EP0152601B1 - Aqueous alcaline bath for chemically plating copper or nickel - Google Patents
Aqueous alcaline bath for chemically plating copper or nickel Download PDFInfo
- Publication number
- EP0152601B1 EP0152601B1 EP84115513A EP84115513A EP0152601B1 EP 0152601 B1 EP0152601 B1 EP 0152601B1 EP 84115513 A EP84115513 A EP 84115513A EP 84115513 A EP84115513 A EP 84115513A EP 0152601 B1 EP0152601 B1 EP 0152601B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- copper
- accordance
- aqueous alkaline
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 13
- 229910052802 copper Inorganic materials 0.000 title claims description 13
- 239000010949 copper Substances 0.000 title claims description 13
- 238000007747 plating Methods 0.000 title description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title 2
- 229910052759 nickel Inorganic materials 0.000 title 1
- 239000008139 complexing agent Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000005234 chemical deposition Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002736 metal compounds Chemical group 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HUQOFZLCQISTTJ-UHFFFAOYSA-N diethylaminoboron Chemical compound CCN([B])CC HUQOFZLCQISTTJ-UHFFFAOYSA-N 0.000 description 1
- 229940120503 dihydroxyacetone Drugs 0.000 description 1
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
Classifications
-
- 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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
-
- 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
Definitions
- the invention relates to an aqueous alkaline bath for the adhesive chemical deposition of copper on printed circuit boards according to the preamble of claim 1 and a method for the adhesive chemical deposition of this metal according to the preamble of claim 5.
- the document US-A-3095 309 describes chemical copper plating solutions which contain, among other things, mannitol or sorbitol as complexing agents and are alkaline.
- the concentrates or rinsing water produced during the operation of the known baths are moreover usually obtained in the form of solutions which can only be disposed of with great technical effort, since their direct return to the working process is not readily possible.
- copper coatings can be deposited from the bath according to the invention, in which the total of impurities in carbon, hydrogen and nitrogen in the copper coatings is 0.03%, while in conventionally deposited coatings, impurities are of the order of magnitude of 0.07 to 0.37% are.
- the quality of the metal coating deposited according to the invention therefore corresponds to that which is otherwise only achieved with electrolytic metal deposition. Purity and the thereby determined properties of the coating deposited according to the invention, such as average internal stress, average lattice distortion and the crystallite size are consequently on a par with the electroplated coatings.
- the bath according to the invention therefore enables the production of printed circuit boards with adhesive layers which are extremely ductile and easy to solder and which are characterized by the lowest internal stresses, which means a breakthrough in technology.
- the complexing agents to be used according to the invention also have the particular advantage of being readily biodegradable and, in contrast to the known complexing agents, of being particularly environmentally friendly.
- the glycerol to be used according to the invention has not been shown to have any damaging effect on organisms, so that, taking further account of its classification as a highly biodegradable substance, it exhibits favorable ecological properties.
- compounds of the metal copper can whose sulfates, nitrates, chlorides, bromides, thiocyanates, oxides, hydroxide, carbonates, basic carbonates, acetates are used, inter alia, in metal concentrations of 10- 4 to 2 mol / liter, preferably 10- 2 up to 1 mol / liter.
- the complex compound Schiff's potassium cupri biuret used according to the invention can be prepared by adding 1 mol of copper acetate to an aqueous solution of 1 mol of biuret and 4 mol of potassium hydroxide by precipitation with a 2% alcoholic potassium hydroxide solution.
- the molar ratio of copper to complexing agent is at least 1: 0.8, preferably from 1: 1 to 1: 6.
- the stability of the metal complexes formed from these complexing agents is extremely high, but can, if desired, be influenced immediately by acidification if the pH changes, which leads to complete precipitation of the metal hydroxide, which can then be returned to the working process.
- the pH of the bath according to the invention should be greater than 10, preferably from 12 to 14, and is kept at the desired value by adding customary pH-regulating substances or mixtures.
- Suitable reducing agents are in particular formaldehyde, sodium borohydride, dimethylaminoborane, diethylaminoborane, hydrazine, glyceraldehyde, dihydroxyacetone and other common re detergent with the exception of sodium hypophosphite.
- the bath is operated at temperatures from 5 ° C to the boiling point, preferably from 20 ° to 80 ° C.
- the bath can additionally contain stabilizers known per se based on polyamines, N-containing compounds, reaction products of N-containing compounds with epihalohydrins, sulfur or selenium compounds with the oxidation state minus one or minus two, mercury compounds or lead compounds, to ensure a sufficient lifespan of the bath.
- the basic composition of the bath according to the invention is as follows: metal compounds
- the bath according to the invention is suitable for the full and partial metallization of conductors and non-conductors after corresponding customary pretreatment, such as degreasing, pickling, cleaning, conditioning, activating and reducing.
- customary pretreatment such as degreasing, pickling, cleaning, conditioning, activating and reducing.
- a preferred field of application is the production of printed circuits.
- the conductors that had been plated through in this bath were, according to the transmitted light method, flawless.
- the deposition rate was approx. 2 pm / h, so that a treatment time of 15-20 minutes is completely sufficient.
- This bath deposits ductile copper coatings at a speed of approx. 5 pm / h, which are particularly suitable for semi or additive technology.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Description
Die Erfindung betrifft ein wässriges alkalisches Bad zur haftfesten chemischen Abscheidung von Kupfer auf Leiterplatten gemäss Oberbegriff des Anspruchs 1 sowie ein Verfahren zur haftfesten chemischen Abscheidung dieses Metalls gemäss Oberbegriff des Anspruchs 5.The invention relates to an aqueous alkaline bath for the adhesive chemical deposition of copper on printed circuit boards according to the preamble of claim 1 and a method for the adhesive chemical deposition of this metal according to the preamble of claim 5.
Bäder der eingangs bezeichneten Art sind allgemein bekannt.Baths of the type described in the introduction are generally known.
So beschreibt die Druckschrift US-A-3095 309 chemische Kupferplattierungslösungen, die als Komplexbildner unter anderem Mannit oder Sorbit enthalten und alkalisch sind.For example, the document US-A-3095 309 describes chemical copper plating solutions which contain, among other things, mannitol or sorbitol as complexing agents and are alkaline.
Bekannte Plattierlösungen enthalten in der Regel beträchtliche Mengen an Komplexbildnern, um das Ausfällen von Metallhydroxiden zu verhindern. Das führt zwangsläufig zu einer unbefriedigenden Qualität der aus diesen Bädern abgeschiedenen Überzüge, die, je nach Badtyp, erhebliche Mengen an Verunreinigungen, wie Kohlenstoff, Stickstoff, Wasserstoff unter anderem enthalten können, welche einen entscheidenden Einfluss auf die Kristallstruktur und somit auf technologisch wichtige Eigenschaften, wie spezifische elektrische Leitfähigkeit, innere Spannung, Haftfestigkeit und Dehnbarkeit beziehungsweise Duktilität, ausüben. Dies wirkt sich zum Beispiel besonders störend bei der Herstellung von Leiterplatten aus, bei denen sich unerwünschte Blasen, Abhebungen und Risse bilden können, und zwar um so mehr, je dicker die abgeschiedene Metallschicht ist.Known plating solutions usually contain considerable amounts of complexing agents in order to prevent the precipitation of metal hydroxides. This inevitably leads to an unsatisfactory quality of the coatings deposited from these baths, which, depending on the bath type, can contain considerable amounts of impurities such as carbon, nitrogen, hydrogen, among other things, which have a decisive influence on the crystal structure and thus on technologically important properties, such as specific electrical conductivity, internal tension, adhesive strength and ductility. For example, this has a particularly disruptive effect in the production of printed circuit boards in which undesired bubbles, lifts and cracks can form, and the more so the thicker the deposited metal layer.
Die beim Betrieb der bekannten Bäder anfallenden Konzentrate beziehungsweise Spülwässer fallen überdies meist in Form von Lösungen an, die nur mit grossem technischen Aufwand entsorgt werden können, da ihre direkte Zurückführung in den Arbeitsprozess nicht ohne weiteres möglich ist.The concentrates or rinsing water produced during the operation of the known baths are moreover usually obtained in the form of solutions which can only be disposed of with great technical effort, since their direct return to the working process is not readily possible.
Aufgabe der vorliegenden Erfindung ist die Schaffung eines Bades und eines Verfahrens, welche eine haftfeste chemische Abscheidung von Kupfer mit einem gegenüber den konventionell abgeschiedenen Überzügen geringeren Anteil an Verunreinigungen bei gleichzeitig technisch problemloser Rückgewinnung des eingesetzten Metalls erlauben.It is an object of the present invention to provide a bath and a process which permit an adherent chemical deposition of copper with a lower proportion of impurities compared to the conventionally deposited coatings with a technically problem-free recovery of the metal used.
Diese Aufgabe wird erfindungsgemäss durch den in den Ansprüchen gekennzeichneten Gegenstand gelöst.This object is achieved according to the invention by the subject matter characterized in the claims.
Vorteilhafte Weiterbildungen sind in den Unteransprüchen beschrieben.Advantageous further developments are described in the subclaims.
Aus dem erfindungsgemässen Bad können überraschenderweise Kupferüberzüge abgeschieden werden, bei denen die Summe der Verunreinigungen an Kohlenstoff, Wasserstoff und Stickstoff in den Kupferüberzügen 0,03% beträgt, während in konventionell abgeschiedenen Überzügen Verunreinigungen in der Grössenordnung von 0,07 bis 0,37% enthalten sind.Surprisingly, copper coatings can be deposited from the bath according to the invention, in which the total of impurities in carbon, hydrogen and nitrogen in the copper coatings is 0.03%, while in conventionally deposited coatings, impurities are of the order of magnitude of 0.07 to 0.37% are.
Die Qualität des erfindungsgemäss abgeschiedenen Metallüberzugs entspricht daher derjenigen, die sonst nur bei elektrolytischer Metallabscheidung erreicht wird. Reinheit und die hierdurch bestimmten Eigenschaften des erfindungsgemäss abgeschiedenen Überzugs, wie mittlere Eigenspannung, mittlere Gitterverzerrung sowie die Kristallitgrösse sind demzufolge den galvanisch abgeschiedenen Überzügen ebenbürtig.The quality of the metal coating deposited according to the invention therefore corresponds to that which is otherwise only achieved with electrolytic metal deposition. Purity and the thereby determined properties of the coating deposited according to the invention, such as average internal stress, average lattice distortion and the crystallite size are consequently on a par with the electroplated coatings.
Das erfindungsgemässe Bad ermöglicht daher die Herstellung von Leiterplatten mit haftfesten Schichten, die äusserst duktil und lötfreudig sind und sich durch geringste innere Spannungen auszeichnen, was technologisch einen Durchbruch bedeutet.The bath according to the invention therefore enables the production of printed circuit boards with adhesive layers which are extremely ductile and easy to solder and which are characterized by the lowest internal stresses, which means a breakthrough in technology.
Die erfindungsgemäss zu verwertenden Komplexbildner haben ausserdem den besonderen Vorteil, biologisch leicht abbaubar und damit im Gegensatz zu den bekannten Komplexbildnern besonders umweltfreundlich zu sein. So ist zum Beispiel bei dem erfindungsgemäss zu verwendenden Glycerin keine schädigende Wirkung auf Organismen bekannt geworden, so dass es unter weiterer Berücksichtigung seiner Zuordnung als hoch biologisch abbaubar einzustufender Stoff günstige ökologische Eigenschaften entfaltet.The complexing agents to be used according to the invention also have the particular advantage of being readily biodegradable and, in contrast to the known complexing agents, of being particularly environmentally friendly. For example, the glycerol to be used according to the invention has not been shown to have any damaging effect on organisms, so that, taking further account of its classification as a highly biodegradable substance, it exhibits favorable ecological properties.
Als Verbindungen des Metalls Kupfer können dessen Sulfate, Nitrate, Chloride, Bromide, Rhodanide, Oxide, Hydroxid-Carbonate, basische Carbonate, Acetate unter anderem verwendet werden, und zwar in Metallkonzentrationen von 10-4 bis 2 Mol/Liter, vorzugsweise 10-2 bis 1 Mol/ Liter.When compounds of the metal copper can whose sulfates, nitrates, chlorides, bromides, thiocyanates, oxides, hydroxide, carbonates, basic carbonates, acetates are used, inter alia, in metal concentrations of 10- 4 to 2 mol / liter, preferably 10- 2 up to 1 mol / liter.
Diese Metallverbindungen bilden mit den erfindungsgemäss eingesetzten Komplexbildnern in der Badlösung Komplexverbindungen, welche die gewünschte Wirkung entfalten. Es versteht sich jedoch, dass diese Komplexverbindungen auch für sich in an sich bekannter Weise hergestellt und erst vor ihrer Verwendung der Badlösung zugefügt werden können.These metal compounds form complex compounds with the complexing agents used according to the invention in the bath solution, which develop the desired effect. However, it goes without saying that these complex compounds can also be prepared per se in a manner known per se and can only be added to the bath solution before they are used.
Beispielsweise lässt sich die erfindungsgemäss eingesetzte Komplexverbindung Schiffsches Kaliumkupri-Biuret durch Zugabe von 1 Mol Kupferacetat zu einer wässrigen Lösung von 1 Mol Biuret und 4 Mol Kaliumhydroxid durch Fällen mit2%iger alkoholischer Kaliumhydroxidlösung herstellen.For example, the complex compound Schiff's potassium cupri biuret used according to the invention can be prepared by adding 1 mol of copper acetate to an aqueous solution of 1 mol of biuret and 4 mol of potassium hydroxide by precipitation with a 2% alcoholic potassium hydroxide solution.
Es hat sich als besonders vorteilhaft erwiesen, wenn das molare Verhältnis von Kupfer zu Komplexbildner mindestens 1:0,8, vorzugsweise von 1:1 bis 1:6, beträgt.It has proven to be particularly advantageous if the molar ratio of copper to complexing agent is at least 1: 0.8, preferably from 1: 1 to 1: 6.
Die Stabilität der aus diesen Komplexbildnern gebildeten Metallkomplexe ist ausserordentlich gross, kann jedoch bei Veränderung des pH-Wertes durch Ansäuern gewünschtenfalls sofort beeinflusst werden, wodurch es zur vollständigen Fällung des Metallhydroxids kommt, das dann dem Arbeitsprozess wieder zurückgeführt werden kann.The stability of the metal complexes formed from these complexing agents is extremely high, but can, if desired, be influenced immediately by acidification if the pH changes, which leads to complete precipitation of the metal hydroxide, which can then be returned to the working process.
Der pH-Wert des erfindungsgemässen Bades soll grösser als 10, vorzugsweise von 12 bis 14, betragen, und wird durch Zusatz üblicher pHregulierender Stoffe oder Stoffgemische auf dem gewünschten Wert gehalten.The pH of the bath according to the invention should be greater than 10, preferably from 12 to 14, and is kept at the desired value by adding customary pH-regulating substances or mixtures.
Als Reduktionsmittel eignen sich insbesondere Formaldehyd, Natriumborhydrid, Dimethylaminoboran, Diäthylaminoboran, Hydrazin, Glycerinaldehyd, Dihydroxyaceton sowie andere übliche Reduktionsmittel mit Ausnahme von Natrium hypophosphit.Suitable reducing agents are in particular formaldehyde, sodium borohydride, dimethylaminoborane, diethylaminoborane, hydrazine, glyceraldehyde, dihydroxyacetone and other common re detergent with the exception of sodium hypophosphite.
Das Bad wird bei Temperaturen von 5°C bis zum Siedepunkt, vorzugsweise von 20° bis 80°C, betrieben.The bath is operated at temperatures from 5 ° C to the boiling point, preferably from 20 ° to 80 ° C.
Sofern gewünscht, kann das Bad zusätzlich an sich bekannte Stabilisatoren auf Basis von Polyaminen, N-haltige Verbindungen, Umsetzungsprodukten von N-haltigen Verbindungen mit Epihalohydrinen, Schwefel- oder Selenverbindungen mit der Oxydationsstufe minus eins oder minus zwei, Quecksilber-Verbindungen oder Bleiverbindungen enthalten, um eine ausreichende Lebensdauer des Bades zu gewährleisten.If desired, the bath can additionally contain stabilizers known per se based on polyamines, N-containing compounds, reaction products of N-containing compounds with epihalohydrins, sulfur or selenium compounds with the oxidation state minus one or minus two, mercury compounds or lead compounds, to ensure a sufficient lifespan of the bath.
Als Netzmittel eignen sich alle für diesen Zweck bekannten Produkte.All products known for this purpose are suitable as wetting agents.
Die Grundzusammensetzung des erfindungsgemässen Bades ist wie folgt: Metallverbindungen
Das erfindungsgemässe Bad eignet sich für die Voll- und Partiellmetallisierung von Leitern und Nichtleitern nach entsprechender üblicher Vorbehandlung, wie Entfetten, Beizen, Reinigen, Konditionieren, Aktivieren und Reduzieren. Ein bevorzugtes Anwendungsgebiet ist die Herstellung von gedruckten Schaltungen.The bath according to the invention is suitable for the full and partial metallization of conductors and non-conductors after corresponding customary pretreatment, such as degreasing, pickling, cleaning, conditioning, activating and reducing. A preferred field of application is the production of printed circuits.
Die folgenden Beispiele dienen zur Erläuterung der Erfindung.The following examples serve to illustrate the invention.
Die in diesem Bad durchkontaktierten Leiter waren, nach der Durchlichtmethode beurteilt, einwandfrei. Die Abscheidungsgeschwindigkeit betrug ca. 2 pm/h, so dass eine Behandlungszeit von 15-20 Minuten vollkommen ausreichend ist. Nach Absenkung des pH-Wertes, mit einer Säure, auf pH 7-10, fiel praktisch das gesamte Kupfer als Kupferhydroxid aus. Nach der Filtration kann es direkt im Bad wieder gelöst werden.The conductors that had been plated through in this bath were, according to the transmitted light method, flawless. The deposition rate was approx. 2 pm / h, so that a treatment time of 15-20 minutes is completely sufficient. After lowering the pH with an acid to pH 7-10, practically all of the copper precipitated out as copper hydroxide. After filtration, it can be dissolved again in the bathroom.
Dieses Bad scheidet mit einer Geschwindigkeit von ca. 5 pm/h duktile Kupferüberzüge ab, die besonders für die Semi- oder Additivtechnik geeignet sind.This bath deposits ductile copper coatings at a speed of approx. 5 pm / h, which are particularly suitable for semi or additive technology.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3404270 | 1984-02-04 | ||
| DE19843404270 DE3404270A1 (en) | 1984-02-04 | 1984-02-04 | AQUEOUS ALKALINE BATH FOR CHEMICAL DEPOSITION OF COPPER, NICKEL, COBALT AND THEIR ALLOYS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0152601A1 EP0152601A1 (en) | 1985-08-28 |
| EP0152601B1 true EP0152601B1 (en) | 1988-12-07 |
Family
ID=6227013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84115513A Expired EP0152601B1 (en) | 1984-02-04 | 1984-12-15 | Aqueous alcaline bath for chemically plating copper or nickel |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4720404A (en) |
| EP (1) | EP0152601B1 (en) |
| JP (1) | JPS60204885A (en) |
| AT (1) | AT384829B (en) |
| CA (1) | CA1254353A (en) |
| DE (2) | DE3404270A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4983428A (en) * | 1988-06-09 | 1991-01-08 | United Technologies Corporation | Ethylenethiourea wear resistant electroless nickel-boron coating compositions |
| DE4412295C1 (en) * | 1994-04-08 | 1996-01-18 | Plastform Gmbh | Process for the galvanic coating of metal surfaces with copper or copper alloys |
| US6054173A (en) * | 1997-08-22 | 2000-04-25 | Micron Technology, Inc. | Copper electroless deposition on a titanium-containing surface |
| US5976614A (en) * | 1998-10-13 | 1999-11-02 | Midwest Research Institute | Preparation of cuxinygazsen precursor films and powders by electroless deposition |
| US6797312B2 (en) * | 2003-01-21 | 2004-09-28 | Mattson Technology, Inc. | Electroless plating solution and process |
| US20060141281A1 (en) * | 2004-12-24 | 2006-06-29 | Tdk Corporation | R-T-B system permanent magnet and plating film |
| EP3190209B1 (en) * | 2016-01-06 | 2018-06-06 | ATOTECH Deutschland GmbH | 1-acylguanidine compounds and the use of said compounds in electroless deposition of nickel and nickel alloy coatings |
| KR101681116B1 (en) * | 2016-05-26 | 2016-12-09 | (주)오알켐 | Method for electroless copper plating through-hole of printed circuit board and method for preparing a catalytic solution used in method thereof |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2430581A (en) * | 1944-11-29 | 1947-11-11 | Rca Corp | Metallizing nonmetallic bodies |
| US2935425A (en) * | 1954-12-29 | 1960-05-03 | Gen Am Transport | Chemical nickel plating processes and baths therefor |
| US2938805A (en) * | 1958-03-31 | 1960-05-31 | Gen Electric | Process of stabilizing autocatalytic copper plating solutions |
| US3095309A (en) * | 1960-05-03 | 1963-06-25 | Day Company | Electroless copper plating |
| US3268353A (en) * | 1960-11-18 | 1966-08-23 | Electrada Corp | Electroless deposition and method of producing such electroless deposition |
| US3383224A (en) * | 1965-11-09 | 1968-05-14 | Shipley Co | Electroless copper deposition |
| US3472660A (en) * | 1965-11-14 | 1969-10-14 | Toshihiko Satake | Separation and polishing of rice grains |
| DE1298827B (en) * | 1966-03-19 | 1969-07-03 | Siemens Ag | Nickel plating solution for electroless nickel plating of silicon wafers |
| US3992211A (en) * | 1968-07-15 | 1976-11-16 | Trans-Metals Corporation | Electroless plating composition |
| US3615735A (en) * | 1968-08-13 | 1971-10-26 | Shipley Co | Electroless copper plating |
| GB1332307A (en) * | 1970-01-17 | 1973-10-03 | Marconi Co Ltd | Electroless plating solutions |
| JPS5149576B2 (en) * | 1971-08-10 | 1976-12-27 | ||
| JPS4928571A (en) * | 1972-07-11 | 1974-03-14 | ||
| JPS4962330A (en) * | 1972-10-19 | 1974-06-17 | ||
| US4287253A (en) * | 1975-04-08 | 1981-09-01 | Photocircuits Division Of Kollmorgen Corp. | Catalytic filler for electroless metallization of hole walls |
| SU740860A1 (en) * | 1978-02-06 | 1980-06-15 | Предприятие П/Я В-8657 | Solution for chemical precipitation of nickel-boron alloy |
| US4268536A (en) * | 1978-12-07 | 1981-05-19 | Western Electric Company, Inc. | Method for depositing a metal on a surface |
| DE2919726A1 (en) * | 1979-05-16 | 1980-11-27 | Bernd Tolkmit | Depositing metal coatings on workpieces - from aq. acid bath contg. polyglycol ether activator, powdered coating metal and reducible metal ions |
| DE2854159C2 (en) * | 1978-12-15 | 1982-04-22 | Bernd 4000 Düsseldorf Tolkmit | Process for applying metallic coatings to metallic workpieces by mechanical-chemical treatment of the workpieces |
| JPS5643109A (en) * | 1979-09-07 | 1981-04-21 | Hitachi Ltd | Book stocking and delivering apparatus |
| DE3121015C2 (en) * | 1981-05-27 | 1986-12-04 | Friedr. Blasberg GmbH und Co KG, 5650 Solingen | Process for activating pickled surfaces and solution for carrying out the same |
| CA1184359A (en) * | 1981-10-23 | 1985-03-26 | Donald A. Arcilesi | Metallic impurity control for electroless copper plating |
-
1984
- 1984-02-04 DE DE19843404270 patent/DE3404270A1/en not_active Withdrawn
- 1984-12-15 DE DE8484115513T patent/DE3475535D1/en not_active Expired
- 1984-12-15 EP EP84115513A patent/EP0152601B1/en not_active Expired
-
1985
- 1985-01-31 AT AT0027385A patent/AT384829B/en not_active IP Right Cessation
- 1985-02-01 CA CA000473446A patent/CA1254353A/en not_active Expired
- 1985-02-04 JP JP60018815A patent/JPS60204885A/en active Pending
-
1986
- 1986-08-07 US US06/896,741 patent/US4720404A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA1254353A (en) | 1989-05-23 |
| AT384829B (en) | 1988-01-11 |
| ATA27385A (en) | 1987-06-15 |
| EP0152601A1 (en) | 1985-08-28 |
| JPS60204885A (en) | 1985-10-16 |
| DE3404270A1 (en) | 1985-08-08 |
| DE3475535D1 (en) | 1989-01-12 |
| US4720404A (en) | 1988-01-19 |
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