EP0317092A1 - Catalyseur pour dépôt chimique - Google Patents

Catalyseur pour dépôt chimique Download PDF

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Publication number
EP0317092A1
EP0317092A1 EP88310037A EP88310037A EP0317092A1 EP 0317092 A1 EP0317092 A1 EP 0317092A1 EP 88310037 A EP88310037 A EP 88310037A EP 88310037 A EP88310037 A EP 88310037A EP 0317092 A1 EP0317092 A1 EP 0317092A1
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Prior art keywords
palladium
substrate
solution
nitrogen
compound
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EP88310037A
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German (de)
English (en)
Inventor
Jeffrey Darken
Janet Mary Moxley
Keith Richard Zone
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OMI International Corp
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OMI International 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
    • C23C18/18—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

  • This invention relates to palladium complexes suitable for catalysing the deposition of a metal from a solution of that metal onto a substrate, for example in an electroless plating process, and to a composition and a process for rendering the substrate catalytic.
  • the invention may find particular use where copper is to be deposited on an at least partially conductive substrate (e.g. on a circuit board) as a thin layer before more copper is deposited by an electroless or electroplating process, although the invention is not limited to this use.
  • the substrate surfaces need to be rendered catalytic or "catalysed", that is coated with a thin layer of a metal which will initiate electroless deposition when bought into contact with the electroless plating solution.
  • catalytic metal for this purpose is palladium.
  • US-A-3011920 and US-A-3672923 describe aqueous palladium catalysts produced by reaction of palladium and tin salts in acidic chloride media.
  • This type of catalyst may contain elemental palladium and a thin catalytic deposit of palladium may be produced on a substrate by the single step of immersion of the substrate in the catalyst.
  • This type of catalyst is therefore termed a "one step" catalyst.
  • the tin-palladium catalyst is widely used but suffers from disadvantages which include:-
  • the solution containing palladium may be referred to as the "sensitiser” whilst the solution containing the reducing agent may be referred to as the "reducer”.
  • the order of process steps may be either sensitiser followed by reducer (which is the most common), or vice versa.
  • DE-A-1621207 describes such a two step process.
  • the sensitiser contains palladium in its +2 valency state complexed with organic 3 valent nitrogen compounds. There is a considerable molar excess of nitrogen compound as compared to palladium.
  • EP-A-0167326 describes a two step catalysing system in which the sensitiser comprises a palladium compound dissolved in an amide, typically a 1% or 2% solution. In such a solution the amide is necessarily in a high molar excess. When using formamide for example, a 2% solution of palladium chloride has a 250 molar excess of formamide.
  • GB-A-1394164 and GB-A-1394165 disclose a process for activating a surface of a non-conductor for chemical metallisation using a solution containing a complex of the formula: M -(L) X - A where M can be palladium, L is a nitrogen-containing radical and A is an inorganic or organic acid radical.
  • X is an integer of at least one, preferably 2, 3 or 4.
  • Palladium complexes that are exemplified include dichloro-2,2′- dipyridyl palladium (II) and dichlorobis (2-aminopyridine) palladium (II).
  • These complexes are prepared by reacting the metal salt with a large excess of nitrogen-containing compound (molar ratios of nitrogen containing compound: palladium exceed 4.2:1) at low pH and have ligand:metal ratios of at least 1:1.
  • the solutions may be, or can adjusted to be, at pH 7.0. At higher pH's with less nitrogen-containing compound present, it is expected that the palladium would precipitate as PdO.nH2O (see "Advanced Inorganic Chemistry", Cotton and Wilkinson, 4th Edtn. p.905).
  • Some complexes are capable of being used as metal (eg. palladium) sensitisers which are water soluble under alkaline conditions, stable and very active and that the useful complexes contain nitrogen compounds or ligands in a low molar ratio to palladium.
  • metal eg. palladium
  • the pH is 7, 9 or even 12 and above.
  • the ratio X/Y may range from 1 to 20, but it is preferred that X/Y ranges from 1 to 5, and it has been found that best results can be obtained with the X/Y ratio from 1 to 2.
  • the palladium will generally be in its +2 oxidation state.
  • the nitrogen-containing ligand is urea, a mono-, di-, tri- or tetra- C1-C6 alkyl N-substituted urea, a C2-C7 acyl amide, a C1-C6 alkyl (mono- or di-) substituted C2-C7 acyl amide, a C1-C6 alkyl cyanide, a compound where the nitrogen atom forms part of an aromatic (such as pyridine or quinoline) ring optionally substituted with one or more amino, C1-C6 alkyl, hydroxy or other substituents, an amino acid, such as an alpha-amino acid, sulphamic acid or a nitrite or cyanate ion.
  • an amino acid such as an alpha-amino acid, sulphamic acid or a nitrite or cyanate ion.
  • the palladium compound is preferably a salt.
  • the salt may be a halide such as a chloride, bromide or iodide, or any other suitable salt such as nitrate.
  • alpha amino acids examples include: alanine, valine, leucine, isoleucine, proline, phenylalanine, tryptophan, methionine, glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine and histidine. It is to be understood that weak acids such as amino acids may exist as salts. The exact nature of the species present will depend on the pH.
  • suitable nitrogen-containing ligands include polymeric nitrogen-containing compounds including polyvinylpyrrolidinone (PVP) , polyacrylamide and polymers of urea (optionally substituted as before) with epichlorohydrin.
  • PVP polyvinylpyrrolidinone
  • polyacrylamide polymers of urea (optionally substituted as before) with epichlorohydrin.
  • the term "polymer” includes homopolymers and copolymers. Polymers of (optionally substituted) urea and epichlorohydrin may be prepared by reacting the urea and epichlorohydrin together (for example in equimolar proportions or with a molar excess of epichlorohydrin) under alkaline conditions.
  • Other suitable polymeric nitrogen-containing compounds include the the reaction products of epichlorohydrin and other amine monomers such as imidazole.
  • the nitrogen-containing ligand is glycine, dimethylamine, acetamide, formamide, N,N-­ dimethylformamide, acetonitrile, 2-hydroxypyridine, 2-­aminopyridine, 2-methylpyridine, pyridine or nitrite.
  • the most preferred nitrogen-containing ligands are urea and mono-, di-, tri- and tetra-N-(C1-C4)alkyl substituted ureas.
  • palladium chloride dissolved in hydrochloric acid.
  • Such a solution contains the palladium in the form of a square planar ion PdCl42 ⁇ (tetrachloropalladate). If a solution of tetrachloropalladate is made alkaline, palladium is precipitated as a hydrous oxide PdO.nH2O. If the procedure is repeated in the presence of an excess of amine a complex Pd(amine)2Cl2 is formed (see Advanced Inorganic Chemistry, Cotton and Wilkinson, 4th Edition, pages 905 and 911).
  • Nitrogen ligands that behave in a similar manner to urea include C1-C6 alkyl N-substituted ureas, C2-C7 acyl amides, a C1-C6 alkyl (mono- or di-) substituted C2-C7 acyl amides, C1-C6 alkyl cyanides, compounds where nitrogen is part of an aromatic (eg C6 or C10) ring optionally substituted with one or more amino, C1-­C6 alkyl hydroxy or other substitutents, amino acids such as glycine, sulphamic acid and nitrite.
  • the common themes that seem to be present amongst the (generally three valent) nitrogen ligands that are most effective are:-
  • Pi-bonded nitrogen-containing ligands may allow pi back-bonding to occur and thus to stabilise the palladium complexes.
  • Complexes in accordance with the first aspect are therefore generally substantially free of complexes in which the ratio of palladium atoms to nitrogen-­containing ligand X/Y ⁇ 1, and/or containing only one palladium atom.
  • substantially free is meant being in association with less than 50%, 40%, 30%, 20%, 10% or even 5% by weight of the single palladium atom containing complexes.
  • Palladium compounds such as palladium halides and nitrogen-containing ligand-forming species are available commercially or may be synthesised appropriately.
  • a source of palladium can be a palladium salt e.g. palladous chloride or nitrate.
  • the palladium salt may be dissolved in a small quantity of hydrochloric, hydrobromic or hydroiodic acid and then diluted with water. To this dilute solution, which may contain up to 5 gram/litre of palladium, can then be added a quantity of a nitrogen-containing ligand-forming species up to 4 x the molar quantity of palladium.
  • the palladium salt may be in solution free of halide.
  • the solution can be stirred and gradually made alkaline, for example by additions of an alkali metal hydroxide such as sodium or potassium hydroxide, or a quaternary ammonium hydroxide N+R1R2R3R4 (where R1 to R4 are all alkyl eg. C1-C6 alkyl or aryl groups).
  • an alkali metal hydroxide such as sodium or potassium hydroxide
  • a quaternary ammonium hydroxide N+R1R2R3R4 where R1 to R4 are all alkyl eg. C1-C6 alkyl or aryl groups.
  • An alternative and preferred method of producing a palladium complex is to predissolve a palladium source, generally under acid conditions, add to this a nitrogen-containing ligand-forming species and then add this mixture with stirring to a dilute alkali hydroxide solution.
  • This procedure generally produces a yellow solution which is believed to contain the palladite (PdO 2 2 ⁇ ) anion. Heating this solution, for example at 60°C to 80°C for l to 3 hours results in the development of the red-orange colour and generates the complex in solution. (It is not known whether this is a true solution or a fine colloid.)
  • the nitrogen-containing ligand-forming species can be added at any time prior to, or less preferably during, early stages of heating.
  • compositions according to a third aspect of the present invention are usually aqueous and may be prepared by admixing a complex in accordance with the first aspect or an aqueous solution of such a complex, with an aqueous pH adjusting solution such as aqueous alkali.
  • composition may contain very low concentrations of palladium, nitrogen-containing ligands and hydroxide it may be beneficial to incorporate a buffer.
  • the buffer may be incorporated into either a concentrate, a working solution or both in order to stabilise the pH when in use.
  • Suitable buffers can be selected dependent on the pH desired but may comprise carbonate, phosphate, borate or phthalate ions.
  • the buffer may be at a concentration from 0.1 g/l to saturation.
  • the buffer is provided at a concentration of 1.0 to 50 g/l and more preferably at a concentration of 5 to 10 g/l.
  • a chelating agent may prevent the precipitation of insoluble metal hydroxides should the sensitiser become contaminated with metals such as calcium, magnesium, manganese or copper.
  • Suitable chelating agents include EDTA, gluconates, glucoheptonates and the like.
  • the chelating agent is preferebly provided at a concentration of from 0.1 to 50 g/l, more preferably at about 5 g/l.
  • the pH of the composition is usually alkaline, ie above 7.
  • the final pH should be above 10 to prevent immersion palladium deposits occuring on the copper surface. If, during the procedure a precipitate is formed, particularly a dark red or orange precipitate, then this can be avoided by either reducing the palladium concentration, or reducing the molar ratio of nitrogen containing compound to palladium, by adding the nitrogen containing compound concurrently with the hydroxide addition, by reducing the initial hydroxide concentration or by more rapid stirring during the mixing of the ingredients.
  • the procedures described can be used to prepare working solutions of the palladium complex in the concentration range of from 1.0 to 0.001g/l, or to prepare more concentrated solutions which may be diluted prior to use.
  • the palladium concentration in the working composition is from 0.02 g/l to 0.3 g/l, or more preferably 0.05 g/l to 0.15 g/l.
  • a method of rendering a substrate catalytic to the electroless deposition of a metal comprising contacting at least part of a surface of the substrate with a complex or composition in accordance with the first or third aspects of the invention.
  • the surface will preferably previously have been conditioned, that is to say contacted with a cationic wetting agent such as a quaternary ammonium wetting agent.
  • the purpose of the quaternary wetting agent is to make the surface(s) of the laminate receptive to a catalyst which, in turn, serves the purpose of rendering the surface(s) catalytic to the deposit of copper.
  • the quaternary wetting agent may be a quaternary ammonium wetting agent of general formula (I): wherein each of R1, R2, R3 and R4 independently represents a C1 to C20, preferably C1-8, alkyl group, a C6 or C10 aryl or a C7 to C30 arylalkyl or alkylaryl group, each optionally substituted with a group -OR5, -NHR5R6, where each of R5 and R6 independently represents a hydrogen atom or a C1 to C20, preferably C1 ⁇ 8, alkyl group; and X n- represents a compatible anion of acidity n, where n is an integer, generally 1 to 4 but preferably 1.
  • substituents on the quaternary ammonium cation will in general be selected so that the cation is sufficiently soluble in and otherwise compatible with the solution.
  • At least two of the substituents R1, R2, R3 and R4 will preferably represent a C1 to C4 alkyl or substituted alkyl group, especially methyl, ethyl or propyl. But it is also preferred that at least one of the substituents R1, R2, R3 and R4 be substituted as described, and that at least one of R5 and R6 represents a C6 to C20 alkyl group such as stearyl.
  • Preferred cations include stearylamidopropyldimethyl-­2-hydroxyethylammonium and oxyethylalkylammonium.
  • Stearylamidopropyldimethyl-2-hydroxyethylammonium phosphate is sold by Ciba-Geigy under the trade mark CYASTAT-SP.
  • the cation may alternatively be a C1-C20 alkyl pyridinium moiety, such as cetyl pyridinium.
  • the cation may alternatively be an imidazolinium cation or be a recurring part of a polymer such as an imidazolinium polymer species.
  • the anion will generally be selected so that it too is sufficiently soluble in and otherwise compatible with the solution. It may be a halide ion such as chloride or bromide, or a nitrate, phosphate, sulphate, hydrogen phosphate or dihydrogen phosphate ion. Preferred anions are nitrate and dihydrogen phosphate.
  • the wetting agent may be present in an amount of 0.1 to 10 g/l, typically 0.5 to 5 g/l, for example 1 to 3 g/l.
  • the aqueous conditioning solution will also preferably contain a complexing agent, which functions to clean the surface by removing oxides.
  • the complexing agent will generally be an amine or amine derivative. Suitable complexing agents include soluble amines, alkanolamines (especially C1-C6 alkanolamines such as monoethanolamine, diethanolamine, triethanolamine), amine carboxylic acids, hydroxycarboxylic acids and amine phosphoric acids. Improved results may be obtainable by using such complexing agents, of which soluble amine carboxylic acids are preferred. Tetraethylene pentamine may also be used. In general it should be noted that the complexing agent should be non-volatile if the composition containing them is to be used above room temperature.
  • the complexing agent may be present in an amount of 1 to 50 g/l, typically 5 to 30 g/l, for example 10 to 20 g/l.
  • nonionic surfactant Another preferred component of the conditioning solution is a nonionic surfactant.
  • suitable nonionic surfactants are ethoxylated linear alkyl alcohols, such as an ethoxylated nonyl phenol containing for example about 12 moles of ethylene oxide.
  • the nonionic surfactant acts as a wetting agent generally to provide a water-­break free surface.
  • the nonionic surfactant may be present in an amount of 0.1 to 20 g/l, typically 0.5 to 5 g/l, for example 1 to 3 g/l.
  • the pH of the conditioning solution is not believed to be critical but may range from 1 to 14; preferably the pH is below 7 as better results appear to be obtained in acid conditions.
  • a method of depositing a metal onto a substrate comprising rendering the substrate (or part of it) catalytic to the electroless deposition of a metal by a method in accordance with the fourth aspect and subsequently depositing metal on the so-catalysed substrate by an electroless deposition process.
  • Methods in accordance with the fourth and fifth aspects find particular application in the manufacture of printed circuit boards for the electronics industry.
  • the fourth and fifth aspects of the invention are therefore embodied in a process for the electroless deposition of a metal (such as copper, nickel, cobalt or gold) onto a substrate, such as treating a board in the manufacture of a printed circuit board, the process comprising the steps of:
  • step (a) comprises only cleaning, conditioning may be left until after step (b) and before step (c).
  • a "pre-dip" may be included directly before step (c) in order to prevent the sensitiser becoming unduly contaminated with, for example, hard water salts.
  • the pre-dip which may be acid or alkali, may contain a metal ion complex or may simply be distilled water.
  • the reducing solution contains at least one compound capable of reducing catalytic metal complexes remaining on the surface of the substrate to elemental metal.
  • the reducing agent is a dimethylamine-borane complex, an alkali metal borohydride (eg. sodium borohydride) or hydrazine, and it is preferred that the reducing agent is present in an amount from 0.1 to 100 g/l, or more preferably at about 10 g/l.
  • the reducing agent composition may be aqueous and alkaline; it may contain sodium hydroxide, e.g. in an amount of about 10 g/l.
  • a typical treatment sequence for the electroless plating of a totally non-conductive substrate (which may require prior etching to ensure adhesion of the plated deposit) or a mixed substrate such as a drilled copper clad printed circuit board (which may be a multilayer printed circuit board and/or which may have been pre-treated in a hole resin desmearing or etchback process with or without glass etching) is as follows:- FUNCTION TIME EXAMPLE 1. Clean/Condition 3-5 mins CIRCUITPREP 1017 Water Rinse 1 min - 2. Copper Etch (only for copper clad substrates) 1.3 mins 100g/l sodium persulphate + 20 ml/l sulphuric acid Water Rinse 1 min - 3.
  • the performance of the sensitiser can be determined by visually observing the coverage of the electroless deposit. On most substrates any areas of misplating can be readily observed.
  • the "backlight test” is used to determine the degree of coverage achieved. After plating, a few chosen holes are cut through longitudinally so that about 50% of the hole wall remains. The sample is then arranged on a microscope so that the hole wall can be observed at a right angle from above whilst a powerful light is placed directly below the sample.
  • the non-conductive substrate, from which a circuit board is normally fabricated, is generally a very good light transmitter. Any discontinuities in the copper deposit on the hole wall will allow light transmission and will show up as bright areas. In this way areas of misplating from tiny pinholes to large voids may be seen.
  • results of the backlight test will reflect the performance of the catalytic treatment if other parameters are maintained unchanged.
  • the results of backlight tests can be graded as follows:- A+ perfect A less than 3 pinholes excellent B less than 6 pinholes acceptable C less than 5% voiding unacceptable D less than 15% voiding unacceptable E more than 15% voiding unacceptable The results of at least 5 holes are averaged in order to reach an overall rating ie. A+ or A/B etc.
  • sensitiser compositions according to the invention can give backlight tests graded A+ at palladium concentrations as low as 20mg/l. This is remarkable in comparison to the performance of the tin-palladium system which operates at palladium concentrations within the much higher range of 100-­300mg/l. The difference between the two systems is even more evident when desmeared or etchback treated circuit boards are processed since these are more difficult to plate completely void free in an electroless copper process.
  • Palladous chloride 1.67g (0.0095 mole) was dissolved in 30 ml of H2O containing 6 ml of concentrated hydrochloric acid by heating to 50°C and stirring until a clear yellow brown solution was obtained. This solution was diluted to 1 litre and then urea 0.6g (0.01 mole) was added and dissolved. The solution was made alkaline by the gradual addition of solid sodium hydroxide. As the pH reached values above 4.5 the solution became very dark red in colour. The sodium hydroxide addition was stopped when the pH reached 12 by which time the solution, which remained clear, had attained an orange-red colouration.
  • this solution which contained 1g/l of palladium, was diluted to 500 ml with distilled water so as to contain 100 mg/l of palladium.
  • the molar ratio of palladium to urea in the complex was 1:1.
  • This solution was used as the sensitiser in the following sequence to plate a 0.5 dm2 piece of double sided copper clad epoxy glass laminate with previously drilled holes of 1 mm diameter with an electroless copper deposit.
  • Example 1 The procedure of Example 1 was followed execpt that the addition of urea was omitted. As the pH increased the palladium precipitated as a light brown solid. The catalytic activity of the supernatant liquid was not investigated.
  • Palladous chloride 0.835 g (0.0047 mole) was dissolved in 10 ml of water containing 2 ml of concentrated hydrochloric acid by heating to 50°C. This solution was diluted to 500 ml and 0.15 g urea (0.0025 mole) was added and dissolved.
  • the pH adjustment, dilution for plating test and plating test procedure were as in Example 1.
  • the copper coverage in the holes was graded A+/A.
  • Palladous chloride 0.167 g (0.00095 mole) was dissolved in 10 ml of water containing 2 ml of concentrated hydrochloric acid. This solution was made up to 1 litre and 0.045 g of dimethylamine (0.00098 mole) added. The pH was increased to 11.5 g by gradual addition of solid sodium hydroxide. This solution which contained 100 mg/litre of palladium was tested as a sensitiser using the procedure given in Example 1. In the backlight test, the copper coverage in the holes was graded A+.
  • Example 3 The procedure for Example 3 was followed except that acetamide 0.3 g (0.005 mole) was used in place of urea. In the backlight test, the copper coverage in the holes was graded A+.
  • Palladous chloride 10 g (0.057 mole) was dissolved in 25 ml of concentrated hydrochloric acid diluted to 100 ml with distilled water. 4.17 ml (0.0024 mole) of the above solution was diluted to 250 ml to give a 1g/litre palladium solution. Glycine, 0.188 g (0.0025 mole) was added with stirring. The pH was increased to 12 by the gradual addition of solid sodium hydroxide. The solution produced was dark orange. The solution dilution and plating procedure were as described in Example 1. In the backlight test, the copper coverage in the holes was graded A+.
  • Example 6 The procedure for Example 6 was followed except that acetonitrile 0.102 g (0.0025 mole) was used instead of glycine. In the backlight test, the copper coverage in the holes was graded A/B.
  • Palladous bromide 0.625 g (0.0024 mole) was dissolved in 10 ml of water containing 1.5 ml of 40% hydrochloric acid. The solution was heated to 60 °C until all the palladous bromide had dissolved. The solution was then diluted to 250 ml. Urea 0.15 g (0.0025 mole) was added and dissolved with stirring. Solid sodium hydroxide was added slowly until the pH reached 12. The solution was orange/red in colour. This solution which contained 1g/l palladium was diluted and tested as in Example 1. In the backlight test, the copper coverage in the holes was graded A.
  • Palladous chloride 0.417 g (0.0024 mole) was dissolved in 30 ml of water containing 2 ml of concentrated hydrochloric acid by heating to 50°C. This solution was diluted to 250 ml and sulphamic acid 25mg, (0.00026 mole) added and dissolved. The molar ratio of palladous chloride to sulphamic acid was thus 9.2:1. Solid sodium hydroxide was added gradually and dissolved until the pH reached 12. The solution produced was dark red/orange. This solution which contained 1g/l palladium was diluted and tested as in Example 1. In the backlight test the copper coverage in the hole was graded A+.
  • Example 8 The procedure of Example 8 was followed except that sulphamic acid 12.5mg (0.00013 mole) was used in place of urea. The molar ratio of palladous bromide to sulphamic acid was thus 18.5:1. In the backlight test the copper coverage in the holes was graded A+/A.
  • Palladous chloride 0.835 g (0.0047 mole) was dissolved in 10 ml of water containing 2 ml of concentrated hydrochloric acid and diluted to 250 ml. Urea, 0.3 g (0.0050 mole) was added and dissolved in this solution. Solid sodium hydroxide was then added gradually and dissolved until the solution pH was in the range 6.0-­6.5. The solution, which had become very dark red in colour was then added dropwise with stirring to 250ml of a solution containing 100g/litre boric acid and 100g/litre sodium hydroxide. The final volume was 500 ml of a red/orange solution containing 1g/litre palladium.
  • Example 11 This solution was diluted to 100 mg/litre palladium (Example 11) and also to 20 mg/litre palladium (Example 12) and these dilute solutions were tested as sensitisers according to the procedure of Example 1.
  • the copper coverage in the holes in the backlight test was graded as follows: Example 11: A at 100 mg/litre palladium
  • Example 12 A/B at 20 mg/litre palladium
  • Palladous chloride 0.835 g (0.0047 mole) was dissolved in 10 ml of water containing 2 ml of concentrated hydrochloric acid and diluted to 250 ml.
  • Urea 0.3 g (0.0050 mole) was added and dissolved in this solution, which was added dropwise to 250 ml of a solution containing 100 g/litre boric acid and 100 g/litre sodium hydroxide.
  • the final volume was 500 ml of a light yellow solution.
  • a sample of this solution was diluted to give a palladium concentration of 100mg/litre. After 1 day standing, the light yellow solution had begun to turn red-orange.
  • Example 3 A sample of the solution produced in Example 3 was taken and diluted to 100 mg/litre palladium concentration. This solution was tested as a sensitiser using the procedure of Example 1 except for the following:
  • Palladous chloride 0.417g (0.0024 mole) was dissolved in 10 ml of water containing 2 ml of concentrated hydrochloric acid and diluted to 250 ml.
  • the solution pH was adjusted to 2.5 with the addition of solid sodium hydroxide.
  • Sodium nitrite 0.1g, (0.00126 mole) was added and dissolved and then the solution pH increased to 12 with solid sodium hydroxide.
  • the solution became dark red/orange in colour.
  • a sample of this solution which contained 1g/litre of palladium was diluted to 100 mg/litre palladium and tested as a sensitiser following the procedure of Example 1. In the backlight test the copper coverage in the holes was graded A+.
  • the solution from Part A (which contained 1 g/l palladium) was diluted with water to a palladium concentration of 100 mg/l and used as a sensitiser in the sequence described in Example 1, except that the substrate used was bare epoxy glass (after stripping the copper cladding) and also except that the following composition was used (at 40°C) in place of the CIRCUITPREP 5540 composition: 12 g/l CuSO4.5H2O 10 g/l NaOH 20 g/l Ethylenediamine tetra-2-hydroxy propyl 3 g/l formaldehyde 5 mg/l 2,2′-bipyridyl
  • a drilled copper clad laminate panel was then processed through the electroless plating line.
  • the panel was conditioned first.
  • the copper coverage in the holes in the backlight test was graded A.
  • Example 3 A sample of the sensitiser produced in Example 3 was taken and diluted to 150mg/l Pd concentration. 5g/l sodium hydroxide was added to the resulting solution. The solution was tested as a sensitiser using the procedure of Example 1 except for the following.

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EP88310037A 1987-10-27 1988-10-26 Catalyseur pour dépôt chimique Withdrawn EP0317092A1 (fr)

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GB8725148 1987-10-27
GB878725148A GB8725148D0 (en) 1987-10-27 1987-10-27 Catalyst

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0367885A1 (fr) * 1988-11-08 1990-05-16 Schering Aktiengesellschaft Composition de conditionnement pour circuits imprimés
DE3938710A1 (de) * 1989-11-17 1991-05-23 Schering Ag Komplexverbindungen mit oligomerem bis polymerem charakter
DE4130135A1 (de) * 1991-09-07 1993-03-11 Schering Ag Verfahren zur herstellung von mikroelektrodenarrays, verwendung von edelmetallhaltigen aktivierungsloesungen zur herstellung von mikroelektrodenarrays und die verwendung von chemischen metallabscheidungsbaedern zur herstellung von mikroelektrodenarrays
US5503877A (en) * 1989-11-17 1996-04-02 Atotech Deutschalnd Gmbh Complex oligomeric or polymeric compounds for the generation of metal seeds on a substrate
WO2002092877A3 (fr) * 2001-05-11 2003-12-31 Ebara Corp Solution de traitement d'application de catalyseur et procede de depot autocatalytique
EP2845922A1 (fr) * 2013-09-04 2015-03-11 Rohm and Haas Electronic Materials LLC Métallisation non galvanique de diélectriques avec catalyseurs d alcaline stable contenant des dérivés de pyrimidine
EP2845923A1 (fr) * 2013-09-04 2015-03-11 Rohm and Haas Electronic Materials LLC Métallisation non galvanique de diélectriques avec catalyseurs d alcaline stable contenant des dérivés de pyrazine
US9918389B2 (en) 2013-09-04 2018-03-13 Rohm And Haas Electronic Materials Llc Electroless metallization of dielectrics with alkaline stable pyrazine derivative containing catalysts

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JP2649750B2 (ja) * 1991-06-13 1997-09-03 石原薬品 株式会社 銅系素材上への選択的無電解めっき方法
JP4669982B2 (ja) * 2001-09-12 2011-04-13 奥野製薬工業株式会社 無電解めっき用触媒液
JP4640583B2 (ja) * 2005-03-11 2011-03-02 日立化成工業株式会社 無電解めっき用前処理液、およびこれを用いた無電解めっき方法
JP4640586B2 (ja) * 2005-04-06 2011-03-02 日立化成工業株式会社 無電解めっき用前処理液、およびこれを用いた無電解めっき方法
JP5327494B2 (ja) * 2005-11-16 2013-10-30 日立化成株式会社 無電解めっき用触媒濃縮液の製造方法とそれを用いためっき触媒付与方法
US8354014B2 (en) 2005-12-06 2013-01-15 Ebara-Udylite Co., Ltd. Palladium complex and catalyst-imparting treatment solution using the same
JP5418336B2 (ja) * 2010-03-18 2014-02-19 コニカミノルタ株式会社 金属パターン形成方法及びそれを用いて形成された金属パターン
JP5375725B2 (ja) * 2010-04-12 2013-12-25 コニカミノルタ株式会社 金属パターン製造方法及び金属パターン
US8591636B2 (en) * 2010-12-14 2013-11-26 Rohm And Haas Electronics Materials Llc Plating catalyst and method
JP6272673B2 (ja) * 2013-10-30 2018-01-31 ローム・アンド・ハース電子材料株式会社 無電解めっき用触媒液

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1481700A (fr) * 1965-06-01 1967-05-19 Photocircuits Corp Perfectionnements apportés aux procédés de dépôt non galvanique de métaux
FR2132172A1 (fr) * 1971-03-30 1972-11-17 Schering Ag
EP0167326A2 (fr) * 1984-06-29 1986-01-08 Hitachi Chemical Co., Ltd. Procédé de sensibilisation d'un substrat pour le dépôt chimique d'un métal et solution utilisée à cet effet

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1481700A (fr) * 1965-06-01 1967-05-19 Photocircuits Corp Perfectionnements apportés aux procédés de dépôt non galvanique de métaux
FR2132172A1 (fr) * 1971-03-30 1972-11-17 Schering Ag
EP0167326A2 (fr) * 1984-06-29 1986-01-08 Hitachi Chemical Co., Ltd. Procédé de sensibilisation d'un substrat pour le dépôt chimique d'un métal et solution utilisée à cet effet

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
METALLOBERFLÄCHE, vol. 31, no. 11, 1977, page 521; J. ANSCHÜTZ: "Aktivierung von elektrischen Nichtleitern mit palladiumhaltigen Katalysator-Lösungen" *
PATENT ABSTRACTS OF JAPAN, vol. 9, no. 166 (C-290)[1889], 11th July 1985; & JP-A-60 36 672 (HITACHI KASEI KOGYO K.K.) 25-02-1985 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0367885A1 (fr) * 1988-11-08 1990-05-16 Schering Aktiengesellschaft Composition de conditionnement pour circuits imprimés
DE3938710A1 (de) * 1989-11-17 1991-05-23 Schering Ag Komplexverbindungen mit oligomerem bis polymerem charakter
WO1991007522A1 (fr) * 1989-11-17 1991-05-30 Schering Aktiengesellschaft Composes complexes de caractere oligomere a polymere
US5503877A (en) * 1989-11-17 1996-04-02 Atotech Deutschalnd Gmbh Complex oligomeric or polymeric compounds for the generation of metal seeds on a substrate
DE4130135A1 (de) * 1991-09-07 1993-03-11 Schering Ag Verfahren zur herstellung von mikroelektrodenarrays, verwendung von edelmetallhaltigen aktivierungsloesungen zur herstellung von mikroelektrodenarrays und die verwendung von chemischen metallabscheidungsbaedern zur herstellung von mikroelektrodenarrays
DE4130135C2 (de) * 1991-09-07 1999-07-22 Atotech Deutschland Gmbh Verfahren zur Herstellung von Formkörpern für Mikroelektrodenarrays
WO2002092877A3 (fr) * 2001-05-11 2003-12-31 Ebara Corp Solution de traitement d'application de catalyseur et procede de depot autocatalytique
EP2845922A1 (fr) * 2013-09-04 2015-03-11 Rohm and Haas Electronic Materials LLC Métallisation non galvanique de diélectriques avec catalyseurs d alcaline stable contenant des dérivés de pyrimidine
EP2845923A1 (fr) * 2013-09-04 2015-03-11 Rohm and Haas Electronic Materials LLC Métallisation non galvanique de diélectriques avec catalyseurs d alcaline stable contenant des dérivés de pyrazine
CN104561947A (zh) * 2013-09-04 2015-04-29 罗门哈斯电子材料有限公司 用包含碱性稳定吡嗪衍生物的催化剂化学镀金属化电介质
CN104561947B (zh) * 2013-09-04 2017-12-19 罗门哈斯电子材料有限公司 用包含碱性稳定吡嗪衍生物的催化剂化学镀金属化电介质
US9918389B2 (en) 2013-09-04 2018-03-13 Rohm And Haas Electronic Materials Llc Electroless metallization of dielectrics with alkaline stable pyrazine derivative containing catalysts
CN104513974B (zh) * 2013-09-04 2018-09-21 罗门哈斯电子材料有限公司 利用含碱稳定嘧啶衍生物的催化剂的化学镀金属化电介质

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