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LEAD-FREE EUTECTIC SOLDER ALLOY COMPRISING ZINC AS THE MAIN COMPONENT AND ALUMINUM AS AN ALLOYING METAL

申请号 EP17159539.0 申请日 2015-04-15 公开(公告)号 EP3192610B1 公开(公告)日 2018-07-11
申请人 Heraeus Materials Singapore Pte. Ltd.; 发明人 PAN, Wei Chih; BAQUIRAN, Joseph Aaron Mesa; REYNOSO, Inciong;
摘要 Lead-free solder alloy comprising zinc (Zn) as the main component and aluminum (Al) as an alloying metal, wherein the solder alloy is a eutectic having a single melting point in the range of 320 to 390 °C (measured by DSC at a heating rate of 5 °C min -1 ), wherein the lead-free solder alloy comprises 6.0 wt.% of aluminum (Al) and 6.0 to 7.2 wt.% of germanium (Ge).
权利要求 Lead-free solder alloy comprising zinc (Zn) as the main component and aluminum (Al) as an alloying metal,
wherein the solder alloy is a eutectic having a single melting point in the range of 320 to 390 °C (measured by DSC at a heating rate of 5 °C min-1),
wherein the lead-free solder alloy consists of
6.0 wt.% of aluminum (Al), 6.0 wt.% of germanium (Ge), 2.0 wt.% of copper (Cu), 1.25 wt.% of tin (Sn), a total of 0 to 0.5 wt.% of one or more doping elements selected among phosphorus (P), nickel (Ni), bismuth (Bi), antimony (Sb) and silicon (Si), up to 0.05 wt.% of inevitable impurities, and of zinc (Zn) as the remainder to make up 100 wt.%.
Use of a lead-free solder alloy of claim 1 as a solder metal present in a form selected from the group consisting of solder wires, solder rods, solder powders and solder preforms.Use of a lead-free solder alloy of claim 1 as the only metal alloy constituent in a solder composition selected from the group consisting of solder pastes and solder wires with fluxes.A lead-free solder alloy of claim 1 present in a form selected from the group consisting of solder wires, solder rods, solder powders and solder preforms.A solder composition selected from the group consisting of solder pastes and solder wires with fluxes, wherein the solder composition comprises a lead-free solder alloy of claim 1 as the only metal alloy constituent.Use of the solder composition of claim 5 for mechanical connection or in electronic or microelectronic applications.
说明书全文

The invention is directed to a lead-free eutectic solder alloy comprising zinc (Zn) as the main component and aluminum (Al) as an alloying metal. The invention is also directed to the use of the lead-free eutectic solder alloy.

Legislation driven by environmental and health concerns is still driving the replacement of lead-containing solder alloys with lead-free alternatives. However, the alternative solder alloy's melting temperature, or to be more precise, its solidus temperature must be high enough, especially with regard to applications in which the finished solder joints experience high temperature as the case may be either in later process steps and/or under field conditions. In die-attach applications, for example, a melting temperature of the solder alloy in the range of 280 to 400 °C is required.

US 2013/0045131 A1 discloses lead-free zinc base solder compositions comprising 82 to 96 wt.% (weight-%) of zinc, 3 to 15 wt.% of aluminum, 0.5 to 1.5 wt.% of magnesium and 0.5 to 1.5 wt.% of gallium.

JP2000208533 A discloses a lead-free zinc base die-bonding alloy of 2 to 9 wt.% of aluminum, 0.01 to 0.5 wt.% of magnesium, 2 to 9 wt.% of germanium and a remainder of zinc and inevitable impurities.

US2012/0313230 A1 claims several lead-free zinc base solder alloys, one with 8 to 20 wt.% of aluminum, 0.5 to 20 wt.% of magnesium and 0.5 to 20 wt.% of gallium, a further one with 1 to 30 wt.% of aluminum, 0.5 to 20 wt.% of magnesium and 0.5 to 6.5 wt.% of tin and also one with 1 to 30 wt.% of aluminum, 0.5 to 20 wt.% of germanium and 0.5 to 20 wt.% of gallium, the rest of the alloys in each case comprising zinc.

JP2012228729 A discloses lead-free zinc base solder alloy comprising 0.01 to 9.0 wt.% of aluminum, at least one of germanium, magnesium, silver and phosphorus in ranges of 0.01 to 8.0 wt.% of germanium, 0.01 to 5.0 wt.% of magnesium, 0.1 to 4.0 wt.% of silver, and at most 0.5 wt.% of phosphorus; and a remainder of Zn and inevitable impurities.

JP11207487 A discloses lead-free zinc base solder alloy consisting of 1 to 7 wt.% of aluminum, 0.5 to 6 wt.% of magnesium, 1 to 25 wt.% of tin, and the balance zinc with inevitable impurities.

US 2013/0251587 A1 claims lead-free zinc base solder alloy consisting of 1.0 to 9.0 wt.% of aluminum, 0.002 to 0.8 wt.% of phosphorus, 0.3 to 3 wt.% of germanium and a balance being zinc with inevitable impurities.

JP2012183558 A discloses a lead-free solder alloy including 1-10 wt.% of Al, one or more elements selected from 0.001-1 wt.% of Ga, 0.1-10 wt.% of In, 0.001-10 wt.% of Ge, 0.1-10 wt.% of Si and 0.1-10 wt.% of Sn as an additive component for improving wettability, and the balance of Zn and unavoidable impurities. Further, 0.0001-1 wt.% of Mn and/or Ti are added and mixed to the composition, whereby reliability of solder joining is improved due to suppression of surface oxidation of a solder joint portion and the like.

JPH11172353 A discloses a Zn alloy for high temperature soldering, having a composition consisting of, by weight, 2-9%, preferably 5-6%, Al, 1-9%, preferably 4-5%, Ge, 1-25%, preferably 5-20%, Sn and/or In, and the balance Zn with inevitable impurities.

There is a desire to find improved lead-free solder alloys.

The invention relates to a lead-free eutectic solder alloy as defined in claim 1, the alloy comprising zinc (Zn) as the main component and aluminum (Al) as an alloying metal. Its eutectic temperature, represented by a single melting point, lies in the range of 320 to 390 °C (measured by DSC at a heating rate of 5 °C min-1).

The abbreviation "DSC" used herein means differential scanning calorimetry.

It has been found that the lead-free eutectic solder alloy of the invention can be used as solder metal or in solder compositions, in particular for use in the electronics and microelectronics field.

The solder joints made from solder compositions comprising or consisting of the lead-free eutectic solder alloy of the invention exhibit surprisingly improved thermal characteristics, microstructural characteristics and reliability. These characteristics result in better performance of products made using these alloys.

The lead-free eutectic solder alloy of the invention consists of 6.0 wt.% of aluminum (Al), 6.0 wt.% of germanium (Ge), 2.0 wt.% of copper (Cu), 1.25 wt.% of tin (Sn), a total of 0 to 0.5 wt.% of one or more doping elements selected among phosphorus (P), nickel (Ni), bismuth (Bi), antimony (Sb) and silicon (Si), up to 0.05 wt.% of inevitable impurities, and of zinc (Zn) as the remainder to make up 100 wt.%. The alloy exhibits a single melting point at 358 °C (measured by DSC at a heating rate of 5 °C min-1).

The phrase "zinc (Zn) as the remainder to make up 100 wt.%" is used herein. It shall mean that zinc is the main component in the respective lead-free eutectic solder alloy, as has already been said above. To avoid misunderstandings, the preceding sentence shall not be understood to exclude other elements which due to prevailing technical conditions may have found their way into the lead-free eutectic solder alloy of the invention, for example, as a consequence of an unintentional but inevitable incorporation during manufacture. In other words, such other elements may be present in the lead-free eutectic solder alloy as inevitable impurities, however only in very minor amounts of, for example, > 0 to 0.05 wt.%. In any case such inevitable impurities are not deliberately added or introduced into the alloy forming composition. Insofar, the phrase "zinc (Zn) as the remainder to make up 100 wt.%" means that the wt.% proportion which is missing to make up 100 wt.% of the alloy consists of zinc plus said inevitable impurities, if the latter are present.

The lead-free eutectic solder alloy of the invention can be prepared by conventional processes known to the person skilled in the art of metal alloys, for example, by melting together the zinc, the aluminum and the other necessary components. It is possible to use an induction furnace and it is expedient to work under vacuum or under an inert gas atmosphere. The materials used can have a purity grade of, for example, 99.99 wt.% and above. The metal alloy melt is typically cast in a mold of room temperature in which it cools down and solidifies.

The lead-free eutectic solder alloy of the invention can directly (i.e. as such in metal form) be used as a solder metal. However, from a practical perspective, it must be brought in a form suitable for an intended soldering task. Examples of suitable forms include solder wires, solder rods, solder powders and solder preforms.

The lead-free eutectic solder alloy of the invention can also be used as the only metal alloy constituent in a solder composition. Examples of solder compositions include solder pastes and solder wires with fluxes.

The lead-free eutectic solder alloy of the invention or the solder compositions comprising the lead-free eutectic solder alloy of the invention as the only metal alloy constituent can be used in many applications including mechanical connection and electronic or microelectronic applications. The lead-free eutectic solder alloy of the invention can be used as a brazing alloy in mechanical connection, for example. It can also be used in electronic or microelectronic applications. The solder compositions comprising the lead-free eutectic solder alloy of the invention can in particular be used in electronic or microelectronic applications. Examples of electronic or microelectronic applications include attachment of wafer die to leadframes, attachment of packaged die to heatsink or soldering of leads to printed circuit board.

When performing a soldering task, in particular an electronic or microelectronic soldering task, with the lead-free eutectic solder alloy of the invention (regardless if directly used as solder metal or in the form of a solder composition as mentioned above), it may be expedient to support the soldering process by application of ultrasonic energy to the applied and molten lead-free eutectic solder alloy. Such application of ultrasonic energy may help in preventing formation of voids in the solder and in forming consistent solder joints in terms of homogeneous solder layer thickness as well as solder formation shape regardless of inconsistent solder dot positioning.

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