Patent Grant
7731831
1. Field of the Invention
This invention relates to a copper foil for use in the manufacture of printed circuit boards and flexible circuits. More particularly, a composite material includes a copper foil layer and a support layer with a release layer disposed between the copper foil and the support layer. Contacting the release layer with a reactive element at an elevated temperature reduces blister formation during subsequent assembly steps.
2. Description of Related Art
Composite materials used for the manufacture of printed circuits and flexible circuits are described in the above-referenced U.S. Pat. Nos. 6,346,335 and 6,569,543. A support layer, typically formed from copper, is coated with a release layer. The copper foil layer is formed on the release layer, typically by electrolytic deposition. Adhesion between the release layer and the copper foil layer is high enough so that the copper foil layer does not separate from the support layer prematurely, but is sufficiently low that separation of the support layer following lamination does not tear or otherwise damage the copper foil layer. Typical release layers include an admixture of a metal selected from the group consisting of chromium, nickel, titanium, copper, manganese, iron, cobalt, tungsten, molybdenum, tantalum and mixtures thereof and a non-metal selected from the group consisting of oxides, phosphate and chromates of those metals. One preferred release layer is an admixture of chromium and chromium oxide.
For the manufacture of printed circuits, the composite material is laminated to a glass-filled epoxy-type board with the copper foil layer contacting the epoxy board. A combination of heat (typically between 180° C. and 250° C.) and pressure (typically between 200 psi and 300 psi) bonds the copper foil layer to the epoxy board. The support layer and release layer are then peeled away from the epoxy board/copper foil assembly.
For the manufacture of flexible circuits or high temperature application devices, the copper foil is sometimes laminated in the absence of pressure. The copper foil is coated with a polymer dielectric, such as polyimide. The coated composite material is then dried and cured at a temperature of between 180° C. and 400° C., for example 360° C. for 30 minutes in a nitrogen atmosphere at one atmosphere of pressure. After curing, the support layer and release layer are then peeled away from the polymer dielectric copper foil assembly.
It is important that when the support layer is peeled from the copper foil layer that the copper foil layer is defect free. One such defect that has been reported is blisters on the surface of the copper foil layer that previously contacted the support layer. These blisters are believed to originate when gasses are evolved at the support layer/copper foil interface and then expand with increasing temperature during the dielectric curing process. The blisters are typically a few thousandths of an inch in diameter with a frequency ranging from a few to several thousand per square foot. Upon separation from the support layer, the blisters leave depressions in the surface of the laminated copper foil. These small depressions render those regions of the laminate unacceptable for the processing of fine-line circuits.
There remains a need for a process to manufacture flexible circuits that reduces or eliminates the formation of such blisters.
Exemplary other copper-base alloys, and their nominal compositions by weight, include C15100—0.05%-0.15% zirconium an the balance (minimum 99.85%) is copper; C18100 0.40%-1.2% chromium, 0.03%-0.06% magnesium, 0.08%-0.20% zirconium, balance (minimum 98.7%) copper; C728—9.5%-10.5% nickel, 7.5%-8.5% tin, 0.10%-0.30% niobium, 0.05%-0.30% manganese, 0.005%-0.15% magnesium and the balance is copper; C7026—1.0%-3.0% nickel, 0.2%-0.7% silicon and the balance is copper; and NK120—0.01%-0.4% chromium, 0.01%-0.25% zirconium, 0.02%-2.0% zinc and the balance is copper.
Non-copper-base substrates useful in accordance with the invention, and their nominal compositions by weight, include aluminum alloy 2219—5.8%-6.8% copper, 0.2%-0.4% manganese, 0.05%-0.15% vanadium, 0.02%-0.10% titanium, 0.1%-0.25% zirconium and the balance is aluminum and stainless steel 32100—17.0%-19.0% chromium, 9.0%-12.0% nickel, maximum of 0.08%, 5×(minimum percent C) of titanium, and the balance is iron.
Use of these alloys is effective to reduce the number of blisters that form, particularly in those applications where blisters are prone to form, such as lamination in the absence of pressure. The mechanism that causes a reduction in blistering is not known. It is believed that one or more of the following cause a reduction in blistering: when alloyed with the support layer material, the reactive elements increase the tensile strength of the support layer such that there is less flexing during processing; when alloyed with the support layer material, the reactive elements change the coefficient of thermal expansion of the support layer; and when either alloyed with the support layer material or coated on a surface of the support layer, the substrate alloy or its constituent phases react with gaseous elements or compounds such as moisture that may form at the release layer interface to suppress blister formation. For example, hydrogen if evolved, would dissolve in the substrate or react to form a hydride by combination with a reactive element. The alloying elements to provide these beneficial effects are preferably selected from the group consisting of titanium, zirconium, barium, magnesium, silicon, niobium, calcium and mixtures thereof.
The reactive alloying elements are present in an amount, by weight, of from 0.001% to 50% and preferably in an amount of from 0.1% to 5%. It is desired for there to be a sufficient quantity to provide the copper alloy with a tensile strength in excess of 30 ksi after being exposed to a lamination temperature of in excess of 180° C. This facilitates handling of the composite material, protects the thin copper foil layer from wrinkles and mechanical damage and can be used as a protective sheet in the circuit board fabrication process, such as for hole punching.
Release layer 14 is disposed between the support layer 12 and a copper foil layer 16. The release layer 14 is selected such that adhesion between the release layer 14 and the copper foil layer 16 is high enough so that the copper foil layer does not separate from the support layer 12 prematurely, but is sufficiently low that separation of the support layer following lamination does not tear or otherwise damage the copper foil layer. Typical release layers include an admixture of a metal selected from the group consisting of chromium, nickel, titanium, copper, manganese, iron, cobalt, tungsten, molybdenum, tantalum and mixtures there of and a non-metal selected from the group consisting of oxides, phosphates and chromates of those metals. One preferred release layer is an admixture of chromium and chromium oxide.
Copper foil layer 16 is electrolytically deposited onto the release layer from any suitable electrolyte, such as an aqueous alkaline or acid solution containing copper ions in the form of for example copper sulfate and/or copper pyrophosphate as disclosed in published US patent application US2002/0192486, “Copper Foil with Low Profile Bond Enhancement,” that is incorporated by reference herein in its entirety. The copper foil layer is thin, on the order of 15 microns in thickness or less and preferably, the thickness is from 0.2 μm to 8.0 μm.
The composite material may then, preferably, be subjected to a heat treatment 30 that is at a temperature which is less than the lamination temperature, such as from about 100° C. to about 350° C. for up to about 48 hours in a nitrogen or forming gas (by volume 96% N2-4% H2) atmosphere. By “about” it is meant that exactitude is not desired and values are ±20%. This heat treatment may be in one or several stages. An exemplary one stage heat treatment 30 is at a temperature of from about 100° C. to about 240° C. for from about 8 hours to about 24 hours. An exemplary two stage heat treatment is a first stage of about 150° C. to about 200° C. for from about 15 hours to about 25 hours followed by about 200° C. to 250° C. for from about ½ hour to about 5 hours.
After the heat treatment 30, a polymer dielectric is deposited 32 onto a surface of the copper foil layer. Exemplary polymer dielectrics include epoxy, polyimide, polytetrafluoroethylene (Teflon) and mixtures thereof. The deposition is by any suitable method such as gravure-roll coating, nip-roll lamination, doctor's blade, spraying or immersion. The polymer dielectric is then dried and cured 34 by heating to an effective temperature for curing, such as 180° C. to 380° C. for from 0.1 hours to 6 hours. Typically, blistering is more pronounced and the benefits of the invention more necessary when the lamination utilizes heat but not pressure.
The cured polymer dielectric 38/copper foil assembly 16 is then peeled from the release layer 14/support layer 12 as illustrated in cross-sectional representation in
A similar process flow is effective to manufacture the composite material illustrated in
While blistering is best reduced or eliminated by the contacting of a reactive element containing-layer with the release layer, some reduction in the amount of blistering is obtained by the low temperature anneal, even without the inclusion of a reactive element containing component.
The benefits of the above embodiments will be better understood by the Example that follows.
Support layers having the compositions and thicknesses recited in Table 1 were coated with a release layer having a thickness of between about 12 Å and about 200 Å and a nominal composition that was a mixture of chromium oxides, chromium, and chromium hydroxides. The release layer was deposited by electrodeposition. A copper foil layer having a nominal thickness of 5 μm was deposited by electrodeposition. The so-formed composite was then heated to 170° C. in an air, nitrogen or forming gas atmosphere for the time recited in Table 1.
The annealed samples were then heated to 360° C. for 30 minutes in a nitrogen atmosphere to simulate a cure cycle for a dielectric. The occurrence and density of blisters was then rated qualitatively to anticipate the quality of imaged copper foil circuit traces on a circuit board, where: 00=excellent; 0=good; Δ=fair; X=poor; and N.R.=not rated. The results are reported in Table 1.
Table 1 illustrates that when the substrate contains a reactive element, such as titanium, silicon or magnesium, and the composite material is heat treated, blistering is substantially eliminated. While the low temperature anneal reduces blistering in a non-reactive element containing alloy (i.e. C110), the improvement is not as pronounced.
It is apparent that there has been provided in accordance with the present invention a composite material and a method to manufacture that composite material such that blister defect formation is reduced during circuit board processing, and that fully satisfies the objects, means and advantages set forth hereinabove. While the invention has been described in combination with embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternative, modifications and variations as fall within the spirit and broad scope of the appended claims.
This application is a continuation of U.S. patent application Ser. No. 10/965,347, filed on Oct. 14, 2004, now issued as U.S. Pat. No. 7,132,158, which relates to and claims priority to U.S. Provisional Patent Application Ser. No. 60/513,367 for “Support Layer for Thin Copper Foil” that was filed on Oct. 22, 2003. In addition, this patent application relates to U.S. Pat. No. 6,346,335, “Copper Foil Composite Including a Release Layer” and U.S. Pat. No. 6,569,543, “Copper Foil with Low Profile Bond Enhancement.” The subject matters of the provisional patent application and both U.S. patents are incorporated by reference herein in their entireties.
| Number | Name | Date | Kind |
|---|---|---|---|
| 454381 | Reinfeld | Jun 1891 | A |
| 3998601 | Yates et al. | Dec 1976 | A |
| 4088544 | Hutkin | May 1978 | A |
| 4169018 | Berdan et al. | Sep 1979 | A |
| 4357395 | Lifshin et al. | Nov 1982 | A |
| 4499152 | Green et al. | Feb 1985 | A |
| 4503112 | Konicek | Mar 1985 | A |
| 4515671 | Polan et al. | May 1985 | A |
| 4568413 | Toth et al. | Feb 1986 | A |
| 4997517 | Parthasarathi | Mar 1991 | A |
| 5049221 | Wada et al. | Sep 1991 | A |
| 5066366 | Lin | Nov 1991 | A |
| 5071520 | Lin et al. | Dec 1991 | A |
| 5096522 | Kawachi et al. | Mar 1992 | A |
| 5114453 | Ross et al. | May 1992 | A |
| 5230932 | Chen et al. | Jul 1993 | A |
| 5322975 | Nagy et al. | Jun 1994 | A |
| 5447619 | Wolski et al. | Sep 1995 | A |
| 5617629 | Ekstrom | Apr 1997 | A |
| 5779870 | Seip | Jul 1998 | A |
| 5800930 | Chen et al. | Sep 1998 | A |
| 6132887 | Clouser et al. | Oct 2000 | A |
| 6183880 | Yoshioka et al. | Feb 2001 | B1 |
| 6235404 | Frater | May 2001 | B1 |
| 6238778 | Schneider | May 2001 | B1 |
| 6270889 | Kataoka et al. | Aug 2001 | B1 |
| 6346335 | Chen et al. | Feb 2002 | B1 |
| 6447929 | Wang et al. | Sep 2002 | B1 |
| 6500566 | Smith | Dec 2002 | B1 |
| 6544663 | Nakano et al. | Apr 2003 | B1 |
| 6569543 | Brenneman et al. | May 2003 | B2 |
| 6596391 | Smith | Jul 2003 | B2 |
| 6630036 | Saita et al. | Oct 2003 | B2 |
| 6689268 | Chen et al. | Feb 2004 | B2 |
| 7026059 | Suzuki et al. | Apr 2006 | B2 |
| 7049007 | Gales et al. | May 2006 | B2 |
| 20020192486 | Chen et al. | Dec 2002 | A1 |
| 20030031867 | Ogura et al. | Feb 2003 | A1 |
| 20030035948 | Fujimaru et al. | Feb 2003 | A1 |
| Number | Date | Country |
|---|---|---|
| 208177 | Oct 1987 | EP |
| 001331088 | Jul 2003 | EP |
| WO0224444 | Mar 2002 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20070141380 A1 | Jun 2007 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60513367 | Oct 2003 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10965347 | Oct 2004 | US |
| Child | 11593949 | US |
