Anti-tombstoning solder alloys for surface mount applications

Metal fusion bonding – Process – Preplacing solid filler

Reexamination Certificate

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C228S245000, C420S557000

Reexamination Certificate

active

06783057

ABSTRACT:

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
N/A
BACKGROUND OF THE INVENTION
Tombstoning effect (also known as Manhattan effect, Drawbridge effect, or Stonehenge effect) is considered a common soldering defect in surface mount electronic assembly of small leadless components such as resistors and capacitors. Recently, the trend toward miniaturization in electronic assembly to achieve smaller, lighter, and higher performing products has resulted in rapidly increasing implementation of small leadless passive and active components. Until recently, the 0603 components (this terminology means that the components are 6 mil×3 mil in size), which have been prevalent for years in high volume production, have produced very high yield and few defects. The 0402 and 0201 components have recently been used more frequently and have presented electronic assemblers the tremendous challenge of decreasing the defects due to increasing use of these components in assembly.
The tombstoning effect is due to the imbalance of the surface tension of the molten solder at both ends of the component during reflow soldering. Because of the small dimensions of these 0402 and 0201 components, the intricate balance of the surface tension may be more easily disturbed by either the change of the solderability of the components or by the differences of time at which the solder paste at each end of the component begins to melt.
One approach to solving the tombstoning problem has been proposed by Taguchi et al (U.S. Pat. No. 6,050,480), which teaches using a solder powder comprising of a solder alloy consisting of 60-65% Sn, 0.1-0.6% Ag, 0.1-2%Sb, and a balance of Pb, to prevent tombstoning during reflow soldering. The essence of Taguchi is to employ Ag and Sb to effectively increase the solidification temperature range and, in turn, to prevent the tombstoning.
BRIEF SUMMARY OF THE INVENTION
The object of this invention is to employ a solder alloy comprising tin/lead/silver in order to provide a wider solidification range and achieve balance between the surface tension of both side of a small leadless component. The expanded solidification range slows the melting and wetting time so as to balance the surface tension of the molten solder, and in turn reduces the tombstoning frequency. The preferred Ag concentration is 0.2-0.5% in weight, while the more preferred Ag concentration is 0.3-0.4% in weight. For reflow soldering of small leadless components, the pastes made with the alloy compositions of Sn62.6Pb37Ag0.4 and Sn63Pb36.6Ag0.4 result in minimization of tombstoning.
DETAILED DESCRIPTION OF THE INVENTION
It has been discovered that the addition of a small amount of silver to a tin/lead solder composition can dramatically reduce the tombstoning, particularly with the extremely small electronic components that have recently been used in electronic assemblies. In particular, it has been found that the amount of silver should be in the range of 0.1-0.7%, preferably 0.2-0.5% (for a tin/lead alloy in the range of approximately Sn63Pb37), more preferably 0.3-0.4%.
This unexpected benefit has been found in solders where the tin content ranges from about 58.0-68.0% (preferably 61.0-65.0% and most preferably 62.0-64.0%), while the lead content can range from about 32.0-42.0% (preferably 35.0-39.0% and most preferably 36.0-38.0%). (Note: it is recognized that, in these three-component tin/lead/silver solders, the maximum amount of each of the three components cannot be used, since the total must not exceed 100%.)
Thus, preferred alloys have been found to be the compositions
a. Sn62.6Pb37Ag0.4,
b. Sn63Pb36.6Ag0.4,
c. Sn62Pb37.6Ag0.4,
d. Sn62.2Pb37.4Ag0.4
In addition, it has been found that deviations from the desired silver content of 0.3-0.4% has resulted in increased tombstoning, as shown in the following table 1. In this test a rosin mildly activated flux was used, the metal load was 90%, and the powder size of the Sn63Pb37 powder was 45-25 microns (i.e., particles passed through 325 mesh, but failed to pass through 500 mesh screens). (Note: this test employs somewhat exaggerated conditions. Under these test conditions, the acceptable range of silver is from 0.1-0.5%. Under normal (i.e., non-test) conditions, we have found acceptable performance using 0.1-0.7% silver.)
TABLE 1*
Ag concentration (weight %)
Tombstoning frequency
0
33% ± 15%
0.1
8% ± 6%
0.4
0% ± 3%
0.6
31% ± 19%
*Because a manual process for vapor phase reflow was employed, relatively large data scattering was observed.
In addition it has been found that Sb does not help reduce the tombstoning frequency. Taguchi teaches using amounts of Ag (0.1-0.6%) and Sb (0.1-2%) to reduce the tombstoning frequency. Note that Taguchi indicates that the presence of less than 0.1% of either of these metals will result in the loss of the antitombstoning benefit. However, in the instant invention, it has been found that the Sb is not needed to reduce tombstoning. (Note that, in analyzing the alloys in the instant invention, only a slight contaminant level of Sb (less than 0.01%) was found.)
Further investigations of the effect of elements such as Ag, Bi, In, Sb, Zn, Cu, and Ge on the expansion of the solidification range of the Sn63Pb37 are tabulated as follows:
TABLE 2
Lower end of
Upper end of
melting
melting
Solidification
Alloys
region
region
range ° C.
Sn63Pb37
181.9
184.7
2.8
Sn62.6Pb37Ag0.4
177.7
184.5
6.8
Sn62.8Pb37Bi0.2
181.4
184.3
2.9
Sn62.6Pb37Bi0.4
180.8
185.2
4.4
Sn62.8Pb37In0.2
181.3
184.5
3.2
Sn62.6Pb37In0.4
180.5
185.0
4.5
Sn62.8Pb37Sb0.2
182.2
186.3
4.1
Sn62.6Pb37Sb0.4
182.4
185.8
3.4
Sn62.8Pb37Zn0.2
181.8
184.5
2.7
Sn62.6Pb37Zn0.3
182.0
185.7
3.7
Sn62.8Pb37Cu0.2
181.0
184.1
3.1
Sn62.6Pb37Cu0.4
181.0
184.3
3.3
Sn62.8Pb37Ge0.2
181.7
184.6
2.9
Sn62.6Pb37Ge0.4
181.7
184.3
2.6
Sn62.4Pb37Ge0.6
181.8
184.1
2.3
It is very clear from table 2 that the addition of 0.4% of Ag resulted in the most expansion of the solidification range (the upper end minus the lower end of the melting range), while the addition of Sb resulted in a much smaller solidification range.
Accordingly, there is little benefit of employing Sb in antitombstoning applications.
Another benefit resulting from the exclusion of antimony is the elimination of exposure to this hazardous material. (For information on the toxicity of Sb and the gastrointestinal and respiratory effect of Sb on humans, see Antimony and Compounds, United States Environmental Protection Agency, Office of Air Quality Planning and Standards. Unified Air Toxics Website. www.epa.gov/ttn/uatw/hlthef/antimony.html.)
Furthermore, the inclusion of one fewer component certainly results in simplification and reduction in cost of the manufacturing and quality control processes. In addition, it is well known that use of more complex alloys (greater than 3 elements) generally results in significant variations of alloy compositions of solder joints. (Chris Bastecki, “A Benchmark Process for the Lead-free Assembly of Mixed Technology PCB's ” Revised 1999, Alpha Metals website, www.alphametals.com)
In a more severe case, a larger pasty range (resulting from an alloy with more than 3 components) could result in “hot tearing” as the solder joints experience thermal excursions. Furthermore, it was also observed that in order to avoid the formation and segregation of low melting point phases, which could cause cracking or hot tearing, the alloy composition should be as close to a eutectic as possible. (Tommi Laine-Ylijorki, Atso Forsten, and Dr. Hector Steen, “Development and Validation of a Lead-free Alloy for Solder Paste Applications”, Future Circuits International, Vol. 2, issue 1, p. 183-185.)
In addition, the solder alloys needed to be close to the eutectic composition because of smaller melting range, lower viscosity, and superior mechanical properties compared with off-eutectic compositions. (J. H. Vincent and G. Humpston, “lead-free Solders for Electronic Assembly”, GEC Journal of Research, Vol. 11, No. 2, 1994, page 76.)
Multi-component doping elements added to the eutectic Sn

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