US3804638A - Electroless deposition of ductile copper - Google Patents

Electroless deposition of ductile copper Download PDF

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US3804638A
US3804638A US00241806A US24180672A US3804638A US 3804638 A US3804638 A US 3804638A US 00241806 A US00241806 A US 00241806A US 24180672 A US24180672 A US 24180672A US 3804638 A US3804638 A US 3804638A
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copper
bath
mol
plating
plating bath
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H Jonker
A Moienaar
F Geertsema
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US Philips Corp
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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
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde

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  • the invention relates to an alkaline aqueous electroless copper-plating bath and provides simplified methods of depositing ductile copper.
  • electroless copper-plating is understood to mean the deposition by chemical reduction of an adherent copper layer on a suitable surface in the absence of an external source of electricity.
  • Such a copper-plating method is used, for example, on a large scale in the manufacture of printed circuits, conducting coatings which are subsequently to be further coated electrically, and for decorative purposes.
  • Such aqueous solutions generally contain cupric ions, formaldehyde, an alkali hydroxide and a complexing agent which prevents the cupric ions from being deposited in an alkaline medium.
  • the copper deposition with the aid of such a bath is effected by reduction of cupric ions to copper by the formaldehyde, which reaction is initiated by a catalytic surface, for example, a catalytic metal or a synthetic resin which has been made catalytic (activated).
  • the known electroless copper-plating baths have a number of drawbacks.
  • the appearance of electroless deposited copper often greatly deviates from that of metallic copper. it is then, for example, not metallically bright but dull and has a dirty dark colour and a great brittleness, a comparatively small specific electrical conductance and a poor solderability.
  • the known solutions which have a comparatively high deposition rate especially at the beginning the quality of the deposition is generally poor and it is characteristic that the deposition rate in many cases is rapidly reduced and sometimes decreases to zero. Consequentiy slow and hence more stable copper-plating solutions are generally used with the aid of which a basic layer having a thickness of 0.!
  • a layer having a thickness in the order of 25-50 punt is generally desired and the electrolytic copper-plating process involves a considerable investment and a number of additional operations.
  • electrolytic depositions Apart from this fact it is generally difficult to use an electrolytical coppenplating process when copper is to be deposited in accordance with a pattern whose parts are not uninterruptedly coherent for example, in addi' tive methods of manufacturing printed circuits).
  • a drawback of electrolytic depositions is also that these depositions often differ in thickness as a result of an irregular current density distribution.
  • the commerciaily available electroless copper-plating solutions are generally of the slow type and are not suitable to deposit in an economic manner thick, ductile, adherent copper layers which are free from blisters. These solutions also generally have the unpleasant property that the deposition rate, being slow as it is, is reduced during deposition.
  • a novel method of electroless copper-plating has recently become known (U.S. Pat. No. 3,329,512) whose major object is to deposit copper up to the thickness of 25 gum or more at a rate of at least 6 uum per hour and preferably more.
  • the complexing agent for cupric ions in the copper-plating solution consists of one or more hydroxyalkylsubstituted tertiary amines, which solution also contains a colloidal soluble non-reactive polymer chosen from the group of cellulose ethers, hydroxyethyl starch, polyvinylalcohol, polyvinylpyrrolidone, gelatin, peptones, polyamides and polyacrylarnides.
  • the polymer addition acts as a brightnening agent.
  • the appearance of the copper layers which are deposited with the aid of such solutions is very satisfactory indeed, but the ductility of the layers is generally marginal and even insufficient when the relevant solutions are used for the manufacture of printed circuits in accordance with an additive method.
  • the ductility may be determined by partially loosening the deposited copper layer from the substrate and bending it in one direction over folding it and bending it back in its original position whereafter the fold is flattened under pressure. This completes one band. The operations are repeated until the layer breaks and thus it is possible to express the ductility in the number of bends which the layer can stand. For obtaining comparable results it is desirable to perform the measurements on copper layers of comparable layer thickness, for example, 15-20 uum.
  • the starting point for the experiment which led to the present invention was that the ductility should be at least two bends with a view to versatile unability.
  • This experiment showed that the ductility of electroless deposited copper depends on the rate of deposition which follows from the following Table which applies for a bath temperature of 50C.
  • Bath composition (moles/litre) Layer thicknessutrnl Average depo- Ductility CuSo,,5H,0 EDTAHNa) NaOH Na,CO, HCHO after it hours sition rate (bends) m/hour) 0.008 0.009 0.10 0.18 20 pm in [3 hours 1.5 S 7 0.014 0.0IS 0.10 0.10 0.18 20 pm in ID hours 2.0 2% 0,020 0.025 0.10 0.10 018 25 pm in 6%hours 3.8 ii
  • Goldie (Plating, Nov. 1964) was able to deposit 1.54 mg Cu/sq.cm (approximately 0.85 yum/hour) at 20C within 2 hours from a bath of the following composition:
  • the starting point was chosen to be the assumption that the improvement in ductility which may be brought about by an addition of, for example, inorganic cyanide, organic nitrile, vanadium pentoxide, sodium arsenite or potassium antimony tartrate should be ascribed to the reduction of the rate of deposition caused by such an addition.
  • the aqueous alkaline electroless copper-plating bath according to the invention for metallizing with ductile copper and containing a soluble copper salt, one or more complexing agents and formaldehyde is characterized in that it is free from an inorganic cyanide, an organic nitrile or a compound of one of the following elements: molybdenum, niobium, tungsten, rhenium, vanadium, arsenic, antimony, bismuth, actinium, lanthanium and the rare earths and that it contains as its essential constituents 0.01 0.10 mol of a copper salt soluble in water, a total of 0.01 0.80 mol of one or more complexing agents which prevent cupric ions from being deposited from the alkaline solution, 0.05 0.50 mol alkalihydroxide (pH approximately: ll l3.5), 0.01 0.35 mol formaldehyde or a compound producing a formaldehyde and to enhance the ductility of the depositing copper an effective concentration
  • an effective concentration of the polyalkylene oxidic compound is understood to mean a concentration which enhances the ductility and when insufficient ductile copper is deposited from the solution without the active compound is at least such that a ductility of at least two bends is obtained. Also, an effective copper concentration substantially always enhances the colour and the smoothness of the deposition and often reduces the number of blisters formed in the surface of the deposited copper and enhances the adhesion of the deposited layer.
  • the deposition rate of copper is generally reduced due to the presence of a polyalkylene oxidic compound according to the invention, it has been found that dependent on the concentrations of the essential constitutents of the copper-plating solution it is not always possible to reduce it to the critical rate at which copper is deposited at a ductility of two bends. For this reason a maximum but still suitable limit concentration is indicated above for each essential constituent of the solution.
  • the minium limit concentrations are determined by the requirement that copper must be deposited at a rate which is still acceptable for practical use.
  • Maximum and still acceptable concentrations of the other constituents are associated with each maximum limit concentration of an essential constituent, which concentrations are generally lower than the mentioned maximum limit concentrations of said constituents.
  • electroless copper-plating baths of the previously described type are known from US. Pat. No. 3,257,215, which baths contain a cyanide compound and a rnercapto compound. It is recommended to add a wetting agent to the bath, the specification mentioning a few agents which satisfy the definition according to the invention. However, it was found that addition of such a wetting agent to such a cyanidecontaining bath does not provide any improvement with regard to ductility as compared with the corresponding bath without a wetting agent. These known baths have the drawbacks already referred to.
  • a large number of suitable polyalkylene oxidic compounds is defined by the following general formula R(OC H,) (OCJi h, (OCQ-IJ R with a+b+c a 4(
  • R, H and R, 01-l.
  • For the polyethylene glycols b is equal to zero and the formula changes into H(OC H,) OH.
  • polypropylene glycols a and c are both zero and n 3 H(OC l-l OH and for the polybutylene glycols both a and c are likewise zero and n 4 H(OC H OH.
  • Polyethylene glycols are satisfactorily soluble in water even when they have a high molecular weight. Thus they are very much suitabie for use within the scope of the present invention. Even a compound having a molecular weight of 500,000 and a c 1,100 is found to be still effective. When the molecular weight of polypropylene and polybutylene glycols increases, the solubility decreases. When the compounds are completely insoluble in the copper-plating solution, they are unsuitable for the method according to the invention.
  • Compounds which are interesting with a view to their suitability are block polymers with a 1, b 1, and c 1 and n 3.
  • the pH of the solution was set at 4.
  • the adherent liquid layer was dried with the aid ofa stream of cold air.
  • the photosensitive layer was subsequently exposed behind a negative of fairly broad lines for 1 minute with the aid of a reprographic mercury vapour lamp (type HPR 150 W) which was at a distance of 42 cms from the negative.
  • a reprographic mercury vapour lamp type HPR 150 W
  • the exposed layer was treated with a solution containing 0.075 mol mercurous nitrate 0.01 mol silver nitrate 0.15 mol nitric acid deionized water up to 1 litre.
  • the latent image formed consisting of metal nuclei was slightly intensified with silver by treating it for 1 1/2 minutes with a solution comprising 0.01 mol silver nitrate 0.025 mol metol 0.10 citric acid deionized water up to 1 litre.
  • the weak image thus obtained consisting of catalytic silver nuclei was finally electroless copper-plated in a copper-plating solution of the composition:
  • EXAMPLE 1 An adhesive layer roughened with chromic acid sulphuric acid and based on a mixture of These minimum effective concentrations c are plotted in FIG. I as a function of the number of ethoxy groups n.
  • the curve through the experimental points separates a region of satisfactory ductile copper from a region of non-satisfactory, non-ductile copper. If copper having a ductility of at least 2 bends is to be deposited, approximately 0.l mol per litre of the compounds including fewer than 8 9 ethoxy groups is to be added. For the compounds having more ethoxy groups much smaller concentrations may be sufficient. Nevertheless it is recommended to use a concentration which is slightly higher than the limit concentration.
  • ductilities of 3 8 bends may be obtained.
  • the ductile copper was deposited in these cases at a rate in the order of I um per hour. It had a better metallic appearance and a slighter oxidation sensitivity than the non-ductile copper deposited from baths containing too little polyethylene glycol. It is to be noted that the method and extent of activating the substrate as well as the composially non-ionic and are eminently suitable for use within the scope of the present invention.
  • R is a paraffin tail such as, for example, a lauryl, cetyl, stearyl, myristyl or oleyl group, then ethoxyl ated fatty alcohols, or more correctly expressed, an
  • ether of a fatty alcohol and a polyethylene glycol are concerned: C,,,H,, (OC,H OH.
  • the alkyl group may alternatively be branched.
  • Numerous active surface-active compounds of this type are commercially available such as, for example:
  • R may alternatively be an alkylaryl group such as, for example, an octylphenyl, nonylphenyl or dodecylphenyl group.
  • Active ethoxylated alkylphenols which are commercially available are, for example:
  • Hyonic PE (series) alkylphenol Nopco Chemical Co.
  • Retzanol NP series alkylphenol Retzlofl' Chemical Co.
  • the final hydroxyl group of alkylethers and alkylaryl ethers of polyethylene glycol may alternatively be esterified with phosphoric acid.
  • R becomes The relevant phosphate esters are anion-active. Examples are:
  • Gafac RE-lO-acid phosphate ester General Aniline & Film Corp.
  • Wascope 9J2 acid phosphate ester of alkylphenylether of polyethylene glycol Wasco Laboratories.
  • fatty acid esters of polyethylene glycols for example, compounds of the Myrj-series (Atlas Chemical lnd.) or of the Tween-series (Atlas Chemical Ind.) greatly reduce the deposition rate of copper from copper-plating solutions when the concentration increases generally before reaching a suitable improvement of the ductility. Consequently they are less suitable for use within the scope of the present invention.
  • the activity of a number of these micelleconstituting surface-active compounds of the non-ionic and anionic type will hereinafter be described in detail.
  • EXAMPLE Two methods of activation of hard paper substrates provided with an adhesive were used: method A: the photochemical production of silver nuclei described in Example I, and; method B: the production of palladium nuclei, Palladium nuclei: Plates (25 sqcm ⁇ of chemically roughened hard paper provided with an adhesive (Example I) were activated for the electroless copper deposition by successively treating them at room temperature in a stationary solution of 10 grams of tin (ll) chloride and i0 mls of hydrochloric acid in 1 litre of deionized water (3minutes),
  • the plates were turned about after 30 seconds in the tin (ll) chloride and palladium (ll) chloride solutions.
  • the copper-plating solution used for this Example had the following composition:
  • C,,,H,,, is a paraffin tail.
  • an ethoxylated secondary amine is concerned when R; H, or an ethoxylated tertiary amine when R,-, is, for example, a polyethoxy group: R, (C- HJJMH.
  • R is then, for example,
  • the copper layer deposited from a solution without polyethoxy compound had a ductility of one-half bend.
  • the layers deposited from solutions including an addition had the following ductilities:
  • organic sulphur compounds enhance the stablity of electroless copper-plating solutions.
  • these compounds increase the brittleness of the deposition and that they can generally be used only in a very small concentration because otherwise they suppress the copper deposition completely.
  • a sulphur atom enhancing the stability and increasing the brittleness and a number of ethoxy groups enhancing the ductility are built in in the W 7 same molecule, such as is the case in the abovementioned ethoxylated thioethers, then it may be expected that the ductility of the deposited copper will be acceptable in the presence of sufficient ethoxy groups while the stability will be enhanced by the presence of the thioether bridge. If necessary the ductilityenhancing effect may be increased by adding a polyalkylene glycol or a surface-active polyethoxy compound of one of the types described so far.
  • the ductility of the copper layer which was deposited from a solution without polyethoxy compound was one-half bend.
  • the ductility of the copper layers deposited from solutions including additions was at least three bends.
  • the durability of a bath including additions was a factor of 3 to 4 better than that of a bath without an addition. Solubility permitting the concentration of the thioether may be increased to 0.1 percent by weight before the copper deposition is unacceptably delayed.
  • the stabilising effect is unmistakably present, but in so far as they can be deposited to the required thickness the copper layers have a completely insufficient ductility.
  • An experiment on the stabilising effect of Z-mercaptobenzothiazole is described in Electronic Industries of Sept. 1962, pages 1 17 e 119.
  • the quantity of l-phenyl-S- mercaptotetrazole which is added is to be between fi iiji a nd l milligram per litre of solution (including the limit values).
  • the following Example illustrates this embodiment of the copper-plating bath according to the invention.
  • EXAMPLE VI Plates of chemically roughened hard paper provided with an adhesive (25 sq.cm) were subjected to the formation of palladium nuclei in the manner as described with reference to Example Ill in order to activate these plates for electroless copper-plating.
  • the plates were copper-plated at 50C while being stationary in 200 mls of the following solution:
  • a copper layer of 20 nm was deposited within 5 hours and had a ductility of at least three bends. When the polyalkosy compound was omitted a brittle copper layer was deposited bend). The durability of the bath was enhanced by a factor of 8 due to the addition of l-phenyl-S-mercaptotetrazole. Similar results are obtained when instead of l g of Carbowax 1540, 2 grams of Triton QS-l5 are added.
  • the choice of the water-soluble copper salt for electroless copperplating solutions is mainly determined by economic considerations. Copper sulphate is preferred, but the nitrate, halogenides, acetates and other soluble salts of copper may alternatively be used.
  • cupric ions and complexing agent constitute complexes at a molecular ratio of l l, but generally an excess of complexing agent will preferably be used.
  • complexing agents for cupric ions Preferably the invention employs Rochelle salt (potassiumsodium tartrate), triethanolamine and alkali salts of N- hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetra-acetic acid and diethylenetriaminepentacetic acid and mixtures thereof.
  • Reducing agents which are used in alkaline electroless copper-plating solutions are formaldehyde and compounds or derivates producing formaldehyde such as paraformaldehyde, glyoxale and trioxane.
  • the baths may contain less essential constituents such as, for example, buffers and sodium carbonate.
  • solutions in which potassium-sodium tartrate, triethanolamine and/or N-hydroxyethylethylenediaminetriacetate (3Na) are used as complexing agents may be used at temperatures of 15C to C; solutions based on ethylenediaminetetraacetate (4 Na) may be used at temperatures of 20C to 80C and solutions based on diethylenetriaminepentaacetate (5 Na) may be used at temperatures of C to 90C.
  • the last-mentioned baths have the advantage that they do not deposit at room temperature and are then very stable. When not in use, these baths are therefore preferably allowed to cool down to room temperature.
  • the following examples illustrate the invention when using the different complexing agents in a temperature range of from l5 to 90C.
  • EXAMPLE Vll Similar activated substrates as those used in Example V] were electroless copper-plated with a layer of 15 20 p.111 thickness.
  • Baths containing weak complexing agents must be used at a comparatively low temperature with a view to the Copper layers of approximately 20 pm thickness were deposited on glass plates which were activated for the electroless copper deposition in the manner as described with reference to Exarnpie IV by treating these plates for 4 hours (deposition rate 5 urn/hour) with the below-mentioned copper-plating solution which was maintained at 35C and which was not stirred.
  • Compo- 5 sition of copper-plating solution :
  • the deposited copper layers could stand three full bends.
  • a similar bath without Carbowax 4000 yielded pm of copper deposition per hour, but the ductility was then l bend.
  • the copper deposition rate was varied by means of the concentration of the copper salt in the copper plating solution.
  • the composition thereof was as follows:
  • Example I chemically roughened hard-paper substrates provided with an adhesive (Example I), photochemically activated for the copper deposition in the manner described in Example I (formation of silver nuclei);
  • Example X mechanically roughened glass substrates (Example X) activated in the manner described in Example X (formation of palladium nuclei).
  • These baths showed signs at spontaneous decomposition at the end of the period it is clearly apparent that the critical rate at which copper having a ductility of at least two bends is deposscribed in Example X from a copper-plating solution of ited increases as the bath temperature increases.
  • the layers which had a thickness of approximately um could stand 4 bends. After deposition the bath was cooled down to room temperature and it was brought to 70C again after 24 hours whereafter glass plates were copper-plated again.
  • An alkaline aqueous electroless copper-plating bath for depositive ductile copper which bath is free of inorganic cyanides, organic nitriles and compounds of La, the rare earths Mo, Nb, W, Re, V, As, Sb, Bi and Ac, said bath having a pH of about lll3.5 and containing per liter of water 0.0] l.l0 mols of a watersoluble copper salt, 0.01-0.35 mols of formaldehyde or a formaldehyde producing compound, 0.01 0.80 mols of at least one coupling compound capable of forming a soluble complex with cupric ions in an alkaline solution, 0.05 0.50 mols of an alkali metal hydroxide and a water soluble polyalkylene oxide compound containing at least four alkylene oxide groups of two to four carbons per molecule in an amount sufficient to cause the resultant copper layer to be ductile.
  • R (C H.O),, (C,,H ,,O),, (C H. 0), R in which formula 0 h c 4, n 0-4, R being H and R being OH when n is 0, 3 or 4, R being alkyl or alkaryl and R, being OH, esterified or unesterified hydroxy, sulfate or bath temperature:
  • R is H and R, is fatty acid amino, fatty acid amino or an alkyl substituted mercapto.
  • polyalkylene oxide compound is a polyalkylene glycol containing at least 4 ethoxy or propoxy groups.
  • polyalkylene oxide compound is an ethoxylated fatty acid amine or an ethoxylated fatty acid amide.
  • the copper-plating bath of claim 1 wherein the complexing agent for cupric ions is selected from the group consisting of potassium-sodium tartrate, triethanolamine and N-hydroxyethylethylene diaminetrisodiumacetate and the temperature of the bath is between 15 and 40C.
  • the copper-plating bath of claim 1 wherein the complexing agent for cupric ions is diethylenetriaminepenta-sodiumacetate, and the temperature of the bath is between 60 and C.

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DE2610470A1 (de) * 1975-03-14 1976-09-30 Hitachi Ltd Loesung zum nichtgalvanischen verkupfern
US4211564A (en) * 1978-05-09 1980-07-08 Hitachi, Ltd. Chemical copper plating solution
EP0021757A1 (de) * 1979-06-15 1981-01-07 Hitachi, Ltd. Bad zur stromlosen Kupferabscheidung
US4301196A (en) * 1978-09-13 1981-11-17 Kollmorgen Technologies Corp. Electroless copper deposition process having faster plating rates
US4371397A (en) * 1980-05-08 1983-02-01 Tokyo Shibaura Denki Kabushiki Kaisha Chemical copper-plating bath
DE3238921A1 (de) * 1981-10-23 1983-05-05 Occidental Chemical Corp., 48089 Warren, Mich. Verfahren zur stromlosen kupferabscheidung auf einem substrat sowie eine loesung zur durchfuehrung dieses verfahrens
US4443257A (en) * 1982-03-09 1984-04-17 Alfachimici S.P.A. Stabilizing mixture for a chemical copper plating bath
US4563217A (en) * 1983-07-25 1986-01-07 Hitachi, Ltd. Electroless copper plating solution
US4908242A (en) * 1986-10-31 1990-03-13 Kollmorgen Corporation Method of consistently producing a copper deposit on a substrate by electroless deposition which deposit is essentially free of fissures
US5925403A (en) * 1994-01-31 1999-07-20 Matsushita Electric Works, Ltd. Method of coating a copper film on a ceramic substrate
US20040058071A1 (en) * 2002-09-24 2004-03-25 International Business Machines Corporation Colloidal seed formation for printed circuit board metallization
US20050016416A1 (en) * 2003-07-23 2005-01-27 Jon Bengston Stabilizer for electroless copper plating solution
US20050067297A1 (en) * 2003-09-26 2005-03-31 Innovative Technology Licensing, Llc Copper bath for electroplating fine circuitry on semiconductor chips
US20050088647A1 (en) * 2003-09-19 2005-04-28 Applied Materials, Inc. Apparatus and method of detecting the electroless deposition endpoint
US20060062897A1 (en) * 2004-09-17 2006-03-23 Applied Materials, Inc Patterned wafer thickness detection system
US20060280872A1 (en) * 2005-06-10 2006-12-14 Enthone Inc. Method for direct metallization of non-conducting substrates
US20160273112A1 (en) * 2013-03-27 2016-09-22 Atotech Deutschland Gmbh Electroless copper plating solution
EP3351657A1 (de) 2017-01-23 2018-07-25 Rohm and Haas Electronic Materials LLC Stromlose kupferplattierungszusammensetzungen
US10294569B2 (en) 2017-10-06 2019-05-21 Rohm And Haas Electronic Materials Llc Stable electroless copper plating compositions and methods for electroless plating copper on substrates
US10655227B2 (en) 2017-10-06 2020-05-19 Rohm And Haas Electronic Materials Llc Stable electroless copper plating compositions and methods for electroless plating copper on substrates
CN113388829A (zh) * 2021-06-11 2021-09-14 惠州金晟新电子科技有限公司 化学镀铜液以及利用化学镀铜液镀铜基板的方法
EP4545680A1 (de) * 2023-10-26 2025-04-30 Atotech Deutschland GmbH & Co. KG Lösung zur stromlosen nickelfreien verkupferung und verfahren zur verwendung der lösung

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US4171225A (en) 1976-01-23 1979-10-16 U.S. Philips Corporation Electroless copper plating solutions
US4548644A (en) * 1982-09-28 1985-10-22 Hitachi Chemical Company, Ltd. Electroless copper deposition solution
CN110498532A (zh) * 2019-08-15 2019-11-26 深南电路股份有限公司 印制线路板废水的处理方法及处理装置

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US3300335A (en) * 1963-11-20 1967-01-24 Dow Chemical Co Electroless metal plating with foam
US3472664A (en) * 1966-09-15 1969-10-14 Enthone Inhibiting stardusting in electroless copper plating
US3485643A (en) * 1966-05-06 1969-12-23 Photocircuits Corp Electroless copper plating
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US3075856A (en) * 1958-03-31 1963-01-29 Gen Electric Copper plating process and solution
US3300335A (en) * 1963-11-20 1967-01-24 Dow Chemical Co Electroless metal plating with foam
US3485643A (en) * 1966-05-06 1969-12-23 Photocircuits Corp Electroless copper plating
US3472664A (en) * 1966-09-15 1969-10-14 Enthone Inhibiting stardusting in electroless copper plating
US3515563A (en) * 1967-12-28 1970-06-02 Photocircuits Corp Autocatalytic metal plating solutions

Cited By (30)

* Cited by examiner, † Cited by third party
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NL6915718A (de) 1971-04-20
BE757573A (fr) 1971-04-15
CH550255A (de) 1974-06-14
AT311145B (de) 1973-10-25
DE2049061B2 (de) 1980-07-24
HK49576A (en) 1976-08-06
DE2049061A1 (de) 1971-04-29
AU2101370A (en) 1972-04-20
DE2049061C3 (de) 1981-04-30
FR2065996A5 (de) 1971-08-06
GB1330332A (en) 1973-09-19
CA947458A (en) 1974-05-21

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