High-temperature lead-free solder alloy

Abstract

Provided is a high-temperature lead-free solder alloy having excellent tensile strength and elongation in a high-temperature environment of 250° C. In order to make the structure of an Sn—Sb—Ag—Cu solder alloy finer and cause stress applied to the solder alloy to disperse, at least one material selected from the group consisting of, in mass %, 0.003 to 1.0% of Al, 0.01 to 0.2% of Fe, and 0.005 to 0.4% of Ti is added to a solder alloy containing 35 to 40% of Sb, 8 to 25% of Ag, and 5 to 10% of Cu, with the remainder made up by Sn.

Claims

1. A high-temperature lead-free solder alloy having an alloy composition comprising: 35 to 40 wt % of Sb, 8 to 25 wt % of Ag, 5 to 10 wt % of Cu as well as at least one selected from the group consisting of 0.003 to 1.0 wt % of Al, 0.01 to 0.2 wt % of Fe and 0.005 to 0.4 wt % of Ti, and a balance of Sn.

2. The high-temperature lead-free solder alloy according to claim 1, further comprising at least one selected from the group consisting of P, Ge and Ga in a total amount of 0.002 to 0.1 wt %.

3. The high-temperature lead-free solder alloy according to claim 1, further comprising at least one selected from the group consisting of Ni, Co and Mn in a total amount of 0.01 to 0.5 wt.

4. The high-temperature lead-free solder alloy according to claim 1, further comprising at least one selected from the group consisting of Zn and Bi in a total amount of 0.005 to 0.5 wt %.

5. The high-temperature lead-free solder alloy according to claim 1, further comprising at least one selected from the group consisting of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr in a total amount of 0.0005 to 1 wt %.

6. The high-temperature lead-free solder alloy according to claim 2, further comprising at least one selected from the group consisting of Ni, Co and Mn in a total amount of 0.01 to 0.5 wt %.

7. The high-temperature lead-free solder alloy according to claim 2, further comprising at least one selected from the group consisting of Zn and Bi in a total amount of 0.005 to 0.5 wt %.

8. The high-temperature lead-free solder alloy according to claim 3, further comprising at least one selected from the group consisting of Zn and Bi in a total amount of 0.005 to 0.5 wt %.

9. The high-temperature lead-free solder alloy according to claim 6, further comprising at least one selected from the group consisting of Zn and Bi in a total amount of 0.005 to 0.5 wt %.

10. The high-temperature lead-free solder alloy according to claim 2, further comprising at least one selected from the group consisting of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr in a total amount of 0.0005 to 1 wt %.

11. The high-temperature lead-free solder alloy according to claim 3, further comprising at least one selected from the group consisting of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr in a total amount of 0.0005 to 1 wt %.

12. The high-temperature lead-free solder alloy according to claim 4, further comprising at least one selected from the group consisting of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr in a total amount of 0.0005 to 1 wt %.

13. The high-temperature lead-free solder alloy according to claim 6, further comprising at least one selected from the group consisting of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr in a total amount of 0.0005 to 1 wt %.

14. The high-temperature lead-free solder alloy according to claim 7, further comprising at least one selected from the group consisting of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr in a total amount of 0.0005 to 1 wt %.

15. The high-temperature lead-free solder alloy according to claim 8, further comprising at least one selected from the group consisting of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr in a total amount of 0.0005 to 1 wt %.

16. The high-temperature lead-free solder alloy according to claim 9, further comprising at least one selected from the group consisting of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr in a total amount of 0.0005 to 1 wt %.

17. A solder paste comprising the high-temperature lead-free solder alloy according to claim 1.

18. A solder preform comprising the high-temperature lead-free solder alloy according to claim 1.

19. A solder joint formed using the high-temperature lead-free solder alloy according to claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a schematic view showing a packaging example of a semiconductor element using a high-temperature lead-free solder alloy according to the invention.

(2) FIG. 2 is a graph showing the DSC curve of a solder alloy in Comparative Example 1.

(3) FIG. 3 is a graph showing the DSC curve of a solder alloy in Example 14.

(4) FIG. 4 is a graph showing the DSC curve of the solder alloy in Comparative Example 1 indicating methods of calculating the liquid phase rate and the solid phase rate.

(5) FIG. 5 is a cross-sectional view of a specimen used in a tensile test.

(6) FIGS. 6(a) to 6(d) are each a micrograph of a fracture surface of a specimen as taken by an optical microscope; FIG. 6(a) is a micrograph in Example 7, FIG. 6(b) a micrograph in Example 10, FIG. 6(c) a micrograph in Example 14 and FIG. 6 (d) a micrograph in Comparative Example 3.

(7) FIGS. 7(a) to 7(d) are each a micrograph of a fracture surface of a specimen as taken by an electron microscope; FIG. 7(a) is a micrograph in Example 7, FIG. 7(b) a micrograph in Example 10, FIG. 7(c) a micrograph in Example 14 and FIG. 7(d) a micrograph in Comparative Example 3.

(8) FIGS. 8(a) to 8(c) are each a micrograph of a cross-sectional surface of a joint interface between a high-temperature lead-free solder alloy of the invention and a Cu heat sink as taken by an electron microscope; FIG. 8(a) is a micrograph in Example 38, FIG. 8(b) a micrograph in Example 39, and FIG. 8(c) a micrograph in Example 40.

DESCRIPTION OF EMBODIMENTS

(9) The present invention will be described below in further detail. Unless otherwise specified, “percentage (%)” regarding the solder alloy composition as used in the specification is “percentage by weight.”

(10) A high-temperature lead-free solder alloy according to the invention has the alloy composition as described below.

(11) Sb: 35 to 40%

(12) The Sb content is in a range of 35 to 40%. Sb promotes generation of an SbSn phase having a high melting point. Sb suppresses generation of a low melting point phase to increase the solidus temperature. In addition, Sb tends to reduce the surface tension of the solder alloy and hence improves the wettability. At an Sb content of less than 35%, the effect of suppressing generation of a low melting point phase cannot be exhibited and the wettability is also deteriorated. At an Sb content in excess of 40%, the liquidus temperature considerably increases to deteriorate the solderability. The Sb content is preferably in a range of 36 to 40% and more preferably 37 to 40%.

(13) Ag: 8 to 25%

(14) The Ag content is in a range of 8 to 25%. Ag reduces the liquidus temperature to 380° C. or less. Ag generates an intermetallic compound of Sn and Ag3Sn to suppress generation of a low malting point phase, thereby improving the strength of the solder alloy. In addition, Ag reduces the surface tension in a temperature range of up to 400° C. and hence improves the wettability.

(15) At an Ag content of less than 8%, the effect of suppressing generation of a low melting point phase as obtained by addition of Ag cannot be exhibited. At an Ag content in excess of 25%, Sb and Ag preferentially form an Ag3Sb phase and hence the Ag3Sb phase appears at the initial stage of solidification. Therefore, a low melting point phase is store likely to be generated in the solder alloy.

(16) Formation of the Ag3Sb phase from Sb and Ag in the initial stage of solidification relatively reduces the Sb and Ag concentrations in the liquid phase remaining in the process of solidifying the solder alloy. Decreases in concentrations of Sb and Ag in the remaining liquid phase reduce the effect of suppressing generation of a low melting point phase to increase the ratio of the low melting point phase at 250° C. or less. Therefore, the heat resistance of the solder alloy is deteriorated. The Ag content is preferably in a range of 10 to 22% and more preferably 12 to 18%.

(17) Cu: 5 to 10%

(18) The Cu content is in a range of 5 to 10%. Cu controls the liquidus temperature in a range of 340 to 380° C. Cu mainly generates Cu3Sn and Cu6Sn5 to suppress generation of a low melting point phase, thereby improving the tensile strength of the solder alloy.

(19) At a Cu content of less than 5%, the effect of suppressing generation of a low melting point phase as obtained by addition of Cu cannot be exhibited. At a Cu content in excess of 10%, Sb and Cu preferentially form a Cu2Sb phase and hence the Cu2Sb phase appears at the initial stage of solidification of the solder alloy. Therefore, a low melting point phase is more likely to be generated in the solder alloy.

(20) Formation of the Cu2Sb phase from Sb and Cu in the initial stage of solidification of the solder alloy relatively reduces the Sb and Cu concentrations in the liquid phase remaining in the process of solidifying the solder alloy. Decreases in concentrations of Sb and Cu in the remaining liquid phase reduce the effect of suppressing generation of a low molting point phase of Sb and Cu to increase the ratio of the low melting point phase at 250° C. or less. Therefore, the heat resistance of the solder alloy is deteriorated. In addition, the liquidus temperature of the solder alloy is increased to reduce the wettability, thereby reducing the solderability. The Cu content is preferably in a range of 6 to 9% and more preferably 6 to 6%.

(21) The low melting point phase is a solidified phase which is formed by solidification segregation at the time of cooling of the solder alloy after melting and which has a melting point of 210 to 250° C. In general, solidification segregation is a phenomenon in which specific ingredients segregate due to a difference in composition between the first solidified portion and the last solidified portion upon solidification of a molten phase. In general, solidification segregation is more likely to occur with decreasing cooling rate. Particularly in a lead-free solder alloy containing a large amount of Sn, a low-melting-point Sn single phase is more likely to segregate. From such a standpoint, the present invention is characterized by suppressing, in the solder joint, generation of a low melting point phase in which the Sn single phase is considered to be a main ingredient.

(22) The low melting point phase includes the Sn single phase as its main ingredient because the solidus temperature which is the melting point of the low melting point phase is at the same level as the melting point of Sn which is 232° C. The rest of the low melting point phase is considered to be composed of a residual phase having a composition closer to Sb2Sn3 having a melting point of about 240° C. and an Sn—Ag—Cu eutectic composition having a melting point of about 220 to 230° C. Therefore, the solidus temperature which is the melting point of the low melting point phase is considered to be a temperature in a range of 210 to 250° C.

(23) The low melting point phase is generated at least in the case of having such an alloy composition that the Sn content exceeds the total content of Sb, Ag and Cu. In other words, the low melting point phase is generated when Sb+Ag+Cu<Sn is satisfied. The reason why generation of the low melting point phase is suppressed as in the present invention when the Ag content is 8 to 25% and the Cu content is 5 to 10% is considered to be preferential formation of intermetallic compounds of Sb, Ag and Cu with Sn during solidification, thus forming a high melting point phase. However, the precise mechanism thereof is not known.

(24) The high melting point phase as used in the invention is a solidified phase composed of an intermetallic compound showing a melting point of 290° C. or more, as exemplified by Cu6Sn5, Cu3Sn, Ag3Sn, SbSn or Ni3Sn4.

(25) A solder joint for which soldering was performed using the solder alloy according to the invention has these intermetallic compounds each constituting the high melting point phase but may contain other intermetallic compounds than the compounds illustrated above as long as the high melting point phase is a solidified phase showing a melting point of 290° C. or more. In other words, since the solidified phase showing a melting point of 290° C. or more accounts for a large portion of the structure, the solder joint obtained by soldering using the solder alloy according to the invention exhibits excellent heat resistance and tensile strength.

(26) At least one selected from the group consisting of 0.003 to 1.0% of Al, 0.01 to 0.2% of Fe and 0.005 to 0.4% of Ti

(27) These elements finely disperse phases respectively composed of intermetallic compounds such as Cu6Sn5, Cu3Sn and Ag3Sn in an SbSn phase to improve the tensile strength and elongation.

(28) In the high-temperature lead-free solder alloy according to the invention, the Sn—Sb—Ag—Cu solder alloy contains Al, Fe and Ti and hence these elements preferentially crystallize during solidification to serve as heterogeneous nucleation seeds, thereby preventing each phase from coarsening. When nucleation of each phase is promoted by heterogeneous nucleation, the number of starting points for nucleation is increased and hence the phases of the intermetallic compounds such as Cu6Sn5, Cu3Sn and Ag3Sn are finely dispersed. Therefore, in the high-temperature lead-free solder alloy according to the invention, the area of the crystal grain boundaries in the solder alloy increases to disperse the stress applied to the grain boundaries and hence various mechanical properties and particularly the elongation are considered to be more significantly improved than a solder alloy in which the respective intermetallic compound phases are coarsened.

(29) Al, Ti and Fe are added in amounts as minute as 0.003 to 1.6%. Therefore, even if a compound having a higher melting point than SbSn is produced as an intermetallic compound containing Sb, Ag and Cu as well as any of Al, Ti and Fe, Sb, Ag and Cu in the solder alloy are not consumed too much. Accordingly, generation of a coarse low melting point phase is suppressed and hence the joint strength of a solder joint is less likely to deteriorate.

(30) The Al content is preferably in a range of 0.01 to 0.8% and more preferably 0.02 to 0.5% in order that the above-described effect may foe sufficiently exhibited. The Fe content is preferably in a range of 0.02 to 0.15% and more preferably 0.02 to 0.1%. The Ti content is preferably in a range of 0.01 to 0.3% and more preferably 0.02 to 0.2%.

(31) If the contents of these elements are less than their lower limit values, there is no effect of refining the solder alloy structure and the tensile strength and elongation are not sufficiently improved. If the contents of these elements exceed their upper limit values, intermetallic compounds containing these elements are coarsened. Therefore, a stress applied to the solder alloy concentrates on the grain boundaries of the intermetallic compounds, thus deteriorating the tensile strength and elongation.

(32) The high-temperature lead-free solder alloy according to the invention may contain the following elements as optional ingredients.

(33) At least one selected from the group consisting of P, Ge and Ga in a total amount of 0.002 to 0.1%

(34) These elements have the effect of improving the wettability by suppressing emergence of oxidizable Al, Fe and Ti on the solder alloy surface during solidification of the solder alloy. Al, Fe and Ti thus remain inside the solder alloy to further promote structure refining by way of the above-described heterogeneous nucleation. As a result, these elements also have the effect of considerably improving the elongation of the solder alloy. The total content of these elements is more preferably in a range of 0.003 to 0.01%. The contents of the respective elements are not particularly limited but in order that the above-described effects may be sufficiently exhibited, the P content is preferably in a range of 0.002 to 0.005%, the Ge content is preferably in a range of 0.002 to 0.006% and the Ga content is preferably in a range of 0.002 to 0.02%.

(35) At least one selected from the group consisting of Ni, Co and Mn in a total amount of 0.01 to 0.5%

(36) These elements suppress diffusion of ingredients of a plated layer formed in a semiconductor element or an external substrate at the time of soldering into the solder alloy. Therefore, these elements have the effect of maintaining the structure of the solder alloy constituting a solder joint while reducing the thickness of an intermetallic compound layer to be formed at the joint interface. Accordingly, these elements can enhance the joint strength of the solder joint. The total content of these elements is more preferably in a range of 0.01 to 0.05%. The contents of the respective elements are not particularly limited but in order that the above-described effect may be sufficiently exhibited, the Ni content is preferably in a range of 0.02 to 0.07%, the Co content is preferably in a range of 0.02 to 0.04% and the Mn content is preferably in a range of 0.02 to 0.05%. Of these elements, Ni is a particularly preferable element as an element exhibiting the above-described effect.

(37) At least one selected from the group consisting of Zn and Bi in a total amount of 0.005 to 0.5%

(38) These elements further increase the solid phase rate of the solder alloy at 280° C. to improve the tensile strength. The total content of these elements is more preferably in a range of 0.005 to 0.4% and most preferably 0.01 to 0.3%. The contents of the respective elements are not particularly limited but in order that the above-described effect may be sufficiently exhibited, the Zn content is preferably in a range of 0.01 to 0.2%, and the Bi content is preferably in a range of 0.02 to 0.3%.

(39) At least one selected from the group consisting of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr in a total amount of 0.0005 to 1%

(40) These elements improve the mechanical ductility at 250° C. as with P, Ge and Ga. These elements are oxidizable and more easily oxidize than Al, Ti and Fe, and have the effect of promoting structure refining as obtained using Al, Ti and Fe by having Al, Ti and Fe remain inside the solder. The total content of these elements is more preferably in a range of 0.01 to 0.03%. The contents of the respective elements are not particularly limited but in order that the above-described effect may be sufficiently exhibited, the contents of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr are each preferably in a range of 0.02 to 0.03%.

(41) The high-temperature lead-free solder alloy according to the invention preferably has a solidus temperature of 280° C. or more and preferably 290° C. or more. The solidus temperature was thus defined for the following reasons:

(42) The solidus temperature was defined to allow the solder joint using the high-temperature lead-free solder alloy according to the invention to have sufficient heat resistance to resist heat generation from an SiC semiconductor element, a GaN semiconductor element and a GaAs semiconductor element which operate at a high temperature of 250° C. or more, to have a solid phase ratio of 98% or more and to ensure good reliability. Another reason for which the solidus temperature is defined to be 280° C. or more and preferably 290° C. or more is that the reflow temperature at the time of joining of another electronic component to a packaging substrate in the subsequent step after a semiconductor element is joined to the packaging substrate may reach 260° C. The solder joint is required to show a solidus temperature of 280° C. or more and preferably 290° C. or more as the temperature capable of coping well with such reflow temperature without remelting. Even in a solder alloy having a solidus temperature of up to 250° C., if the solid phase rate at 280° C. is 98% or more, the mechanical strength and in particular the elongation of the solder joint at 250° C. are good and connection can also be maintained at the time of repeated reflowing.

(43) The “solid phase ratio” as used in the invention refers to a ratio (%) of the area of endothermic peaks as detected at 280° C. or more to the total area of endothermic peaks in a DSC curve as measured at a temperature elevation rate of 5° C./min using a solder alloy solidified at a cooling rate of 1° C./min as the sample.

(44) The high-temperature lead-free solder alloy according to the invention preferably has a liquidus temperature of up to 400° C. The soldering temperature needs to be a temperature elevated above the liquidus temperature. Therefore, at a liquidus temperature above 400° C., the soldering temperature needs to be higher than this temperature but at such a high temperature, the running cost at the time of production is high and the workability is deteriorated. Furthermore, the liquidus temperature is more preferably up to 380° C. from the standpoints of heat resistance of a semiconductor component itself and protection of circuit wiring inside the semiconductor component.

(45) The high-temperature lead-free solder alloy according to the invention can also be used in die bonding of a semiconductor element, in other words, in joining of a semiconductor element to a heat sink. The high-temperature lead-free solder alloy according to the invention can also be applied to soldering of connector terminals and motherboards, to mounting of DIP ICs or the like on printed circuit boards, to assembly and mounting of electronic components such as capacitors, to sealing of ceramic packages, to attachment of leads to diodes and the like, and to solder preforms for semiconductor soldering.

(46) The high-temperature lead-free solder alloy according to the invention can be suitably used in the form of a solder preform or solder paste. Such a preform material is in the shape of a washer, a ring, a pellet, a disk, a ribbon, a wire, a ball or the like.

(47) A solder preform may be used for joining in a reducing atmosphere without using flux. Joining in a reducing atmosphere does not cause contamination of joined portions with flux, so it has the advantages that not only does it become unnecessary to clean the joined portions in a step following the joining but also that voids in solder joints can be greatly decreased.

(48) The high-temperature lead-free solder alloy according to the invention can be used in the form of solder paste. The solder paste is in a paste form and is obtained by mixing solder alloy powder with a small amount of flux. The high-temperature lead-free solder alloy according to the invention may be used in the form of solder paste when mounting electronic components on a printed circuit board by a reflow soldering method. The flux for use in solder paste may be a water-soluble flux or a water-insoluble flux. Typically, a rosin flux which is a rosin-based water-insoluble flux is used.

(49) FIG. 1 is a schematic view showing a packaging example of a semiconductor element using a high-temperature lead-free solder alloy according to the invention. The high-temperature lead-free solder alloy according to the invention may be used as a high-temperature solder alloy for joining (die bonding) a semiconductor element to a heat sink. As shown in FIG. 1, each of a semiconductor element 1 and a heat sink 2 has a plated layer 3 made of Cu, Ni, Ni/Au, Ag, or the like. A high-temperature lead-free solder alloy 4 according to the invention connects the plated layers 3 to each other to form a solder joint.

(50) The solder joint according to the invention is formed using the high-temperature lead-free solder alloy according to the invention. For example, referring to FIG. 1, the solder joint according to the invention includes the plated layers 3 and the solder alloy 4.

(51) As for the conditions for manufacturing the solder joint according to the invention, the cooling rate at the time of solidification is preferably in a range of 0.8 to 50° C./sec. The cooling rate within this range covers the cooling rate in most of currently used soldering devices. Therefore, in a case where the solder alloy according to the invention is used to perform soldering, it is not particularly necessary to make any particular changes to the cooling rate at the time of soldering. Owing to such excellent effects of the invention, even in a case where a semiconductor element is joined to a large-scale printed circuit board or heat sink having a large heat capacity, it is not necessary to change the cooling rate in the high-temperature lead-free solder alloy according to the invention, and soldering is performed under conventional cooling conditions. This is because the high-temperature lead-free solder alloy according to the invention can exhibit excellent connection reliability while suppressing generation of a low melting point phase even when the slow cooling is performed at 0.8° C./sec. The cooling rate is more preferably 1 to 10° C./sec.

(52) The high-temperature lead-free solder alloy according to the invention exhibits its effects particularly in cases where a semiconductor element as described above which operates at a high temperature of about 250 to 280° C. is soldered to a heat sink. As a matter of course, the high-temperature lead-free solder alloy according to the invention does not generate a low melting point phase and can exhibit sufficiently high connection reliability even when used for a solder joint having a required heat resistant temperature of up to 250° C.

(53) The solder alloy according to the invention manufactured using a high purity material or a low alpha material is a low alpha solder alloy. Software errors can be prevented from occurring by using it on the periphery of a memory.

EXAMPLES

(54) Solder alloys having the respective alloy compositions shown in Tables 1 and 2 were melted at 430° C. and then each solder alloy was cooled at a cooling rate of 1° C./sec in order to simulate the formation of each solder joint after soldering. The cooling rate is controlled by a thermocouple which detects the furnace temperature of DSC. To be more specific, the cooling rate of 1° C./sec is a value obtained when a solder alloy having been completely melted at 430° C. is then cooled to 180° C. at a temperature reduction rate of 1° C./sec.

(55) A DSC curve of the cooled solder alloy was obtained by increasing the temperature at 5° C./min in air using DSC (model: Q2000) manufactured by TA Instruments Japan Inc. From the resulting DSC curve, the solidus temperature, the liquidus temperature, the liquid phase rate and the solid phase rate were determined. The results are compiled in Tables 1 and 2.

(56) FIG. 2 is a graph showing the DSC curve of a solder alloy in Comparative Example 1. FIG. 3 is a graph showing the DSC curve of a solder alloy in Example 14. These DSC curves are obtained by increasing the temperature of the solder alloys solidified at a cooling rate of 1° C./sec at 5° C./min.

(57) In the DSC curve shown in FIG. 2, the temperature at the start of endotherm of the first endothermic peak is the solidus temperature, and the temperature at the completion of endotherm of the last endothermic peak is the liquidus temperature. However, in a case where there is only one endothermic peak as shown in FIG. 3, the temperature at the start of endotherm of the endothermic peak is the solidus temperature, and the temperature at the completion of endotherm of this endothermic peak is the liquidus temperature.

(58) As is clear from FIG. 2, in the solder alloy of Comparative Example 1 in which the alloy composition is outside the range of the invention, two endothermic peaks were observed, and the solidus temperature shown was 227° C. On the other hand, as is clear from FIG. 3, in the solder alloy of Example 14 in which the alloy composition is within the range of the invention, only one endothermic peak was observed, and the solidus temperature shown was 323° C.

(59) In the alloy compositions shown in Comparative Examples except Comparative Examples 4, 5 and 10, an endothermic peak was observed at a temperature below 280° C.

(60) Methods of calculating the liquid phase rate and the solid phase rate will be described in detail, taking the DSC curve in Comparative Example 1 as shown in FIG. 4 as an example.

(61) The liquid phase rate at 280° C. was determined as follows: First, as shown in FIG. 4, a baseline 8 was drawn, and the area V.sub.0(V.sub.0=V.sub.1+V.sub.2) surrounded by the baseline 8 and a DSC curve 9 was determined. A dividing line 10 was then drawn at 280° C. and the area V.sub.1 surrounded by the dividing line 10, the DSC curve 9 at 280° C. or less and the baseline 8 was determined. Finally, the liquid phase rate (percentage) at 280° C. was calculated by (V.sub.1/V.sub.0)×100. On the other hand, in a case where no endothermic peak was observed at a temperature of 280° C. or less as shown in FIG. 3, the area V.sub.1 is 0 and hence the liquid phase rate at 280° C. becomes 0%.

(62) The solid phase rate at 280° C. was determined as follows: The area V.sub.2 surrounded by the dividing line 10, the DSC curve 9 at 280° C. or more and the baseline 8 as shown in FIG. 4 was determined. The liquid phase rate at 280° C. was then calculated by (V.sub.2/V.sub.0)×100 to obtain the solid phase rate. On the other hand, in a case where an endothermic peak was observed only at 280° C. or more as shown in FIG. 3, V.sub.2 is equal to V.sub.0, so the solid phase rate at 280° C. becomes 100%. The measurement results are shown in Tables 1 and 2.

(63) In addition, a solder alloy having each alloy composition shown in Tables 1 and 2 was cast into a mold to prepare a specimen having a predetermined shape. Methods of measuring the tensile strength and the elongation at break are as described below.

(64) A specimen has a shape shown in FIG. 5. Its parallel portion has dimensions of 8 mm in diameter (φ) and 30 mm in length. The specimen was obtained by melting each solder alloy at the liquidus temperature of each composition+100° C., casting the molten solder alloy into a split mold made by working according to the above-described dimensions, cooling the cast solder alloy with air until the temperature decreases to room temperature and taking the cooled solder alloy out of the split mold. A thermocouple was attached to the casting portion of the split mold and the temperature history during solidification was measured. As a result, the cooling rate was about 1 to 3° C./sec. A tensile test was performed in a thermostatic chamber at 250° C. in air at a crosshead speed of 0.09 mm/min using Autograph 5966 manufactured by Instron.

(65) The tensile strength and the elongation at break were calculated from the load and the displacement values read from a load cell of the tensile tester. According to the invention, in a case where a solder alloy showed a tensile strength of 5 MPa or more and an elongation at break of 5% or more, the solder alloy was deemed to have sufficient mechanical properties to prevent easy fracture at high temperature even when used for a solder joint.

(66) TABLE-US-00001 TABLE 1 Alloy composition [%] Sn Sb Ag Cu Al Fe Ti P Ge Ga Co Mn Ni Bi Zn In V Ca Pt Example 1 bal. 35 8 5 0.003 Example 2 bal. 37 8 7 0.01 Example 3 bal. 37 15 6 0.013 Example 4 bal. 37 8 7 0.03 Example 5 bal. 40 20 8 0.08 Example 6 bal. 35 15 5 0.11 Example 7 bal. 37 8 7 0.33 Example 8 bal. 37 15 8 1 Example 9 bal. 37 8 7 0.01 Example 10 bal. 37 15 8 0.02 Example 11 bal. 37 8 7 0.045 Example 12 bal. 40 20 8 0.1 Example 13 bal. 37 8 7 0.005 Example 14 bal. 37 15 6 0.02 Example 15 bal. 37 8 7 0.04 Example 16 bal. 40 20 8 0.2 Example 17 bal. 36 15 6 0.01 0.003 Example 18 bal. 35 15 5 0.085 0.003 Example 19 bal. 36 15 5 0.015 0.005 Example 20 bal. 36 15 6 0.01 0.01 Example 21 bal. 37 15 6 0.08 0.04 Example 22 bal. 37 15 6 0.05 0.02 Example 23 bal. 37 15 6 0.08 0.03 Example 24 bal. 37 15 6 0.1 0.3 Example 25 bal. 37 15 6 0.007 0.3 Example 26 bal. 37 15 5 0.003 0.9 Example 27 bal. 37 15 6 0.01 0.005 Example 28 bal. 37 15 6 0.008 0.1 Example 29 bal. 37 15 6 0.004 0.0098 Example 30 bal. 37 15 6 0.05 Example 31 bal. 35 15 6 0.003 Solidus Liquidus Liquid Solid Tensile Elongation Alloy composition [%] temp. temp. phase rate phase rate strength at break Pd Ce Mo Nb Zr Mg Au [° C.] [° C.] [° C.] [° C.] [Mpa] [%] Example 1 228.4 380.3 1.5 98.5 26.9 5.3 Example 2 300.2 358.9 0.0 100.0 33.3 36.9 Example 3 297.7 357.0 0.0 100.0 29.9 40.2 Example 4 300.8 359.5 0.0 100.0 12.9 45.6 Example 5 338.2 375.1 0.0 100.0 26.0 72.9 Example 6 227.8 348.2 1.9 98.1 17.5 124.0 Example 7 298.5 358.8 0.0 100.0 14.1 85.7 Example 8 228.6 359.8 1.9 98.1 14.2 24.1 Example 9 304.6 358.9 0.0 100.0 33.2 35.2 Example 10 326.1 356.5 0.0 100.0 30.9 39.1 Example 11 303.9 358.5 0.0 100.0 38.3 11.9 Example 12 327.6 373.6 0.0 100.0 38.7 75.1 Example 13 301.3 359.0 0.0 100.0 34.7 53.1 Example 14 323.6 356.2 0.0 100.0 32.2 117.9 Example 15 301.0 358.6 0.0 100.0 12.6 74.2 Example 16 328.6 375.2 0.0 100.0 33.4 96.8 Example 17 324.7 354.7 0.0 100.0 30.1 112.3 Example 18 227.3 346.9 1.5 98.5 11.0 346.0 Example 19 322.2 356.7 0.0 100.0 28.7 63.3 Example 20 322.1 358.2 0.0 100.0 27.7 71.2 Example 21 299.3 348.1 0.0 100.0 18.7 134.9 Example 22 301.0 350.1 0.0 100.0 20.0 181.7 Example 23 299.5 356.4 0.0 100.0 19.5 120.5 Example 24 227.6 351.4 0.7 99.3 13.4 26.5 Example 25 228.9 352.3 0.3 99.7 20.9 272.0 Example 26 221.6 346.1 1.3 98.7 8.6 209.1 Example 27 304.4 358.0 0.0 100.0 25.5 153.6 Example 28 225.6 358.5 0.4 99.6 27.5 23.9 Example 29 300.3 365.9 0.0 100.0 23.6 43.0 Example 30 0.015 305.1 358.7 0.0 100.0 23.5 102.6 Example 31 0.049 324.2 380.0 0.0 100.0 28.0 125.6

(67) TABLE-US-00002 TABLE 2 Alloy composition [%] Sn Sb Ag Cu Al Fe Ti P Ge Ga Co Mn Ni Bi Zn In V Ca Pt Example 32 bal. 37 15 6 0.003 Example 33 bal. 37 15 6 0.03 Example 34 bal. 37 15 6 0.03 0.1 Example 35 bal. 37 15 6 0.009 Example 36 bal. 37 15 6 0.04 Example 37 bal. 40 20 8 0.046 0.003 0.003 0.002 0.004 0.09 0.01 0.016 0.05 0.044 0.53 0.03 0.012 0.04 0.012 Comparative bal. 34 5 5 Example 1 Comparative bal. 35 8 5 Example 2 Comparative bal. 35 15 5 Example 3 Comparative bal. 37 8 7 Example 4 Comparative bal. 40 20 6 Example 5 Comparative bal. 37 8 7 0.25 Example 6 Comparative bal. 37 8 7 0.43 Example 7 Comparative bal. 35 8 5 0.002 Example 8 Comparative bal. 37 15 6 1.14 Example 9 Comparative bal. 37 8 7 0.006 Example 10 Comparative bal. 35 8 5 0.004 Example 11 Solidus Liquidus Liquid Solid Tensile Elongation Alloy composition [%] temp. temp. phase rate phase rate strength at break Pd Ce Mo Nb Zr Mg Au [° C.] [° C.] [° C.] [° C.] [Mpa] [%] Example 32 0.0025 326.0 360.4 0.0 100.0 31.8 66.8 Example 33 0.003 225.7 358.4 0.0 100.0 13.3 6.0 Example 34 0.0008 224.0 354.2 0.5 99.5 31.3 8.9 Example 35 0.0045 226.6 354.7 0.5 99.5 28.2 56.7 Example 36 0.02 225.5 358.0 0.2 99.8 29.3 33.2 Example 37 0.03 0.02 0.023 0.002 0.0007 0.002 0.01 333.5 375.0 0.0 100.0 29.3 140.8 Comparative 227.0 357.2 8.8 91.2 0.6 2.1 Example 1 Comparative 228.4 382.9 2.2 97.8 3.2 1.1 Example 2 Comparative 226.9 356.9 0.4 99.6 29.9 1.8 Example 3 Comparative 303.2 359.2 0.0 100.0 35.1 2.8 Example 4 Comparative 336.9 375.3 0.0 100.0 28.9 1.9 Example 5 Comparative 226.4 359.1 2.7 97.3 15.4 0.3 Example 6 Comparative 227.2 359.4 3.0 97.0 13.1 0.3 Example 7 Comparative 227.9 362.8 2.4 97.6 4.5 1.8 Example 8 Comparative 228.5 359.6 3.7 96.3 12.8 3.2 Example 9 Comparative 302.8 359.2 0.0 100.0 33.2 2.9 Example 10 Comparative 229.1 362.3 1.5 98.5 7.7 1.2 Example 11

(68) Each of Examples 1 to 37 in which the alloy composition is within the range of the invention showed a solid phase rate of 98% or more, a liquidus temperature of up to 376° C., a tensile strength at 250° C. of 5 MPa or more, and an elongation at break of 5% or more. On the other hand, each of Comparative Examples 1 to 11 in which Al, Fe and Ti are not contained or Al, Fe and Ti are contained in amounts outside the ranges of the invention only showed an elongation at break value of less than 4%. For example, each of Comparative Examples 3, 4, 5, 10 and 11 shows a solid phase rate at 250° C. of 98% or more, thus satisfying sufficient heat resistance but shows an elongation at break at 250° C. of less than 3%, thus not satisfying mechanical ductility. However, in Examples 2, 4, 5, 6, 7, 9, 11, 12, 13, 15, 16, 18 and 37 in which Al, Fe or Ti is added in a specific amount, the mechanical ductility is considerably improved.

(69) Comparative Examples 1 to 5 in which Al, Fe or Ti is not contained each have an elongation at break of up to 3% although some of them show a high tensile strength. Comparative Examples 6 to 11 in which the Al, Fe and Ti contents are outside the ranges of the invention each have a low elongation at break value although some of them show a high tensile strength.

(70) FIGS. 6(a) to 6(d) are each a micrograph of a fracture surface of a specimen as taken by an optical microscope; FIG. 6(a) is a micrograph in Example 7, FIG. 6(b) a micrograph in Example 10, FIG. 6(c) a micrograph in Example 14 and FIG. 6(d) a micrograph in Comparative Example 3. The micrographs shown in FIGS. 6(a) to 6(d) are taken at a to magnification of 20×.

(71) FIGS. 7(a) to 7(d) are each a micrograph of a fracture surface of a specimen as taken by an electron microscope; FIG. 7(a) is a micrograph in Example 7, FIG. 7(b) a micrograph in Example 10, FIG. 7(c) a micrograph in Example 14 and FIG. 7(d) a micrograph in Comparative Example 3. The micrographs shown in FIGS. 7(a) to 7(d) are taken at a magnification of 200×.

(72) As shown in FIGS. 6(a) to 6(d), it was revealed that grain regions surrounded by cracks seen in the fracture surface in FIGS. 6(a) to 6(c) are clearly smaller in size than those in FIG. 6 (d). It was also revealed that phases of intermetallic compounds such as Ag3Sn and Cu3Sn are finely dispersed in an SbSn phase in FIGS. 7(a) to 7(c), whereas an SbSn phase and coarse phases of intermetallic compounds such as Ag3Sn and Cu3Sn form a lamellar structure in FIG. 7(d).

(73) In the high-temperature lead-free solder alloy according to the invention, the phases of Ag3Sn, Cu6Sn5, Cu3Sn and the like are finely dispersed in the SbSn phase as shown in FIGS. 7(a) to 7(c) to increase the area of crystal grain boundaries, thereby reducing the concentration of stress. Therefore, the grain regions surrounded by the cracks seen in the fracture surface as shown in FIGS. 6(a) to 6(c) are considered to be smaller in size than the grain regions surrounded by the cracks seen in the fracture surface as shown in FIG. 6(d).

(74) The high-temperature lead-free solder alloy according to the invention can thus reduce the concentration of stress due to strain while suppressing the fracture of each grain boundary and hence is considered to show excellent tensile strength and elongation at break.

(75) In addition, each solder alloy according to the invention was used to form a solder joint on a heat sink and the state of the joint interface between the solder alloy and the heat sink was examined.

(76) TABLE-US-00003 TABLE 3 Solidus Liquidus Liquid Solid Thickness of Alloy composition [%] temperature temperature phase rate phase rate IMC layer Sn Sb Ag Cu Al Ni [° C.] [° C.] [° C.] [° C.] [μm] Example 38 bal. 37 15 6 0.02 0 328.0 358.4 0.0 100.0 4.0 Example 39 bal. 37 15 6 0.02 0.03 326.0 358.6 0.0 100.0 3.5 Example 40 bal. 37 15 6 0.02 0.07 327.0 358.7 0.0 100.0 2.3

(77) Each of Examples 38, 39 and 40 in which the alloy composition is within the range of the invention shows a solid phase rate of 100% and a liquidus temperature of up to 376° C., and has good heat resistance. Moreover, since the Al content is within the range of the invention, the mechanical strength and the ductility are also obviously satisfied. In addition, an intermetallic compound layer (IMC) formed at the joint interface with the heat sink is thinner in Examples 39 and 40 than in Example 38 in which Ni is not contained. It is commonly known that the joint reliability reduces at the joint interface between the solder alloy and the heat sink if the intermetallic compound layer formed in the vicinity of the joint interface has a large thickness. In other words, by further adding Ni to a solder alloy obtained by incorporating Al, Ti and Fe in an Sn—Sb—Ag—Cu alloy within the scope of the invention, the intermetallic compound layer can be prevented from having an increased thickness, thereby further improving the joint reliability.

(78) FIGS. 8(a) to 8(c) are each a micrograph of a cross-sectional surface of a joint interface between a high-temperature lead-free solder alloy of the invention and a Cu heat sink as taken by an electron microscope. The Cu heat sink has a size of 30×20×2 mm and is made of Cu. An Si chip has a size of 5×5×0.5 mm and joint electrode portions are flash-plated with Ni/Au.

(79) Reflow soldering was performed by applying proper flux to the central portion of a Cu heat sink, putting solder alloy having a weight of about 10 mg on the flux and mounting an Si chip thereon. Joining conditions are as follows. A vacuum H.sub.2 soldering device manufactured by Shinko Seiki Co., Ltd. was used; temperature elevation rate: 1.8 [° C./sec]; peak temperature: 367 [° C.]; solder alloy melting time: 80 seconds; and cooling rate: 1.7 [° C./sec].

(80) FIG. 8(a) is an electron micrograph of a cross-sectional surface of a joint interface between a solder alloy in Example 38 (Sn-37% Sb-6% Cu-15% Ag-0.02% Al) and a Cu heat sink; FIG. 8(b) is an electron micrograph of a cross-sectional surface of a joint interface between a solder alloy in Example 39 (Sn-37% Sb-6% Cu-15% Ag-0.02% Al-0.03% Ni) and a Cu heat sink; and FIG. 8(c) is an electron micrograph of a cross-sectional surface of a joint interface between a solder alloy in Example 40 (Sn-37% Sb-6% Cu-15% Ag-0.02% Al-0.07% Ni) and a Cu heat sink.

(81) As shown in FIGS. 8(a) to 8(c), the solder joint in Example 33 forms a CuSb intermetallic compound phase with a thickness of about 4 (μm) at the joint interface with the Cu heat sink. The solder joints using the solder alloys described in Examples 39 and 40 have IMC thicknesses of 3.5 (μm) and 2.3 (μm), respectively. FIGS. 8(a) to 8(c) reveal that liquation of Cu electrode ingredients from the Cu heat sinks into the solder alloys is suppressed and the layers made of various intermetallic compounds as formed at the joint interfaces are thin.

(82) From the above, the high-temperature lead-free solder alloy according to the invention has excellent tensile strength and elongation under a high temperature environment of 250° C. Therefore, the high-temperature lead-free solder alloy according to the invention can reduce thermal stress applied to a solder joint that may be caused by thermal strain due to a difference in coefficient of thermal expansion between each substrate and a joined component. As described above, in the high-temperature lead-free solder alloy according to the invention, the solder joint does not cause fracture with respect to a semiconductor element capable of high temperature operation. The high-temperature lead-free solder alloy according to the invention can also be used without any problem even in such an environment that the solder alloy may be exposed to high temperature.