In addition, do not observe the decomposition of chemical copper plating solution.
By found that of embodiment 8,, still obtain effect of the present invention even sulfide and cerium compound use together.
Use has the chemical copper plating solution of the composition of embodiment 8, measures by vertical and handles sedimentary copper layer thickness over time.Test is carried out under following condition: aging step, 60 ℃, 5 minutes; The etch step, 25 ℃, 1 minute; Load P d-Sn catalyzer step, 43 ℃, 5 minutes.Carried out 20 minutes at 60 ℃ with the step that formaldehydeless chemical copper plating solution is handled, and press the layer thickness of time measurement deposited copper.The result is represented by Fig. 1.
Comparative example 1
[table 9]
Table 9
| Step | Treatment temp | Treatment time |
| Aging etch load P d-Sn catalyst chemical copper plating solution * copper electroplating | 60℃ 25℃ 43℃ 60℃ 25 |
5 minutes 1 |
*: chemical copper plating solution
| Copper sulfate pentahydrate EDTA formaldehyde 2,2 '-dipyridyl pH | 4g/L 45g/L 20g/L 10mg/L 12.5 |
The time of electroless copper processing requirements is 1 minute in the comparative example 1, and is identical with embodiment 5 and 6.Yet do not observe the deposition of copper.Promptly, observed 100 holes that diameter is 0.3mm, shown that its coating performance has 100% space incidence, and use the deposition of the copper of this chemical copper plating solution can not determine about the coating performance of copper electroplating layer.Do not observe the decomposition of chemical copper plating solution.
In the comparative example 1, reach the copper layer that can be used for the electro-coppering degree of treatment, further continue electroless copper and handle, and measure the layer thickness of deposited copper in time in order to deposit a layer thickness.The copper layer that deposits 0.1 micron needs 20 minutes.The variation of the copper layer that passs in time thickness is shown in Fig. 1.
As shown in Figure 1, use the conventional chemical copper plating solution that contains formaldehyde, after handling, do not observe the deposition of copper immediately with chemical copper plating solution.On the other hand, in the embodiment 8 that uses chemical copper plating solution of the present invention, after handling, electroless copper observes the deposition of copper immediately.This layer thickness almost increases linearly up to handling back 1 minute of beginning, and the sedimentation velocity of copper layer is 0.06 micron/minute.Deposition reaction is finished substantially beginning to handle within back 2 minutes.At this moment layer thickness is 0.075 micron.
Just as already mentioned, use the chemical copper plating solution that contains formaldehyde, when not carrying out the accelerate process of catalyzer, the deposition of copper postpones greatly.Yet, can find clearly that by embodiment 1～8 result displayed chemical copper plating solution of the present invention can improve the sedimentation velocity of copper greatly, even catalyzer does not stand accelerate process.Shown in embodiment 1～8, implement copper electroplating on the thin layer that electroless copper plating method of the present invention forms in addition, the matrix material that obtains has outstanding thermotolerance and adhesion property.In addition, reduced the space incidence of described matrix material.Therefore prove that electroless copper plating method of the present invention can form the copper layer that is suitable for copper electroplating at short notice.
Embodiment 9
[table 10]
Table 10
| Step | Treatment temp | Treatment time |
| The aging formaldehydeless chemical copper plating solution * of etch load P d-Sn catalyzer copper electroplating | 60℃ 25℃ 43℃ 60℃ 25℃ | 30 40 minutes 30 seconds of second of 15 seconds, 15 seconds |
*: formaldehydeless chemical copper plating solution
| Copper sulfate pentahydrate T10 sodium borohydride trolamine sodium sulfate cerous acetate pH | 4g/L 30g/L 0.5g/L 4g/L 10mg/L 15mg/L 13.0 |
When handling, finish electroless copper to handle the required time be 1 minute and 30 seconds from beginning to handle with aforesaid method; And it is 30 seconds that electroless copper is handled the required time.The copper layer thickness that obtains is 0.03 micron.Copper layer sedimentation velocity is 0.06 micron/minute.
In performance test,, there be not coming off of binding substances between internal layer Copper Foil and copper sulfate coating even under the situation of the thermal test that comprises 100 circulations (260 ℃ of oil/10 seconds, 25 ℃ of methyl alcohol/10 seconds).Observe 100 holes that diameter is 0.3mm, show the copper electroplating layer tight, show that the result is good.In addition, do not observe the decomposition of chemical copper plating solution.
The result of comparing embodiment 9 and embodiment 8, the sedimentation velocity that does not contain the embodiment 9 of iodine element is 0.06 micron/minute, and the sedimentation velocity that contains the embodiment 8 of iodine element is 0.10 micron/minute.Therefore, the adding of having verified iodine can improve sedimentation velocity.
[table 11]
Table 11
| Step | Treatment temp | Treatment time |
| The aging formaldehydeless chemical copper plating solution * of etch load P d-Sn catalyzer copper electroplating | 60℃ 25℃ 43℃ 60℃ 25 |
5 minutes 1 |
*: formaldehydeless chemical copper plating solution
| Copper sulfate pentahydrate sodium borohydride trolamine thallium chloride sodium iodide pH | 4g/L 0.5g/L 4g/L 15mg/L 10mg/L 13.0 |
When handling, finish electroless copper to handle the required time be 12 minutes from beginning to handle with aforesaid method; And it is 1 minute that electroless copper is handled the required time.The copper layer thickness that obtains is 0.06 micron.Copper layer sedimentation velocity is 0.06 micron/minute.
In performance test,, there be not coming off of binding substances between internal layer Copper Foil and copper sulfate coating even under the situation of the thermal test that comprises 100 circulations (260 ℃ of oil/10 seconds, 25 ℃ of methyl alcohol/10 seconds).Observe 100 holes that diameter is 0.3mm, show the copper electroplating layer tight, show that the result is good.In addition, do not observe the decomposition of chemical copper plating solution.
The result of comparing embodiment 10 and embodiment 2, the sedimentation velocity that does not contain the embodiment 2 of iodine element is 0.01 micron/minute, and the sedimentation velocity that contains the embodiment 10 of iodine element is 0.06 micron/minute.Therefore verified that the adding of iodine has improved sedimentation velocity greatly.
[table 12]
Table 12
| Step | Treatment temp | Treatment time |
| The aging formaldehydeless chemical copper plating solution * of etch load P d-Sn catalyzer copper electroplating | 60℃ 25℃ 43℃ 60℃ 25 |
5 minutes 1 |
*: formaldehydeless chemical copper plating solution
| Copper sulfate pentahydrate sodium borohydride trolamine 8-hydroxyl-7-iodo-5-quinoline sulfonic acid pH | 4g/L 0.5g/L 4g/L 10mg/L 13.0 |
When handling, finish electroless copper to handle the required time be 12 minutes from beginning to handle with aforesaid method; And it is 1 minute that electroless copper is handled the required time.The copper layer thickness that obtains is 0.06 micron.Copper layer sedimentation velocity is 0.06 micron/minute.
In performance test,, there be not coming off of binding substances between internal layer Copper Foil and copper sulfate coating even under the situation of the thermal test that comprises 100 circulations (260 ℃ of oil/10 seconds, 25 ℃ of methyl alcohol/10 seconds).Observe 100 holes that diameter is 0.3mm, show the copper electroplating layer tight, show that the result is good.In addition, do not observe the decomposition of chemical copper plating solution.
The result of comparing embodiment 11 and embodiment 1 does not contain 0.01 micron/minute of the sedimentation velocity of the embodiment 1 of iodine element, and the sedimentation velocity that contains the embodiment 11 of iodine element is 0.06 micron/minute.Therefore verified that the adding of iodine obviously improves sedimentation velocity.Simultaneously, in embodiment 1, observe the decomposition of chemical copper plating solution, yet in embodiment 11, do not observe decomposition.
Find that thus iodine element improves the stability of sedimentation velocity and chemical copper plating solution simultaneously.
Observe the outward appearance of the copper layer among the embodiment 1～11 by visual inspection.Each chemical copper plating solution contains iodine element in embodiment 5～8,10 and 11, and its outward appearance has the gloss of metal tone.On the other hand, each chemical copper plating solution does not contain iodine element in embodiment 2～4 and embodiment 9, the lackluster or metal tone of their outward appearance.Therefore the adding that demonstrates iodine element makes the metallic copper that is plated have glossy outward appearance and metal tone.
Embodiment 1～11 and comparative example 1 result's summary hereinafter is provided.
[table 13]
[table 13] (1)
The result of embodiment 1～11 and comparative example 1 summarizes
[table 13] (2)
The result of embodiment 1～11 and comparative example 1 summarizes
| Treatment process | Sedimentation velocity (micron/minute) | The film thickness of deposited copper (micron) | The treatment time of chemical copper plating solution (minute) | Voidage (%) | The copper film outward appearance | |
| Embodiment 1 | Vertically | 0.01 | 0.05 | 5 | 26 | X |
| Embodiment 2 | Vertically | 0.01 | 0.05 | 5 | 16 | X |
| Embodiment 3 | Vertically | 0.04 | 0.08 | 2 | 0 | X |
| Embodiment 4 | Vertically | 0.04 | 0.08 | 2 | 0 | |
| Embodiment | ||||||
| 5 | Vertically | 0.06 | 0.06 | 1 | 0 | O |
| Embodiment 6 | Vertically | 0.06 | 0.06 | 1 | 0 | O |
| Embodiment 7 | Level | 0.10 | 0.05 | 0.5 | 0 | O |
| Embodiment 8 | Horizontal vertical | 0.10 0.06 | 0.05 0.075 | 0.5 2 | 0 N | O O |
| Embodiment 9 | Level | 0.06 | 0.03 | 0.5 | 0 | |
| Embodiment | ||||||
| 10 | Vertically | 0.06 | 0.06 | 1 | 0 | O |
| Embodiment 11 | Vertically | 0.06 | 0.06 | 1 | 0 | O |
| Comparative example 1 | Vertically | 0 | 0 0.10 | 1 20 | 100 N |
Annotate) in last table, " " expression does not comprise corresponding composition, and "+" expression comprises corresponding composition." N " expression ' is not measured '.On film appearance luster hurdle: " O " expression obtains glossy outward appearance and metallic copper tone; And the opposite situation of " X " expression.
Embodiment 12 and comparative example 2
The bath stability effect of water-soluble thallium compound
Comparative example 2 shown in the preparation hereinafter and the chemical copper plating solution of embodiment 12, and compare their bath stabilities as chemical copper plating solution.
As the method for estimating bath stability, in the chemical copper plating solution of comparative example 2 and embodiment 12, add the catalyzer that contains 350g/L palladium and 10g/L tin.Add catalyzer and obviously decompose, relatively add the quantity of catalyzer up to plating bath.
[table 14]
Table 14
| Comparative example 2 plating baths are formed | Embodiment 12 plating baths are formed |
| Copper sulfate pentahydrate 15g/L trolamine 5mL/L sodium borohydride 0.5g/L 2,60 ℃ of 2 '-dipyridyl 10mg/L pH, 13.0 temperature | Copper sulfate pentahydrate 15g/L trolamine 5mL/L sodium borohydride 0.5g/L 2,60 ℃ of 2 '-dipyridyl 10mg/L thallic sulfate 14mg/L pH, 13.0 temperature |
| Bath stability adds the Pd solution of 2mL/L, and plating bath is decomposed | Bath stability adds the Pd solution of 20mL/L, and plating bath is decomposed |
By found that of above-mentioned test, the present invention contains the bath stability of the electroless copper plating bath of water-soluble thallium compound, than big ten times of the chemical copper plating solutions that does not contain water-soluble thallium compound and formaldehyde.
Embodiment 13 and comparative example 3
The bath stability effect of water-soluble cerium compound
With the mode same, prepare the electroless copper plating bath of following comparative example 3 and embodiment 13 with comparative example 2 and embodiment 12.Compare bath stability subsequently as chemical copper plating solution.
As the method for estimating bath stability, in the chemical copper plating solution of comparative example 3 and embodiment 13, add the catalyzer that contains 200g/L palladium and 10g/L tin.The quantity that compares the catalyzer that when plating bath decomposes, adds.
[table 15]
Table 15
| Comparative example 3 plating baths are formed | Embodiment 13 plating baths are formed |
| Copper sulfate pentahydrate 15g/L trolamine 5mL/L sodium borohydride 0.5g/L 2,60 ℃ of 2 '-dipyridyl 10mg/L pH, 13.0 temperature | Copper sulfate pentahydrate 15g/L trolamine 5mL/L sodium borohydride 0.5g/L 2,60 ℃ of 2 '-dipyridyl 10mg/L cerous sulfate 14mg/L pH, 13.0 temperature |
| Bath stability adds the Pd solution of 2mL/L, and plating bath is decomposed | Bath stability adds the Pd solution of 14mL/L, and plating bath is decomposed |
By found that of above-mentioned test, the electroless copper plating bath that contains water-soluble cerium compound of the present invention compares with the chemical copper plating solution that does not contain water-soluble cerium compound, and the former bath stability is 7 times of the latter.
Embodiment 14 and comparative example 4
The bath stability effect of water-soluble cerium compound
With the mode same, prepare the electroless copper plating bath of following comparative example 4 and embodiment 14 with comparative example 3 and embodiment 13.Compare bath stability subsequently as chemical copper plating solution.
As the method for estimating bath stability, in the chemical copper plating solution of comparative example 4 and embodiment 14, add the catalyzer that contains 200g/L palladium and 10g/L tin.The quantity that compares the catalyzer that when plating bath decomposes, adds.
[table 16]
Table 16
| Comparative example 4 plating baths are formed | Embodiment 14 plating baths are formed |
| 60 ℃ of copper sulfate pentahydrate 15g/L three ethanol 5mL/L sodium borohydride 0.5g/L yellow prussiate of potash 10mg/L pH 13.0 temperature | 60 ℃ of copper sulfate pentahydrate 15g/L trolamine 5mL/L sodium borohydride 0.5g/L yellow prussiate of potash 10mg/L cerous sulfate 14mg/L pH 13.0 temperature |
| Bath stability adds the Pd solution of 2mL/L, and plating bath is decomposed | Bath stability adds the Pd solution of 14mL/L, and plating bath is decomposed |
By found that of these tests, the present invention contains the bath stability that the electroless copper plating bath of water-soluble cerium compound has, and is bigger seven times than the electroless copper plating bath that does not contain water-soluble cerium compound.
Also find no matter the type of coating improving agent is a yellow prussiate of potash or 2 for example 2 '-dipyridyl, the effect that the plating bath of the present invention that all is inhibited decomposes.
[effect of the present invention]
As mentioned above, electroless copper plating method of the present invention, contain copper ion and reducing agent by use but do not contain the chemical copper plating solution of formaldehyde, can form all copper layers of even densification at resin base material, independent acceleration treatment step is still like this even without carrying out. Use method of the present invention, can form all copper laminas of even densification at resin base material. Use said method also to improve heat resistance, and if on electroless copper re-plating copper, said method also improves the adhesive property between the copper electroplating layer that copper facing thin layer that electroless copper obtains and electro-coppering obtain. In addition and importantly, use formaldehydeless electroless copper plating method can avoid and the harm of using this chemicals to interrelate such as carcinogenicity, teratogenesis and mutagenicity.
In addition, accelerate to process even without the catalyst that carries out as a separate processes, electroless copper plating method of the present invention also can form copper lamina at resin base material at short notice, and greatly improves the productivity ratio of copper-resin composite materials. The reason that obtains the above results is can begin rapidly the deposition reaction of copper in electroless copper is processed.
In addition, compare with the copper lamina that conventional chemical copper electroplating method known in the art obtains, the copper lamina that above-mentioned electroless copper plating method forms is more evenly also finer and close. Therefore when being applied to electrolytic copper plating, the deposition velocity of copper is rapider than the copper layer that conventional copper facing known in the art generates in the electrolytic copper plating. So can think that electroless copper plating method of the present invention is suitable for forming a kind of copper lamina, this copper lamina can be preferably by electro-coppering.
Further, adopt the present invention, can by in chemical copper plating solution of the present invention, adding any water-soluble cerium compound, water-soluble thallium compound and/or water-soluble sulfide, stablize chemical copper plating solution.
The present invention can also realize the raising of electroless copper bath stability and the raising of copper deposition velocity simultaneously by add I in chemical copper plating solution. This effect can realize under the general condition of electroless copper plating method of the present invention. And advantage in the case is that the copper that deposits becomes fine and close, thereby the tone of the glossiness outward appearance of copper layer tool and metallic copper. In the electroless copper field, the outward appearance of the copper layer of deposition is important, and the coating with glossy appearance and metal tone is preferred. Therefore the benefit that adds I is provided with regard to this point.
In addition, adopt the present invention, can accelerate the deposition velocity of copper by in chemical copper plating solution, adding hydantoins.
[accompanying drawing summary]
[Fig. 1]
When Fig. 1 is to use the chemical copper plating solution of embodiment 8 and comparative example 1, the graphic representation of expression copper sedimentation velocity; Wherein the treatment time of electroless copper is plotted on the axis of abscissa, and sedimentary copper layer thickness is plotted on the length axis.
Claims (11)
1. electroless copper plating method, it may further comprise the steps:
1) palladium or palladium-tin catalyst are deposited on the resin base material; And
2) handle described resin base material with formaldehydeless chemical copper plating solution, this solution contains cupric ion, reductive agent and 1mg/L iodine or water-soluble iodine compound or its mixture to 1000mg/L, and wherein finishes the accelerate process of not carrying out catalyzer after described catalyst deposit is handled.
2. according to the electroless copper plating method of claim 1, wherein chemical copper plating solution also contains complexing agent.
3. according to the electroless copper plating method of claim 1 or 2, wherein reductive agent is selected from the derivative of sodium borohydride, POTASSIUM BOROHYDRIDE, dimethylamino borine, front three amino borane, hydrazine, these compounds and their mixture.
4. according to electroless copper plating method any among the claim 1-3, wherein chemical copper plating solution also contains water-soluble cerium compound, water-soluble thallium and/or water-soluble sulfide.
5. according to electroless copper plating method any among the claim 1-4, wherein chemical copper plating solution also contains glycolylurea and/or hydantoin derivatives.
6. according to electroless copper plating method any among the claim 1-5, wherein the sedimentation velocity of copper is 0.05 micron/minute or bigger.
7. according to the chemical copper plating solution that uses in the electroless copper plating method any among the claim 1-6.
8. according to the matrix material of method any one among claim 1-6 preparation.
9. matrix material according to Claim 8, the copper layer thickness that wherein deposits on the resin base material is 0.05 micron or bigger.
10. the method for an electro-coppering is characterized in that further electro-coppering on the matrix material of claim 8 or 9.
11. matrix material according to the method preparation of claim 10.
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| EP0251302A2 (en) * | 1986-07-02 | 1988-01-07 | Blasberg-Oberflächentechnik GmbH | Alcaline chemical copper plating bath |
| JP2001214278A (en) * | 1999-11-22 | 2001-08-07 | Learonal Japan Inc | Accelerator bath solution for direct plating and direct plating method |
-
2002
- 2002-11-20 CN CNB02151397XA patent/CN100402700C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0251302A2 (en) * | 1986-07-02 | 1988-01-07 | Blasberg-Oberflächentechnik GmbH | Alcaline chemical copper plating bath |
| JP2001214278A (en) * | 1999-11-22 | 2001-08-07 | Learonal Japan Inc | Accelerator bath solution for direct plating and direct plating method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103898489A (en) * | 2012-12-26 | 2014-07-02 | 罗门哈斯电子材料有限公司 | Formaldehyde free electroless copper plating compositions and methods |
| CN103898489B (en) * | 2012-12-26 | 2016-08-24 | 罗门哈斯电子材料有限公司 | Formaldehydeless electroless copper composition and method |
| CN110983309A (en) * | 2019-12-26 | 2020-04-10 | 广东东硕科技有限公司 | Application of 2-thiohydantoin compound or salt thereof |
| CN110983309B (en) * | 2019-12-26 | 2023-01-03 | 广东东硕科技有限公司 | Application of 2-thiohydantoin compound or salt thereof |
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| Publication number | Publication date |
|---|---|
| CN1502720A (en) | 2004-06-09 |
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