EP0109402B1 - Solutions catalytiques permettant d'activer des substrats non conducteurs et procede de placage sans passage de courant electrique - Google Patents

Solutions catalytiques permettant d'activer des substrats non conducteurs et procede de placage sans passage de courant electrique Download PDF

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Publication number
EP0109402B1
EP0109402B1 EP19830901290 EP83901290A EP0109402B1 EP 0109402 B1 EP0109402 B1 EP 0109402B1 EP 19830901290 EP19830901290 EP 19830901290 EP 83901290 A EP83901290 A EP 83901290A EP 0109402 B1 EP0109402 B1 EP 0109402B1
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Prior art keywords
metal
bath
copper
substrate
salts
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EP19830901290
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German (de)
English (en)
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EP0109402A1 (fr
EP0109402A4 (fr
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Harold L. Rhodenizer
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MacDermid Inc
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MacDermid Inc
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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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating

Definitions

  • the present invention relates to electroless plating, and particularly to improved catalyst solutions for activating non-conductive substrates and an improved electroless plating process.
  • Metallization processes for non-conductive substrates using noble metal baths as activators are well known. These processes are useful for applying decorative metal to articles such as glass and are particularly useful in metallizing printed circuit boards, especially those having holes punched or drilled therein.
  • metal baths are used sequentially, by providing first a film of Group IV metal ion reducing agent, e.g., stannous ion, followed by a bath which provides a film of reduced precious metal, e.g., palladium, on the surface of the substrate.
  • This process activates or sensitizes the surface of the substrate for subsequent electroless metal deposition.
  • Various 2-step activation systems and improvements are found in the art. These processes presented problems, especially with copper clad laminates as substrates, such as inadequate metal-to-metal bonding in the subsequent electroless metal deposition, lack of uniformity of results and unstable activator baths.
  • the activating baths typically contain a protective metal, the preferred embodiment being a tin-palladium sol, the tin being the protective metal, as disclosed for example by Shipley U.S. Patent 3,011,920.
  • unitary metal activator baths have been called colloidal or semi-colloidal in most prior art or solutions as in U.S. Patent 3,672,938 to Zeblisky. Regardless of the physical description, they are all unitary noble metal sol activators as opposed to the 2-step activator systems and will be referred to herein as unitary or single step activator sols or baths.
  • the presence of the protective metal causes other problems in the electroless metal deposition step, such as lengthy initiation times for metal deposition and blistering of metal from substrates after metal deposition when using non-metallic substrates. When copper clad substrates are used, poor copper-to-copper adhesion can result after copper deposition.
  • Hole wall pullaway or separation of the plate composite from the hole wall of thru-holes in printed circuit boards can also be a problem.
  • the pullaway can happen in operations subsequent to electroplating either during fusing of the tin lead coating or during soldering on components of the finished printed circuit board. Studies have shown that with elimination of acceleration, an increase in the amount of pullaway will result.
  • the acceleration step has been said to be optional, the preferred use of the protective metal necessitates the use of an acceleration step as disclosed, for example, in U.S. Patent 3,011,920 to Shipley. This is particularly preferred when using the tin-palladium single step activator sol systems with copper clad laminates as substrates, and is also useful with other systems. Acceleration is also stated as preferable rather than necessary in other patents, such as U.S. Patent 3,650,913 to D'Ottavio.
  • the acceleration step besides adding to the length of the plating process, can cause problems itself. Poor metal coverage or voiding in the electroless deposition step can be caused by over-acceleration. It is assumed that over-acceleration removes some of the catalytic metal from the substrate while removing the protective metal, thus rendering the substrate less active to metal deposition. Conversely, under-acceleration can cause poor adhesion of metal to substrate or blistering in the electroless plating step. Novel accelerators have been developed to try to overcome this control problem, for example, in U.S. Patent 4,204,013 to Arcilesi et al, the accelerator bath contains an alkyl amine, including certain amino acids.
  • phenol or aromatic alcohol type compounds are used as additives to the activator bath. Acceleration in fluoboric acid is included.
  • EDTA is used as an additive at a specified low pH although EDTA shows very little solubility at this low pH.
  • a stripping step is included after activation.
  • the activator solution comprises an aliphatic sulphonic acid as at least part of the acid. Again, however, the use of an acceleration step is disclosed employing fluoboric acid.
  • FR-A-2,364,958 there is disclosed the preparation of a solid composition which can be diluted to form an activating solution for electroless plating and which comprises:
  • a composition for activating a substrate for electroless metallization in the form of an aqueous solution comprising: at least one salt of a noble metal that is catalytic to chemically reducing dissolved salts of the metal to be plated in an electroless plating bath, at least one salt capable of forming a protective metal sol in water, a source of halide ions in excess of any which may be provided by the noble metal salts and salts for forming the protective metal sol, and 10 to 80 g/l of at least one organic acid, which is substantially soluble in the plating bath, selected from aliphatic carboxylic acids, aromatic carboxylic acids, amino acids, and combinations of these.
  • the invention is preferably employed for electrolessly plating copper and nickel, most preferably copper, but can also be employed for activating substrates prior to plating gold, palladium and cobalt.
  • This invention also comprehends the use of the above activator sols in an overall combination of steps constituting a complete chemical plating system which combination provides not only fewer steps than the conventional system, but comparable or improved results.
  • the activator baths which are used for prior art comparison in the examples, are commonly used in an electroless plating cycle which includes the acceleration step followed by various electroless metallization baths. These activator baths comprise palladium chloride, stannous chloride, sodium chloride, and/or hydrochloric acid without the organic acid of this invention.
  • Metex Electroless Copper 9048 is a high speed bath run at about 130°F, 54.5°C.
  • Metex Copper 9027 is a high speed room temperature bath.
  • MACu Dep 60 is a medium temperature (about 100°F, 38°C) high speed bath.
  • MACu Dep 20 is a room temperature, slow speed bath. High speed provides a thicker metal film than slow speed in the same time. They are used depending on production needs.
  • These copper baths include the major components of electroless copper baths and comprise: a solvent, usually water; a source of cupric ions; a source of hydroxide ions; a complexor or chelator, such as EDTA, to maintain the copper in solution; and a reducing agent, such as formaldehyde.
  • the activator bath prepared according to D'Ottavio in U.S. Patent 3,532,518 is a sol which comprises water, hydrochloric acid, stannous chloride, sodium stannate and palladium.
  • the preferred activator baths of this invention are prepared by dilution of this sol with water before use, and the inclusion of an organic acid selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, amino acids, and combinations of these.
  • the preferred range of concentrations encompasses from 0.0398 to 0.1194 gm/I palladium and from 2 to 6 gm/I stannous ion.
  • workability is not limited to this range, but encompasses from .02 gm/I to 8 gm/I palladium and from 1 gm/l to 300 gm/I stannous ion.
  • chloride normalities of the activator bath of the invention range from 3.4 to 4.6 normal.
  • Chloride normalities for workability range from 0.1 N to saturation.
  • the activator bath of this invention comprises one or more organic acids, such as tartaric, citric, maleic, malonic, glycolic, and gluconic, as illustrated in the examples, the preferred acids being tartaric and/or citric acids. Also effective are glutaric acid, glycine, and salicylic acid.
  • the preferred embodiment of this invention comprises 10% by volume hydrochloric acid, 7.5 gm/I tartaric acid, and 3.0 gm/I citric acid in water.
  • the bath also comprises about 0.0597 gm/I palladium and about 3 gm/I stannous ion.
  • Chloride normality of about 3.6N is obtained by addition of sodium chloride.
  • the plating process of this invention comprises first cleaning the nonconductive substrate with suitable cleaners known to the art, followed by appropriate rinses.
  • the substrate then is usually etched with a chemical etchant, several of which are commercially available for this purpose, in order to prepare the surface for reception of the activating metal. Acid dips, neutralizers, and water rinses may be included before and after etching if applicable.
  • the etched substrate is then contacted with the activator of this invention for from about 2 to 5 minutes and water rinsed for about 3 minutes, although these times may vary somewhat.
  • a predip in a bath containing halide ions may be included before activation.
  • the substrates are next chemically plated, and any number of electroless metal compositions and methods known to the art can be used. This then can be followed if desired, by electroplating in the conventional manner with copper or any other desired metal.
  • the process of this invention differs substantially from the traditional prior art plating process which typically requires an acceleration step, usually in an acid after the activation step.
  • a water rinse is also usually included after acceleration before electroless metallization.
  • a prior art noble metal-protective metal (usually palladium-tin) activator bath which does not include the organic acid of this invention is used in the prior art plating process in the comparisons below.
  • the activator bath of this invention in its preferred embodiment, comprising 0.0597 gm/I palladium, 3 gm/i stannous ion, 7.5 gm/I tartaric acid, and 3.0 gm/I citric acid, was prepared for use in a 30 gal tank. Chloride normality of the bath was maintained at 3.5 to 4.5N.
  • the plating cycle of this invention as described above was used.
  • the control cycle for the purposes of prior art comparison was a commercially available prior art plating cycle known as MacDermid Metex PTH Process which includes an acid acceleration bath, Metex PTH Accelerator 9071.
  • the control cycle contained a commercially available activator bath, MacDermid Metex PTH Activator 9070 (D'Ottavio U.S.
  • Patents 3,532,518 and 3,650,913 The substrates used were copper clad laminate production printed circuit boards with thru-holes. Half of the boards were run through the cycle of this invention and the other half through the control cycle which was in use for the production at the time of this testing procedure. Times and temperatures were the same for both cycles as were the compositions of the bath except for the activator baths and the accelerator bath for the control cycle. Both sets of boards were electrolessly plated in a commercially available copper bath, MacDermid MACu Dep 60. Copper coverage and copper-to-copper adhesion were found to be substantially the same on both sets of boards. After electroless copper plating, the boards were electrolytically copper plated and then electroplated with tin-lead.
  • thru-holes were subjected to a solder-shock test which consists of immersion in 550°F (288°C) solder for 10 seconds. Cross-sections were taken and examined. The incidence of hole wall pullaway was the same for both sets of boards. No voiding was observed in either set of boards. The number of rejected finished boards was also substantially the same for both sets of boards.
  • the cycle and activator bath of this invention showed results comparable to the commercial prior art activator bath and cycle and have the advantage of deleting the acceleration step and subsequent rinse.
  • an activator bath was prepared using the preferred concentration of palladium, stannous ion, and chloride without the organic acid of this invention.
  • the plating process of this invention as stated in Example 1 was used with the above prior art bath. Copper clad substrates were used. Blistering of the copper from the copper-clad substrate was observed after electroless deposition on all samples.
  • the prior art activator bath which does not contain the organic acid of this invention gives poor results when used with the plating process of this invention.
  • Activator baths of this invention in its preferred embodiment were prepared with chloride normalities of 3.4, 3.6, and 4.6.
  • the plating process of this invention as stated in Example 1 was used with copper clad substrates. Copper-to-copper adhesion was found to be good on all samples after copper deposition.
  • Example 1 The plating process of this invention as stated in Example 1 was used for Examples 6-11. All substrates were electroless plated in Metex Copper 9027.
  • MacDermid Metex PTH Accelerator 9074 was used for prior art comparison (Examples 12 and 13).
  • the plating cycle used for Examples 12 and 13 was MacDermid Metex PTH Process.
  • the amount of copper deposited on the substrate was measured in average microinches (pm) of copper coverage after electroless deposition.
  • the data shows 16 to 18 microinches (0.4-0.46 pm) more copper is deposited on the epoxy surface than on the copper clad surface in the same deposition time (Examples 6-11, Table I).
  • the data shows that 9 microinches (0.23 pm) more of copper is deposited on the epoxy than the copper clad substrate in the same deposition time.
  • the larger differential is advantageous when printed circuit boards having composite copper clad and epoxy or non-metallic surfaces are used as substrates, since it is the epoxy that is important to be plated, not the copper cladding.
  • Activator baths of this invention comprising 0.0597 gm/I palladium, 3 gm/I stannous ions, and a chloride normality of 3.4N were prepared.
  • the plating process of this invention as stated in Example 1 was used. Epoxy panels were used as substrates. Various concentrations of tartaric acid were used in the activator baths. Metex Copper 9027 was used for electroless deposition. All substrates were held in the copper plating bath for three minutes.
  • Examples 15-18 showed more copper deposited than Example 14 (prior art) which has no tartaric acid in the activator bath. With all samples, no acceleration was used in the plating cycle. In a short plating time (3 minutes), more copper was deposited on the epoxy substrates when the activator bath of this invention was used than when the prior art activator bath was used.
  • Activator baths of this invention were prepared comprising 0.1194 gm/I palladium and 6 gm/I stannous ion, having a chloride normality of 3.6N with each bath containing 10 gm/I of one of the following acids: tartaric, citric, maleic, malonic, glycolic, gluconic.
  • Copper clad substrates were subjected to the plating process of this invention as described in Example 1 using the above described activator baths. Two commercially-available electroless copper baths were used, Metex Copper 9027 and MACu Dep 20. The substrates were inspected for copper-to-copper adhesion after electroless plating. Good adhesion was found with all samples.
  • organic acids chosen to be tested were indicative of a range of aliphatic carboxylic acids including hydroxy substituted and some that were not hydroxy substituted. It is obvious that usefulness would not be limited to the acids in this example, but would encompass other aliphatic carboxylic acids.
  • Activator baths comprising 0.1194 gm/I palladium, 6 gm/I stannous ion, and 10 gm/I of an aromatic carboxylic acid such as salicylic acid or an amino acid such as glycine were prepared. Chloride normalities were 3.6N. The procedure of Example 19 was followed with these baths and subsequent electroless deposition of copper.
  • Bath #1 comprises a commercially-available activator bath, MacDermid Mactivate 10 which comprises 0.0597 gm/I palladium and 3.0 gm/I stannous ion and had a chloride normality of 3.6N.
  • Bath #2 comprises the preferred embodiment of this invention, comprising 0.0597 gm/I palladium and 3.0 gm/I stannous ion. Chloride normality is 3.6N.
  • Bath #2 also comprises 7.5 gm/i tartaric acid and 3.0 gm/I citric acid.
  • a series of copper clad substrates were immersed in both baths for the same length of time. Copper build-up in the baths in ppm was measured by the atomic absorption method. Bath #2 (invention) showed significantly less copper build-up than Bath #1 (prior art). The copper build-up in the baths is shown in the attached Figure.
  • An activator bath comprising 7% MacDermid Metex PTH Activator 9070 (D'Ottavio U.S. Patents 3,532,518 and 3,650,913) was prepared. Analysis showed working bath concentrations to be 0.0597 gm/I palladium and 3 gm/I stannous ion. Chloride normality was 4.6N. Copper clad laminates were subjected to the commercially-available MacDermid Metex PTH plating process which differs from the plating process of this invention by inclusion of the acceleration step in Metex PTH Accelerator 9071. Absorption data showed 0.69 mg/sq cm palladium and 0.8 mg/sq cm tin on the substrates after the activation. After electroless copper plating, the substrates had a dark pink color and poor metal coverage, especially on the edges of the substrate.
  • An activator bath of this invention in its preferred embodiment comprising 0.0597 gm/I palladium and 3 gm/I tin, chloride normality of 3.6N, 7.5 gm/I tartaric acid and 3.0 gm/I citric acid was prepared. Copper clad laminates were subjected to the plating process of this invention. Analysis verified that the bath contained 0.0597 gm/I palladium and 3 gm/I stannous ion. Absorption data showed 0.8 mg/sq cm palladium and 2076 mg/sq cm tin on the substrate after activation. Good copper coverage and no voids were found after electroless copper plating.
  • the activator bath of this invention gives good results at a lower working concentration of palladium using the plating process of this invention which does not include acceleration compared to the prior art activator bath used in the prior art plating process which includes acceleration.
  • Substrates consisting of panels of ABS plastic and epoxies were subjected to the activator bath of this invention in its preferred embodiment and the plating process of this invention.
  • a commercially available nickel bath was used for electroless plating known as MacDermid MACuplex 9340 Electroless Nickel.
  • the plating process used comprised subjecting the substrates to the following steps:

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Abstract

Composition d'activation améliorée permettant de préparer des substrats pour effectuer une métallisation dans un bain de placage sans passage de courant électrique. Un procédé amélioré est également décrit pour activer des substrats avant d'effectuer la métallisation, ainsi qu'un procédé amélioré de métallisation utilisant le procédé d'activation amélioré. Le dépôt sans passage de courant électrique qui consiste à réduire chimiquement les ions du métal à plaquer à partir du bain de placage et sur une surface activée d'un substrat, est amélioré en utilisant un acide organique dans le bain d'activation qui active la surface du substrat. Des bains d'activation préférés contiennent des ions halogénure de palladium pour former une surface catalytique sur le substrat, des ions halogénure stanneux pour former un sol protecteur, une source d'ions d'un halogénure supplémentaire, et un acide organique tel que des acides citriques ou tartariques. La composition et le procédé permettent l'élimination d'une étape d'accélération conventionnellement requise, tout en donnant des résultats d'une qualité sensiblement supérieure spécialement avec des substrats ayant des trous traversants nécessitant un revêtement, tels que des plaques à circuits imprimés sur lesquelles doit être effectué un placage de cuivre.

Claims (13)

1. Composition pour activer un substrat destiné à une métallisation autocatalytique, sous la forme d'une solution aqueuse comprenant au moins un sel d'un métal précieux, qui est catalytique vis-à-vis de la réduction chimique de sels dissous du métal à déposer dans un bain de dépôt autocatalytique, au moins un sel à même de former un sol métallique protecteur dans l'eau, une source d'ions halogénure venant en excédant par rapport à tous ions halogénure pouvant être apportés par les sels de métaux précieux et les sels à même de former le sol métallique protecteur, et de 10 à 80 g/I d'au moins un acide organique, lequel est pratiquement soluble dans le bain de métallisation, choisi parmi les acides carboxyliques aliphatiques, les acides carboxyliques aromatiques, les acides aminés et leurs combinaisons.
2. Composition selon la revendication 1, dans laquelle le métal précieux est le palladium.
3. Composition selon la revendication 2, dans laquelle le sel de métal précieux est un halogénure de palladium.
4. Composition selon la revendication 2 ou la revendication 3, dans laquelle le sel à même de former un sol métallique protecteur est un sel stanneux.
5. Composition selon la revendication 4, dans laquelle ledit sel stanneux est un halogénure stanneux.
6. Composition selon la revendication 4 ou la revendication 5, qui comprend de l'eau, de 0,02 à 8 g par litre de palladium et de 1 à 300 g par litre de l'ion stanneux.
7. Composition selon la revendication 6, qui a une concentration en chlorure comprise entre 0,1 normal et la concentration à la saturation.
8. Composition selon la revendication 7, dans laquelle la concentration des chlorures est comprise entre 3,4 et 4,6 normal.
9. Composition selon la revendication 8, qui contient de 0,0398 à 0,1194 g par litre de palladium et de 2 à 6 g par litre de l'ion stanneux.
10. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'acide est l'acide citrique, l'acide tartrique ou une combinaison de ces acides.
11. Procédé pour activer un substrat destiné à une métallisation autocatalytique dans un bain de métallisation par dépôt autocatalytique contenant des ions réductibles du métal à déposer, procédé consistant à mettre en contact un substrat avec un bain d'activation aqueux comprenant au moins un sel d'un métal précieux à même de catalyser la réduction chimique des ions du métal à déposer, des sels à même de former un sol métallique protecteur dans l'eau, une source d'ions halogénure en excès par rapport aux ions halogénure fournis par les sels du métal précieux et les sels à même de former le sol métallique protecteur, et de 10 à 80 g par litre d'au moins un acide organique, soluble dans le bain de métallisation, choisi entre les acides carboxyliques aliphatiques, les acides carboxyliques aromatiques, les acides aminés et leurs mélanges.
12. Procédé pour métalliser un substrat non-conducteur, dasn lequel sont aménagés des trous, consistant à mettre en contact un substrat avec un bain d'activation aqueux comprenant au moins un sel d'un métal précieux à même de catalyser la réduction chimique des ions du métal à déposer, des sels à même de former un sol métallique protecteur dans l'eau, une source d'ions halogénure en excès par rapport aux ions halogénure fournis par les sels de métal précieux et les sels à même de former le sol métallique protecteur, et de 10 à 80 g par litre d'au moins un acide organique, soluble dans le bain de métallisation, choisi parmi les acides carboxyliques aliphatiques, les acides carboxyliques aromatiques, les acides aminés et leurs combinaison; et, sans soumettre le substrat à un traitement accélérateur, à mettre en contact le substrat avec un bain de métallisation par dépôt autocatalytique contenant des ions . réductibles du métal à déposer.
13. Procédé selon la revendication 12, dans lequel le métal déposé est le nickel ou le cuivre.
EP19830901290 1982-05-26 1983-03-02 Solutions catalytiques permettant d'activer des substrats non conducteurs et procede de placage sans passage de courant electrique Expired EP0109402B1 (fr)

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JP4069248B2 (ja) * 2002-12-09 2008-04-02 大阪市 無電解めっき用触媒組成物
CN104593751B (zh) * 2014-12-27 2017-10-17 广东致卓环保科技有限公司 铜表面化学镀镍用超低浓度离子钯活化液及工艺
KR101681116B1 (ko) * 2016-05-26 2016-12-09 (주)오알켐 인쇄 회로 기판의 스루홀을 무전해 동 도금하는 방법 및 그 방법에 사용되는 촉매 용액을 제조하는 방법

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Also Published As

Publication number Publication date
JPH0239594B2 (fr) 1990-09-06
DE3376852D1 (en) 1988-07-07
EP0109402A1 (fr) 1984-05-30
CA1199754A (fr) 1986-01-28
EP0109402A4 (fr) 1984-10-29
WO1983004268A1 (fr) 1983-12-08
JPS59500870A (ja) 1984-05-17

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