Process for electroless plating and a solution used for the same

Abstract

A process of pretreatment for selective application of electroless metallization to a surface of a non-conductive material and a solution useful for the pretreatment are provided. The process achieves good coverage in areas to be plated on the surface of non-conductive materials without skip plating or over plating.

Claims

1. A catalyst solution consisting of a) one source of catalytic palladium ions chosen from palladium chloride, palladium sulfate, palladium acetate, palladium bromide and palladium nitrate to generate the catalytic palladium ions in amounts of 1 to 50 ppm in the catalyst solution; b) an acid having at least one sulfonate group selected from the group consisting of methane sulfonic acid and sulfuric acid; c) one source of chloride ions chosen from sodium chloride, hydrochloric acid and potassium chloride to provide the chloride ions in the catalyst solution; and d) water; wherein a weight ratio of the catalytic palladium ions to the chloride ions in the catalyst solution is between 1 to 10 and 1 to 1000.

2. The catalyst solution of claim 1, wherein the weight ratio of the catalytic palladium ions to the chloride ions in the catalyst solution is between 1 to 20 and 1 to 500.

3. The catalyst solution of claim 1, wherein the weight ratio of the catalytic palladium ions to the chloride ions in the catalyst solution is between 1 to 50 and 1 to 200.

4. The catalyst solution of claim 1, wherein the catalytic palladium ions are in amounts of 5 to 25 ppm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a photograph of a molded resin sample with good coverage of deposited copper.

(2) FIG. 2 is a photograph of a molded resin sample with slight skip plating.

(3) FIG. 3 is a photograph of a molded resin sample with no plating.

DETAILED DESCRIPTION OF THE INVENTION

(4) As used throughout this specification, the abbreviations given below have the following meanings, unless the content clearly indicates otherwise: g=gram; mg=milligram; L=liter; m=meter; min.=minute; s=second; h.=hour; ppm=parts per million; g/L=grams per liter.

(5) As used throughout this specification, the word “deposition”, “plating” and “metallization” are used interchangeably. As used throughout this specification, the word “solution” and “bath” are used interchangeably. Unless the content clearly indicates otherwise, the solution and bath comprise water.

(6) The process of the present invention relates to selective metallization of a surface of a non-conductive material. In this embodiment, the word ‘selective metallization’ means metallization (plating) only in those areas intended to be plated on a surface of a material, with substantially no deposition in the areas other than the intended areas. When the deposition in the areas intended to be plated is not sufficient (skip plating), the required conductive performance cannot be obtained. When there is substantial deposition in areas not intended to be plated (over plating), the functionality of the circuit path structure is degraded, thus causing problems in the electronic circuit due to short circuiting. The process comprises four steps.

(7) The first step of the process is (a) preparing a surface of a non-conductive material by chemically or physically modifying the areas of the surface that are to be plated.

(8) The non-conductive material is preferably a thermoset or thermoplastic. Examples of plastics which could be used as the non-conductive material include polycarbonate (PC), polyethylene telephtalate (PET), polybutylene terephthalate (PBT), polyacrylate (PA), liquid crystal polymer (LCP), (poly phthalamide?) (PPA), and acrylonitrile butadiene styrene copolymer (ABS) and mixtures thereof. Preferred plastics are molded plastics produced using the thermoplastics described above.

(9) The non-conductive material optionally contains one or more inorganic fillers which are conventionally used, such as alumina, silicate, talc or derivatives thereof. The non-conductive material optionally contains one or more metal or metal compounds. Metal compounds include metal oxides, metal silicates, metal phosphates and metal chelates. The metal or metal compound is mixed with the non-conductive material, and a portion of those compounds emerge on the surface of the material after chemical or physical modification and become activated to behave as catalysts for the deposition of metals. Examples of metals include but are not limited to, precious metals such as palladium, transition metals such as copper, chromium, cobalt, iron, zinc and mixtures thereof. U.S. Pat. No. 7,060,421 discloses such materials.

(10) The material is modified chemically or physically in the areas to be plated. Examples of chemical modification of the surface of the non-conductive material include etching by alkaline or acid solutions. Examples of physical modification include treatment by a laser such as a Nd:YAG laser. The areas to be plated are selected based on the requirements to form conductive traces on the surface of the materials. The chemical or physical modification creates a microscopically rough surface, useful for anchoring the deposited metal layer. Such materials are commercially available, such as from LPKF Laser and Electronic AG, Germany.

(11) The second step of the process is (b) contacting the non-conductive material with a pretreatment solution comprising a conditioning agent and an alkaline material.

(12) The pretreatment solution is a composition which shows the property of selectively enhancing absorption of catalyst material on the laser treated surfaces. Preferred conditioning agents include anionic surfactants and organic acids. The preferred compositions of anionic surfactants for the invention include polyoxyethylene alkyl phenol phosphate and polyether phosphate. The examples of preferred compositions of organic acid are alkyl sulfonic acids or aromatic sulfonic acids such as phenol sulfonic acid. The concentration for the conditioning agent depends on the kind of composition, but when an anionic surfactant is used as the conditioning agent, the preferred concentration is normally between 1 to 50 g/L, and more preferably 2.5 to 15 g/L. When a sulfonic acid, such as an aromatic sulfonic acid is used as the conditioning agent, the preferred concentration is normally 1 to 50 g/L, and more preferably 2.5 to 25 g/L.

(13) The alkaline material is normally added as an alkali metal hydroxide. The concentration of alkali metal hydroxide in the pretreatment solution is normally, 1 to 200 g/L, and preferably, 10 to 90 g/L.

(14) The pretreatment solution optionally contains a poly hydroxyl compound. The preferable concentration of this component is normally 0 to 100 g/L, and preferably 10 to 50 g/L. The pH of the solution is normally more than 12, and preferably, more than 13.

(15) The method for contacting the material to be plated with the solution could be any kind of method, such as dipping or spraying. The conditions for contacting the material with the pretreatment solution are, for example, dipping the material in the solution at 40 to 90 degrees C. for 1 to 20 minutes. Preferably, the above step may be followed by a water rinse.

(16) The third step of the process is (c) contacting the non-conductive material with a catalyst solution comprising a catalytic metal ion, an acid having at least one sulfonate group, and chloride ion. The catalytic metal ion is preferably a precious metal ion such as palladium ion. Any kind of palladium ion source can be used for the solution as long as the palladium ion source generates palladium ion in the solution. Examples of palladium ion sources comprise palladium chloride, palladium sulfate, palladium acetate, palladium bromide and palladium nitrate.

(17) The acid having at least one sulfonate group comprises both organic acid and inorganic acid. Examples of organic acid include methane sulfonic acid, and examples of inorganic acid include sulfuric acid. Preferably the acid is sulfuric acid.

(18) Any kind of chloride ion source can be used for the solution as long as the chloride ion source provides chloride ions in the solution. Examples of chloride ion sources comprise sodium chloride, hydrochloric acid and potassium chloride. The preferred chloride ion source is sodium chloride.

(19) The preferred amounts of each ingredient in the solution is normally 1 to 50 ppm of catalytic metal ion, 50 to 150 g/L of sulfuric acid, and 0.1 to 10 g/L of chloride ion based on the weight of the solution. More preferably, the amount of each ingredient in the solution is 5 to 25 ppm of catalytic metal ion, 75 to 125 g/L of sulfuric acid, and 5 to 5.0 g/L of chloride ion based on the weight of the solution.

(20) The ratio of catalytic metal ion to chloride ion in the solution is preferably between 1 to 10 and 1 to 1000, more preferably between 1 to 20 and 1 to 500, and further more preferably between 1 to 50 and 1 to 200. If the ratio of chloride ion is over 1000, skip plating may be observed. If the ratio of chloride ion is under 10, overplating may be observed.

(21) Optionally, the solution of this invention may comprise one or more of a variety of additives used for pretreatment solutions for electroless plating, such as surfactants, complexing agents, pH adjusters, buffers, stabilizers, copper ions and accelerators. The pH of the solution is normally 0.2 to 2, preferably 0.2 to 1. Preferred surfactants used for this solution are cationic surfactants. The amount of surfactant depends on the kind of surfactant, but is normally 0.1 to 10 g/L based on the weight of the solution.

(22) The method for contacting the solution could be any kind of method, such as dipping or spraying. The conditions for contacting the material with the catalyst solution are, for example, dipping the material in the solution at 20 to 80 degrees C., preferably 50 to 70 degrees C. for 1 to 20 minutes, preferably 5 to 20 minutes. Preferably, the above step may be followed by a water rinse.

(23) The fourth step of the process is (d) electrolessly plating areas to be metalized on the surface of the non-conductive material. Electroless plating methods and compositions for plating copper are well known in the art. Conventional methods and electroless copper plating baths may be used. Examples of such copper baths include 1 to 5 g/L of copper ion, 10 to 50 g/L of complexing agent, 0.01 to 5 g/L of surfactant, 5 to 10 g/L of sodium hydroxide and 2 to 5 g/L of reducing agent. Conventional electroless copper baths may be used, such as CIRCUPOSIT™ 71 HS Electroless Copper, CIRCUPOSIT™ LDS 91 Electroless Copper available from Dow Electronic Materials.

(24) The conditions for electroless plating are, for example, dipping the material in the electroless copper plating bath at 20 to 70 degrees C., preferably 45 to 65 degrees C. for a time sufficient to deposit the required thickness of copper, for example 20 to 300 minutes. Preferably, the above step may be followed by one or more water rinses.

(25) The catalyst solution of this invention is useful as a pretreatment solution for selective electroless plating of a non-conductive material. The contents of the solution are same as the solution described in the third step. The weight ratio of catalytic metal ion to chloride ion in the solution is between 1 to 10 and 1 to 1000.

(26) The process of this invention enables the elimination of the electroless copper strike bath used in a conventional process. The process enables direct metallization only within the specific areas to be plated on the surface of non-conductive materials. The materials obtained by the process of the present invention are selectively metalized only within those areas modified chemically or physically, i.e. with good coverage and uniform thickness, without over plating or skip plating. In addition, the deposition rate is acceptable for industrial processing.

EXAMPLES

Example 1

(27) An LDS substrate sample made from a blend of PC and ABS (PC/ABS) resins was laser treated in those areas to be plated (LPKF Laser and Electronic AG). The substrate sample was dipped in a pretreatment solution containing 70 g/L NaOH and 5 g/L anionic surfactant (polyester phosphate, supplied by Dow Electronics Materials as TRITON™ QS-44 surfactant) for 5 minutes at 70 degrees C. The pH of the solution was approximately 14. After rinsing with deionized water, the substrate sample was dipped in a catalyst solution containing 18.4 mg/L palladium sulfate (9.5 ppm palladium ion), 60 mL/L 98% sulfuric acid and 1.7 g/L sodium chloride for 10 minutes at 69 degrees C. The substrate sample was then rinsed with deionized water, and electroles sly plated for 120 minutes at 56 degrees C. (CIRCUPOSIT™ 71 HS Electroless Copper, Dow Electronic Materials). The plated substrate sample was rinsed with water, and then rated by the standard described below. The thickness of the copper layer was 9 micrometers measured by X-ray Fluorescence (XRF) and rating of deposition quality was 5-5. FIG. 1 shows complete copper deposit on the laser treated surface.

(28) Rating

(29) The deposition of copper was observed using an optical microscope and rated from 1 to 5 both within the laser treated areas and the non-treated areas. The first digit indicated the performance within the laser treated areas, while the second digit indicated the performance in non-laser treated areas. In laser treated areas, “1” indicates there was no deposition and “5” indicates complete copper coverage with no skip plating. A rating of “3” indicates coverage of copper is not complete. Other rating numbers indicate behavior between these defined levels. In non-laser treated areas, “5” indicates there is no deposition on that area (no overplating) and “1” indicates a large amount of excess plating was observed (serious overplating). A rating of 5-5 indicates the best overall performance.

Example 2

(30) The procedure of Example 1 was repeated except that the pretreatment solution containing 70 g/L NaOH and 5 g/L anionic surfactant was replaced with a pretreatment solution containing 39 g/L of NaOH and 17 g/L phenolsulfonic acid, and the dipping time of the pretreatment solution was changed from 5 minutes to 10 minutes. The thickness of the copper layer was 8.4 micrometers and the rating of deposition quality was 4-5.

Example 3

(31) The procedure of Example 1 was repeated except that the pretreatment solution containing 70 g/L NaOH and 5 g/L anionic surfactant was replaced with a pretreatment solution containing 30 g/L of NaOH, 8.7 g/L phenolsulfonic acid and 36.8 g/L glycerol, and dipping time of the pretreatment solution was changed from 5 minutes to 10 minutes. The thickness of the copper layer was 8.8 micrometers and the rating of deposition quality was 4.5-5. FIG. 2 shows complete copper coverage on the flat laser treated surface, but with slight skip plating in the hole area.

(32) TABLE-US-00001 TABLE 1 Example 1 2 3 Pretreatment solution Polyester phosphate (g/L) 5 Phenolsulfonic acid (g/L) 17 8.7 Glycerol (g/L) 36.8 NaOH (g/L) 70 39 30 Dipping time of the pretreatment solution 5 10 10 Catalyst solution Palladium sulfate (mg/L) 18.4 18.4 18.4 Sulfuric acid (mL/L) 60 60 60 Sodium chloride (g/L) 1.7 1.7 1.7 Results Thickness (micron) 9 8.4 8.8 Rating 5-5 4-5 4.5-5

Comparative Example 1

(33) The procedure of Example 1 was repeated except that the pretreatment solution containing 70 g/L NaOH and 5 g/L anionic surfactant was replaced with a pretreatment solution containing 5 g/L of anionic surfactant. The thickness of the copper layer was 8.4 micrometers and the rating of deposition quality was 3-5.

Comparative Example 2

(34) The procedure of Example 1 was repeated except the catalyst solution containing 18.4 mg/L palladium sulfate, 60 mL/L 98% sulfuric acid and 1.7 g/L sodium chloride was replaced with a catalyst solution containing 18.4 mg/L palladium sulfate and 60 mL/L 98% sulfuric acid. The thickness of the copper layer was 3.0 micrometers and the rating of deposition quality was 1-5. FIG. 3 shows no plating on the laser treated surface.

(35) TABLE-US-00002 TABLE 2 Comparative Example 1 2 Pretreatment solution Polyester phosphate (g/L) 5 5 NaOH (g/L) 0 70 Catalyst solution Palladium sulfate (mg/L) 18.4 18.4 Sulfuric acid (mL/L) 60 60 Sodium chloride (g/L) 1.7 0 Results Thickness (micron) 8.4 3.0 Rating 3-5 1-5