Compositions: coating or plastic – Coating or plastic compositions – Metal-depositing composition or substrate-sensitizing...
Reexamination Certificate
2000-01-25
2002-05-07
Klemanski, Helene (Department: 1755)
Compositions: coating or plastic
Coating or plastic compositions
Metal-depositing composition or substrate-sensitizing...
C106S001260, C427S443100, C427S437000
Reexamination Certificate
active
06383269
ABSTRACT:
BACKGROUND OF THE INVENTION
Composite coatings of electroless nickel-phosphorous or nickel-boron followed by a thin coating of immersion gold have been used successfully as solderable finishes on fine pitch, high density circuitry. The nickel deposit serves as a diffusion barrier to the underlying copper while the gold acts as a noble metal protective layer to inhibit the underlying nickel deposit from oxidation.
All electroless immersion processes, also referred to as displacement or replacement processes, depend on the oxidation of the less noble metal surface to supply electrons for the reduction of the more noble metal from solution. As such, all immersion processes can be considered as a combination of corrosion of the one metal with balanced reduction of another driven by the thermodynamic potential couple between them. The reaction continues until a uniform coating of the more noble metal is produced on the substrate surface, sealing off the corrosion sites and neutralizing the potential difference between them. In the case of electroless nickel/immersion gold, the nickel deposit is oxidized and dissolves into solution while the gold in solution is reduced to metal on the nickel surface.
Under certain conditions that are not yet fully understood, the nickel surface can undergo particularly high levels of corrosion during the gold displacement reaction, giving rise to a dramatic structural transformation of the nickel surface. The corroded nickel surface generally is black in appearance and, in cases where electroless nickel-phosphorous is used, the nickel surface is found to contain excessively high amounts of phosphorous. Recently, the term “black nickel” has been coined to describe this particular phenomena. One of the more damaging results of this effect is a loss in solderability due to the inability of the black nickel deposit to be properly wetted with solder. This in turn can lead to weak and unreliable solder joints between the component to be soldered and the plated pads of the printed circuit board.
It is believed that in order for this effect to occur, a potential gradient between surface features on the circuit board must exist, with some features acting anodically relative to others. The galvanic difference observed between features could be caused by a designed capacitance that is built into the various layers or planes of a multilayer circuit board, or by the natural potential difference that exists between two dissimilar metals, which in this case would be nickel and gold. At the very initial stages of gold deposition onto nickel, there will be exposed areas of both nickel and gold. A galvanic cell between the two dissimilar metals could be created, whereby the nickel will be anodically attacked. The corrosion that results is sometimes referred to as “bipolar attack”.
In addition to the possibilities stated above, a relative difference in surface activity/passivity between adjacent features resulting from slight variations in surface cleanliness of the features could also promote the occurrence of a similar corrosion reaction.
Gold is also used to protect the electroless nickel plated circuitry from oxidation during storage, thereby better ensuring the nickel will be solderable during the component assembly process. When a galvanic difference as described above exists, certain features such as fine pitch surface mount or ball grid array (“BGA”) pads can undergo an accelerated anodic corrosion during processing in the conductive immersion gold solution, consequently increasing substantially the dissolution rate of the nickel deposit. Simulation tests have shown that when a sufficient anodic potential is externally applied to a nickel plated circuit board while in the immersion gold solution, “black nickel” will occur.
Thus, there is a need for improvements in this area in order to avoid or minimize “black nickel” as well as to improve the solderability of the resultant deposit.
SUMMARY OF THE INVENTION
The present invention provides an aqueous electrolyte composition for immersion plating of gold onto a substrate including one or more water soluble gold compounds, one or more organic conductivity salts, one or more reducing agents, and water.
The present invention also provides a method of producing gold coatings on nickel including the step of contacting a substrate including nickel with an immersion gold plating solution including the electrolyte described above.
The present invention further provides a method for manufacturing printed circuit boards including the steps of (a) providing a circuit board having a circuit pattern including one or more of traces, holes or lands of copper; (b) optionally covering areas the circuit pattern with a soldermask; (c) contacting the circuit board with an electroless nickel plating solution for a period of time sufficient to obtain an electroless nickel plated circuit board comprising a nickel layer having a thickness in the range of 0.5 to 10 microns; and (d) contacting the electroless nickel plated circuit board with an immersion gold plating solution for a period of time sufficient to provide a gold finish at a thickness sufficient to protect the nickel layer from oxidation, wherein the immersion gold plating solution comprises the electrolyte described above.
DETAILED DESCRIPTION OF THE INVENTION
As used throughout this specification, the following abbreviations shall have the following meanings: g=gram; &mgr;m=micron; 1=liter; ° C.=degrees centigrade; and ° F.=degrees Fahrenheit. All numerical ranges are inclusive.
This invention relates to producing a protective immersion gold coating onto nickel containing substrates, such as printed circuit boards, while greatly reducing or eliminating the tendency for excessive corrosion and dissolution of the nickel layer to occur. This in turn improves the solderability of the resulting deposit. An other advantage of the present invention is that “bipolar attack” in the deposit during plating can be virtually eliminated or significantly reduced.
Specifically, the invention relates to electrolyte compositions for use in an immersion gold process used for depositing thin films of gold upon a substrate containing a nickel layer. As used herein, “substrates containing a nickel layer” include substrates having a nickel metal or nickel alloy layer, and preferably a nickel layer. It will be appreciated by those skilled in the art that nickel metal or nickel alloys alone, i.e. not supported on a substrate, may be advantageously gold plated according to the present invention. Any nickel alloy may be advantageously used in the present invention. Suitable substrates include, but are not limited to, printed wiring boards or other electronic devices. Such substrates may be nickel plated electrolytically or electrolessly. It is preferred that the substrates contain an electroless nickel layer. It is further preferred that the electroless nickel layer is plated with conventional electroless nickel-phosphorus or nickel-boron solutions.
The electrolyte compositions of the present invention contain water, one or more water-soluble gold compounds, one or more conductivity salts (or complexing agents) and one or more reducing agents. While not wishing to be bound by theory, it is believed that the conductivity salt complexes trace metal ions in the solution and assists in the electroless deposition of the gold deposit. While not wishing to be bound by theory, it is believed that the function of the reducing agent is to minimize or eliminate the corrosion that could occur through bipolar attack. It is believed that the reducing agent is oxidized sacrificially in preference to the excess dissolution of the base metal which could otherwise cause this defect, as described above. In this regard, and as a general protection against non-uniform dissolution or oxidation of the nickel, it is also contemplated that use of the reducing agent in the processing steps between nickel and gold plating would be beneficial.
Any water-soluble gold compound is suitable for us
Enomoto Haruki
Martin James L.
Ohta Yasuo
Takizawa Yasushi
Toben Michael P.
Cairns S. Matthew
Klemanski Helene
Shipley Company L.L.C.
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