• 专利附录
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    • 专利摘要:
    high temperature unleaded solder alloy, solder paste, precast solder and weld joint The present invention relates to providing a high temperature unleaded solder alloy with excellent tensile and elongation resistance in an environment high temperature of 250 ° c. To make the structure of a sn-sb-ag-cu weld thinner and to cause dispersion of the stress applied to the weld alloy, at least one material selected from the group consisting of, % by mass, 0.003 to 1.0% of al, 0.01 to 0.2% of fe, and 0.005 to 0.4% of ti to a solder alloy containing 35 to 40% sb, 8 to 25 % ag, and 5 to 10% cu, the remainder consisting of sn.
    公开号:BR112015002414B1
    申请号:R112015002414-9
    申请日:2013-07-29
    公开日:2019-10-01
    发明作者:Rei Fujimaki；Minoru Ueshima
    申请人:Senju Metal Industry Co., Ltd.；
    IPC主号:
    专利说明:

    HIGH TEMPERATURE LEAD WITHOUT ALLOY, WELDING PASTE, PRE-MOLDED WELDING AND WELDING JOINT
    TECHNICAL FIELD [001]. The present invention relates to a high temperature lead-free solder alloy based on Sn-Sb-Ag-Cu.
    BACKGROUND OF THE INVENTION [002]. In recent years, as higher levels of properties of semiconductor elements are required, their environment of use also becomes increasingly demanding. Therefore, Si (hereinafter referred to as a semiconductor element of Si) that was conventionally used as a material of the semiconductor element must be replaced by SiC, GaAs, GaN and the like. These are referred to as a SiC semiconductor element, a GaAs semiconductor element and a GaN semiconductor element, respectively. Each of the semiconductor elements of SiC, GaAs and GaN has excellent properties, including excellent pressure resistance, an increase in operating temperature and an extended bandwidth, and is applied to power transistors and optical devices such as LEDs. These semiconductor elements are called new generation semiconductors and are necessary for operation at high temperatures, and therefore the solder joints used for them can also reach a temperature of approximately 250 to 280 ° C. Thus, it is necessary to use a high temperature solder in the aforementioned new generation semiconductors.
    [003]. In addition, in general, a semiconductor element can be connected to a heat sink, such as a metal core or a ceramic plate for heat dissipation, and a high temperature solder is also used for said connection purposes.
    [004]. So far some high-temperature solders and an Au-20Sn solder alloy which is an Au-Sn eutectic composition alloy are known
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    2/32 is known as a conventional high temperature lead-free solder alloy. The Au-20Sn solder alloy has a eutectic temperature of 280 ° C and therefore can be used at 250 ° C or more, but below 280 ° C. However, this is a very expensive material.
    [005]. A low cost example, high temperature lead-free solder alloys include a Sn-Sb-based solder alloy, a Bi-based solder alloy, a Zn-based solder alloy and a sintered alloy containing Ag. Of these, a solder alloy based on Sn-Sb is better than a solder alloy based on Bi, a solder alloy based on Zn and a sintered alloy containing Ag in terms of thermal conductivity, corrosion resistance and strength of Joins.
    [006]. Each of the Patent Processes 1 to 3 discloses a Sn-Sb-Ag-Cu solder alloy obtained by adding Ag and Cu to a Sn-Sb solder alloy, such as a high temperature solder alloy, which also can be used in a temperature range of 250 to 280 ° C.
    [007]. In other words, each of the Patent Processes 1 to 3 discloses a Sn-Sb-Ag-Cu solder alloy having a solid temperature above 250 ° C to improve heat resistance.
    [008]. In addition, Patent Process 4 proposes a solder alloy obtained by adding Fe to a Sn-Sb-Ag-Cu solder alloy to improve the heat cycle properties.
    LIST OF QUOTE [009]. Patent Process 1: JP 2005-340267 A [0010]. Patent Process 2: JP 2007-152385 A [0011]. Patent Process 3: JP 2005-340268 A [0012]. Patent Process 4: JP 2005-177842 A
    BRIEF DESCRIPTION OF THE INVENTION
    TECHNICAL PROBLEMS [0013]. In general, it is assumed that the cooling rate at the time of the light weld is about 0.8 to 50 ° C / sec. According
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    3/32 α recent technical welding trend, a considerably low cooling rate of, for example, 1 ° C / sec, can be adopted for common reflow soldering. It can be concluded that this condition is considerably serious as the weld condition. In the descriptive report, for convenience, this is collectively referred to as slow cooling.
    [0014]. However, in some of the solder alloys disclosed in Patent Processes 1 to 3, a low melting point phase is formed, which melts at 210 to 250 ° C by slow cooling in an amount greater than 2%. In these solder alloys, the low melting point phase melts at the operating temperature of a semiconductor element ranging between 250 and 280 ° C, where a solder joint has a low resistance part, where solid and liquid coexist. If a load is still applied to the low resistance part, the tensile strength is considerably reduced. Therefore, a solder joint obtained by soldering using a solder alloy that has a large amount of a low melting point phase as selected from the solder alloys disclosed in Patent Processes 1 to 3 is inferior in strength. joins because the low melting phase melts at 250 ° C or more.
    [0015]. In general, in a welding device, the cooling rate of the molten weld is limited within a certain interval, taking into account the device's description and is not an operational factor that must be controlled every time a weld is made. In addition, excessively rapid cooling can apply unnecessary thermal stress to an electronic device on which a weld is made. Therefore, the following description is based on the premise of slow cooling.
    [0016]. At the operating temperature of a semiconductor element ranging between 250 and 280 ° C, warping occurs in the weld joint due to the thermal stress between a substrate and a component
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    4/32 semiconductor caused by the generation of heat from the semiconductor element itself.
    [0017]. In general, it is known that when fracturing a metallic material, displacements occur close to the granular limits of crystal due to the stress applied to cause the fracture of the granular limit. When stress is concentrated in the granular limits due to the applied tension and stress resulting from them, fracture of the granular limit occurs. In contrast, in the case where the granular crystal boundaries are finely dispersed, the applied stress is reduced, as this is dispersed in the adjacent granular boundaries. In other words, when tension is applied, a solder joint obtained by means of slow cooling solder using a solder alloy, which can form grains of thick crystals, is more likely to break the granular boundaries of the weld alloy intermetallic compounds. This is reflected in the tensile strength and elongation, which are the mechanical properties of the weld alloy. Therefore, a weld joint obtained by welding a weld alloy with a thick structure has a lower resistance in the joint and the elongation force compared to a weld joint obtained by welding a weld alloy with a thin structure. .
    [0018]. The Sn-Sb-Ag-Cu solder alloys disclosed in Patent Processes 1 to 3 are thus brittle and with lower elongation and, consequently, the solder joints obtained by soldering these solder alloys are more susceptible to become brittle and break during use as a result of slow cooling.
    [0019]. Patent Process 4 examines a SnSb-P-Ag-Cu-Fe solder alloy in Example 31. However, that solder alloy contains Fe in a considerably large amount of 1% or more. With a high Fe content, slow cooling will cause intermetallic compounds containing Fe that must be dispersed coarsely in the weld alloy. Therefore, this solder alloy is considered to have low resistance to
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    5/32 traction and elongation, as fracture is more likely to occur at the granular limits of intermetallic compounds when stress is applied.
    [0020]. In addition, as a result of slow cooling, the solder alloy described in Example 31 of Patent Process 4 is considered to have a solid phase rate at 250 ° C of up to 95% and must be transformed into a semi-molten state. Therefore, it is considered that the resistance of the solder joint cannot be maintained in an environment of use of 250 to 280 ° C. This is due to the following reasons: The solid phase rate of Sn-40Sb at 250 ° C is approximately 90%; the solid phase rate of Sn-40Sb-7Cu at 250 ° C is 95%; and these solder alloys have a solid phase rate below 98% and a considerable low tensile strength at 250 ° C. According to the above, since the solid phase rate is increased by adding 7% by weight of Cu to Sn-40Sb, Cu is considered to have an effect of increasing the solid phase rate. The solder alloy composition described in Example 31 of Patent Process 4 is Sn-40Sb-0.1P-1Ag-1Cu-1Fe. The total content of the elements other than Sn and Sb is only 3.1% by weight. Even if Ag, Fe and P have the same effect as Cu in increasing the solid phase rate, the total content of the added elements is less than 7% by weight. Therefore, the solder alloy described in Example 31 of Patent Process 4 is considered to be lower in tensile strength at 250 ° C due to its lower solid phase rate than Sn-40Sb-7Cu.
    [0021]. An object of the present invention is to provide a high temperature lead-free solder alloy, with excellent tensile and elongation resistance, even under a high temperature environment of 250 ° C.
    TROUBLESHOOTING [0022]. To begin with, the inventors of the present invention studied the relationship between the liquid phase rate and the structure in solder alloys and as a result they came to the conclusion that a solder alloy
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    6/32 which has a liquid phase rate of up to 2% exhibits consistent high tensile strength, while a weld alloy with a thick structure exhibits a low elongation value at 250 ° C, even if the liquid phase rate is up to 2%. Then, the inventors of the present invention did an intensive study in the refinement of a Sn-Sb-Ag-Cu solder alloy structure based on the assumption that the liquid phase rate is up to 2%, to improve resistance to tensile strength and elongation of the weld alloy itself at 250 ° C, which are indicators of joint strength and the reliability of a welded joint. As a result, the inventors of the present invention unexpectedly came to the conclusion that the structure of the solder alloy can be improved by adding at least one material selected from the group consisting of Al, Ti and Fe in a small amount for an alloy of Sn-SB- Ag-Cu. The inventors of the present invention also obtained a result that Cu3Sn, Cu6Sn5, Ag3Sn and similar compositions, are finely dispersed in a SbSn phase through the addition of Al, Ti and Fe, thus achieving a high tensile strength and, particularly, improving elongation of the weld alloy, and the present invention has been completed.
    [0023]. The present invention is carried out as follows:
    (1) A high temperature lead-free solder alloy with an alloy composition, comprising: 35 to 40% by weight of Sb, 8 to 25% by weight of Ag, 5 to 10% by weight of Cu, as well as at least one material selected from a group consisting of 0.003-1.0% by weight of Al, 0.01 to 0.2% by weight of Fe and 0.005 to 0.4% by weight of Ti, and a balance of Sn .
    (2) The high temperature lead-free solder alloy according to (1) above, which further comprises at least one material selected from a group consisting of P, Ge and Ga in a total amount of 0.002 to 0.1% in weight.
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    7/32 (3) The high temperature lead-free solder alloy according to (1) or (2) above, which further comprises at least one material selected from the group consisting of Ni, Co and Mn in a total amount from 0.01 to 0.5% by weight.
    (4) The unleaded high temperature solder alloy according to any one (1) to (3) above, which further comprises at least one material selected from a group consisting of Zn and Bi in a total amount of 0.005 to 0.5% by weight.
    (5) The high temperature unleaded solder alloy according to any one (1) to (4) above, which further comprises at least one material selected from a group consisting of Au, Ce, In, Mo, Nb , Pd, Pt, V, Ca, Mg and Zr, in a total amount of 0.0005 to 1% by weight.
    (6) A solder paste including the high temperature lead-free solder alloy in accordance with any one of (1) to (5) above.
    (7) A weld preform including the high temperature lead-free solder alloy according to any one of (1) to (5) above.
    (8) A solder joint formed using the high temperature lead-free solder alloy according to any of (1) to (5) above.
    BRIEF DESCRIPTION OF THE DRAWINGS [0024]. Figure 1 is a schematic view showing an example of packaging a semiconductor element using a high temperature lead-free solder alloy according to the present invention.
    [0025]. Figure 2 is a graph showing the DSC curve of a weld alloy in Comparative Example 1.
    [0026]. Figure 3 is a graph showing the DSC curve of a weld alloy in Example 14.
    [0027]. Figure 4 is a graph showing the DSC curve of the solder alloy in Comparative Example 1, indicating the methods for calculating the liquid phase rate and the solid phase rate.
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    8/32 [0028]. Figure 5 is a cross-sectional view of a sample used in a tensile test.
    [0029]. Figures 6 (a) to 6 (d) are each a micrograph of a sample fracture surface that was used by an optical microscope; Figure 6 (a) is a micrograph in Example 7, Figure 6 (b) a micrograph in Example 10, Figure 6 (c) a micrograph in Example 14 and Figure 6 (d) a micrograph in Comparative Example 3.
    [0030]. Figures 7 (a) to 7 (d) are each a micrograph of a sample fracture surface that was used by an electron microscope; Figure 7 (a) is a micrograph in Example 7, Figure 7 (b) a micrograph in Example 10, Figure 7 (c) a micrograph in Example M and Figure 7 (d) a micrograph in Comparative Example 3.
    [0031]. Figures 8 (a) to 8 (c) are each a micrograph of a cross-sectional surface of an interface between a high temperature lead-free solder alloy of the present invention and a Cu heatsink as it was taken by an electron microscope; Figure 8 (a) is a micrograph in Example 38, Figure 8 (b) a micrograph in Example 39, and Figure 8 (c) a micrograph in Example 40.
    DETAILED DESCRIPTION OF THE INVENTION [0032]. The present invention will be described in more detail below. Unless otherwise specified, the percentage (%) of the solder alloy composition as used in the specification is the percentage by weight.
    [0033]. A high temperature lead-free solder alloy according to the present invention has the composition of the alloy, as described below.
    Sb: 35 to 40% [0034]. The Sb content is in a range of 35 to 40%. The Sb promotes the generation of a SbSn phase with a high melting point. The Sb suppresses
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    9/32 generation of a low melting point phase to increase the solid temperature. In addition, Sb tends to reduce the surface tension of the weld alloy and therefore improves the water absorption capacity. With a Sb content of less than 35%, the suppression effect of generating a low melting point phase cannot be exhibited and the water absorption capacity is also impaired. With a Sb content above 40%, the liquid temperature increases considerably, deteriorating the welding capacity. The Sb content preferably remains in a range of 36 to 40% and ideally from 37 to 40%.
    Ag: 8 to 25% [0035]. The Ag content is in the range of 8 to 25%. The Ag reduces the liquid temperature to 380 ° C or less. The Ag generates an intermetallic compound of Sn and Ag3Sn to suppress the generation of a low melting point phase, thus improving the resistance of the solder alloy. In addition, Ag reduces surface tension in a temperature range of up to 400 ° C and therefore improves the water absorption capacity.
    [0036]. With an Ag content below 8%, it is not possible to exhibit the suppression effect of generating a low melting point phase as obtained by adding Ag. With an Ag content in excess of 25%, Sb and Ag preferably form an Ag3Sb phase and, therefore, the Ag3Sb phase appears in the initial solidification stage. Therefore, a low melting point phase is more likely to be generated in the weld alloy.
    [0037]. The formation of the Ag3Sb phase of Sb and Ag in the initial solidification stage reduces relatively the concentrations of Sb and Ag in the remaining liquid phase in the solder alloy solidification process. Decreases in Sb and Ag concentrations in the remaining liquid phase reducing the suppression effect of generating a low melting phase to increase the ratio between the low melting phase at 250 ° C or less. Therefore, the heat resistance of the solder alloy is deteriorated. The content
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    10/32 Ag remains preferably in a range of 10 to 22% and ideally 12 to 18%.
    Cu: 5 to 10% [0038]. The Cu content is in a range of 5 to 10%. Cu controls the liquid temperature in the range of 340 to 380 ° C. It mainly generates Cu3Sn and Cu6Sn5 to suppress the generation of a low melting point phase, thereby improving the tensile strength of the weld alloy.
    [0039]. With a Cu content below 5%, it is not possible to exhibit the suppression effect of generating a low melting phase as obtained by adding Cu. With a Cu content in excess of 10%, Sb and Cu preferably form a Cu2Sb phase and, therefore, the Cu2Sb phase appears in the initial solidification stage of the weld alloy. Therefore, a low melting point phase is more likely to be generated in the weld alloy.
    [0040]. The formation of the Cu2Sb phase of Sb and Cu in the initial solidification stage of the solder alloy relatively reduces the concentrations of Sb and Cu in the remaining liquid phase in the solder alloy solidification process. Decreases in Sb and Cu concentrations in the remaining liquid phase reducing the suppression effect of generating a low melting point of Sb and Cu to increase the ratio between the low melting phase at 250 ° C or less. Therefore, the heat resistance of the solder alloy is deteriorated. In addition, the solder alloy liquid temperature is increased to reduce the water absorption capacity, thereby reducing the welding capacity. The Cu content preferably remains in the range of 6 to 9% and ideally from 6 to 8%.
    [0041]. The low melting point phase is a solidified phase which is formed by the segregation of the solidification at the time of cooling the solder alloy after melting, and which has a melting point of 210 to 250 ° C. In general, segregation of solidification is a phenomenon in which specific ingredients are segregated due to a difference in
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    11/32 composition between the first and the last solidified part after the solidification of a molten phase. In general, solidification segregation is more likely to occur with a decrease in the cooling rate. Particularly in a lead-free solder alloy that contains a large amount of Sn, segregation of the low melting point of single-phase Sn is more likely to occur. From this point of view, the present invention is characterized by the suppression, in the weld joint, the generation of a low melting point phase in which the single-phase Sn is considered as a main ingredient.
    [0042]. The low melting phase includes single-phase Sn as its main ingredient, as the solid temperature, which is the melting point of the low melting phase, is at the same level as the melting point of Sn, which is 232 ° C. The remainder of the low melting point phase is considered to be composed of a residual phase, having a composition closer to Sb2Sn3 with a melting point of approximately 240 ° C and a Sn-Ag-Cu eutectic composition having a melting at approximately 220 to 230 ° C. Therefore, the solid temperature, which is the melting point of the low melting point phase, is considered to be a temperature in the range of 210 to 250 ° C.
    [0043]. The low melting point phase is generated, at least, if there is an alloy composition, with the Sn content exceeding the total content of Sb, Ag and Cu. In other words, the low melting point phase is generated when the following equation Sb + Ag + Cu <Sn is met. The reason why the 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 the formation preferential use of Sb, Ag and Cu intermetallic compounds with Sn during solidification, thus forming a high melting point phase. However, the exact mechanism is not known.
    [0044]. The high melting point phase as used in the present
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    The invention is a solidified phase composed of an intermetallic compound that shows a melting point of 290 ° C or more, as exemplified by Cu6Sn5, Cu3Sn, Ag3Sn, SbSn or Ni3Sn4.
    [0045]. A solder joint, in which a solder was made using the solder alloy, according to the present invention has these intermetallic compounds that constitute the phase of each high melting point, but may contain other intermetallic compounds in addition to the compounds illustrated above, provided that the high melting point is a solidified phase having a melting point of 290 ° C or more. In other words, once the solidified phase has a melting point of 290 ° C or more or a greater amount for a large part of the structure, the solder joint obtained by welding it, according to the present invention , has excellent heat resistance and tensile strength.
    [0046]. At least one material selected from a group consisting of 0.003 to 1.0% Al, 0.01 to 0.2% Fe and 0.005 to 0.4% Ti.
    [0047]. These elements are subtly dispersed in the phases respectively formed by intermetallic compounds such as Cu6Sn5, Cu3Sn and Ag3Sn in a SbSn phase to improve tensile strength and elongation.
    [0048]. In the high temperature lead-free solder alloy according to the present invention, the Sn-Sb-Ag-Cu solder alloy contains Al, Fe and Ti and, therefore, these elements are preferably crystallized during solidification to serve as seeds heterogeneous nucleation, thus preventing each thickening phase. When the nucleation of each phase is promoted by means of heterogeneous nucleation, the number of starting points for the nucleation is increased and, therefore, the phases of intermetallic compounds such as Cu6Sn5, Cu3Sn and Ag3Sn are subtly dispersed. Therefore, in the high temperature lead-free solder alloy according to the present invention, the
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    13/32 area of the granular limits of crystal in the weld alloys increases to make the dispersion of the applied stress in the granular limits and, therefore, several mechanical properties are considered and particularly the elongation with a significant improvement, more than a weld alloy, in which the respective phases of intermetallic compounds are insensitive.
    [0049]. Al, Ti and Fe are added in amounts as small as 0.003 to 1.6%. Therefore, even if a compound with a melting point greater than SbSn is produced as an intermetallic compound containing Sb, Ag and Cu, as well as any one with Al, Ti and Fe, Sb, Ag and Cu in the weld alloy, they are not consumed much. Therefore, the generation of a coarse low melting point phase is suppressed and, therefore, the strength of a weld joint is less susceptible to deterioration.
    [0050]. It is preferable that the Al content is in the range of 0.01 to 0.8% and ideally 0.02 to 0.5%, so that the effect described above can be sufficiently noted. The Fe content preferably remains in the range of 0.02 to 0.15% and ideally from 0.02 to 0.1%. The Ti content remains preferably in the range of 0.01 to 0.3% and ideally from 0.02 to 0.2%.
    [0051]. If the contents of these elements are lower than their minimum limit values, there is no effect of refinement of the weld alloy structure and the tensile strength and elongation are not sufficiently improved. If the content of these elements exceeds the maximum limit values, the intermetallic compounds containing these elements are thickened. Therefore, a tension applied to the weld alloy is concentrated at the granular limits of the intermetallic compounds, thus deteriorating the tensile strength and elongation.
    [0052]. The high temperature lead-free solder alloy according to the present invention may contain the following elements as
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    14/32 optional ingredients.
    [0053]. At least one ingredient selected from a group consisting of P, Ge and Ga, in a total amount of 0.002 to 0.1% [0054]. These elements have the effect of improving the water absorption capacity by suppressing the emergence of oxidizable Al, Fe and Ti on the surface of the weld alloy during its solidification. In this way, Al, Fe and Ti remain inside the weld alloy to further promote the refining structure through the heterogeneous nucleation described above. As a result, these elements also have the effect of considerably improving the elongation of the weld alloy. The total content of these elements becomes even more ideal in a range between 0.003 and 0.01%. The contents of the respective elements are not particularly limited, but, so that the effects described above can be sufficiently displayed, the P content remains preferably in the range of 0.002 to 0.005%, the Ge content remains preferably in the range of 0.002 to 0.006% and the GA content remains preferably in the range of 0.002 to 0.02%.
    [0055]. At least one ingredient selected from a group consisting of Ni, Co and Mn, in a total amount of 0.01 to 0.5% [0056]. These elements suppress the diffusion of ingredients from a flat layer formed on a semiconductor element or on an external substrate at the time of welding on the solder alloy. Therefore, these elements have the effect of maintaining the weld alloy structure constituting a weld joint, while a reduction in the thickness of a layer of intermetallic compounds must be formed at the joint interface. In this way, these elements can increase the strength of the weld joint. The total content of these elements becomes even more ideal in a range between 0.01 and 0.05%. The contents of the respective elements are not particularly limited, but, so that the effects described above can be sufficiently displayed, the Ni content remains preferentially
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    15/32 in a range of 0.02 to 0.07%, the Co content remains preferably in a range of 0.02 to 0.04% and the Mn content preferably remains in a range of 0.02 to 0.05% . Of these elements, Ni is a particularly preferred element as an element that exhibits the effect described above.
    [0057]. At least one ingredient selected from a group consisting of Zn and Bi, in a total amount of 0.005 to 0.5% [0058]. These elements further increase the solid phase rate of the solder alloy to 280 ° C to improve tensile strength. The total content of these elements becomes even more ideal in a range between 0.005 and 0.04% and ideally between 0.01 and 0.3%. The contents of the respective elements are not particularly limited, but, so that the effects described above can be sufficiently displayed, the Zn content preferably remains in a range of 0.01 to 0.2%, and the Bi content preferably remains in a range from 0.02 to 0.3%.
    [0059]. At least one element selected from a group consisting of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr, in a total amount of 0.0005 to 1%.
    [0060]. These elements improve mechanical ductility at 250 ° C, with P, Ge and Ga. These elements are oxidizable and oxidize more easily than Al, Ti and Fe, and have the effect of promoting the refining structure as obtained with the use of Al, Ti and Fe with these three elements remaining inside the weld. The total content of these elements becomes even more ideal in a range between 0.01 and 0.03%. The contents of the respective elements are not particularly limited, but, so that the effects described above can be sufficiently displayed, the content of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr remains preferably in a 0.02 to 0.03%.
    [0061]. The high temperature lead-free solder alloy according to the present invention preferably has a solid temperature
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    16/32 of 280 ° C or more and ideally 290 ° C or more. The solid temperature was thus defined for the following reasons:
    [0062]. The solid temperature was set to allow the solder joint using the high temperature lead-free solder alloy according to the present invention to have sufficient heat resistance to withstand the generation of heat from a SiC semiconductor element, a semiconductor element of GaN and a semiconductor element that GaAs that operates at an elevated temperature of 250 ° C or more, to obtain a solid phase ratio of 98% or more and to ensure good reliability. Another reason why the solid temperature is defined as being 280 ° C or more and preferably 290 ° C or more is that the reflux temperature, when another electronic component is joined to a packaging substrate in the step subsequent after a semiconductor element is the bond to the packaging substrate that can reach 260 ° C. The solder joint is necessary because it has a solid temperature of 280 ° C or more and preferably 290 ° C or more, since the temperature is capable of handling this reflux temperature very well, without remelting. Even in a solder alloy with a solid 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 weld joint, at 250 ° C is good and the connection can also be maintained at the time of repeated reflux.
    [0063]. The solid phase relationship, as used in the present invention refers to a proportion (%) of the area of the endothermic peaks, as detected at 280 ° C or more for the total area of endothermic peaks in a DSC curve, measured at a rate of temperature rise of 5 ° C / min, using a solidified solder alloy at a cooling rate of 1 ° C / min as the sample.
    [0064]. The high temperature lead-free solder alloy according to the present invention preferably has a temperature of
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    17/32 liquid up to 400 ° C. The soft solder temperature must be a temperature high above the liquid temperature. Therefore, at a liquid temperature above 400 ° C, the weld temperature needs to be higher than that temperature, but at such a high temperature, the cost of execution at the time of production is high and the work capacity is deteriorated. . In addition, a liquid temperature of up to 380 ° C is preferred from the point of view of the heat resistance of a semiconductor component itself and the protection of the electrical wiring of the circuit inside the semiconductor component.
    [0065]. The high temperature lead-free solder alloy according to the present invention can also be used in the connection of the matrix of a semiconductor element, in other words, in the union of a semiconductor element with a heat sink. The high temperature lead-free solder alloy according to the present invention can also be applied in the light solder of the connector terminals and the motherboards, in the assembly of DIP ICs or similar in the printed circuit boards, for the assembly and assembly of electronic components, such as capacitors, for sealing ceramic packages, for attaching cables to diodes and the like, and for soldering preforms of welds in the soft soldering of semiconductors.
    [0066]. The high temperature lead-free solder alloy according to the present invention can be suitably used in the form of a solder preform or solder paste. Said preform material is in the shape of a washer, a ring, a bead, a disc, a ribbon, a cable, a ball or the like.
    [0067]. A weld preform can be used at the junction of a reducing atmosphere, without using flux. Joining in a reducing atmosphere does not cause contamination of parts joined with flow, so it has the advantage of not only becoming unnecessary for cleaning the parts that joined in a step following the joint, but it can also reduce
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    18/32 considerably the empty spaces in the weld joints.
    [0068]. The high temperature lead-free solder alloy according to the present invention can be used in the form of a solder paste. The solder paste is in a pasty form and is obtained by mixing the solder alloy powder with a small amount of flux. The high temperature lead-free solder alloy according to the present invention can be used in the form of solder paste during the assembly of electronic components on a printed circuit board using a reflow soldering method. The flow for the use of the solder paste can be a water-soluble or insoluble flow. Usually a resin flow is used, which is a water-insoluble resin-based flow.
    [0069]. Figure 1 is a schematic view showing an example of packaging a semiconductor element using a high temperature lead-free solder alloy according to the present invention. The high temperature lead-free solder alloy according to the present invention can be used as a high temperature solder alloy to join (matrix connection) a semiconductor element in a heat sink. As illustrated in Figure 1, each part of the semiconductor element 1 and a heatsink 2 has a plated layer 3 made of Cu, Ni, Ni / Au, Ag, or similar materials. A high temperature lead-free solder alloy 4 according to the present invention connects the plated layers 3 to form a solder joint.
    [0070]. The solder joint according to the present invention is formed by using the high temperature lead-free solder alloy according to the present invention. For example, referring to Figure 1, the solder joint according to the present invention includes plated layers 3 and solder alloy 4.
    [0071]. As with the weld joint manufacturing conditions, according to the present invention, the cooling rate in the
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    19/32 solidification time preferably occurs in a range of 0.8 to 50 ° C / sec. The cooling rate within this range covers the cooling rate in most welding devices used today. Therefore, in a case where the solder alloy, according to the present invention, is used to perform the welding, it is not particularly necessary to make any specific changes in the cooling rate at the time of the light solder. Due to these excellent effects of the present invention, even in a case where a semiconductor element is attached to a large-scale printed circuit board or heat sink that has a large heat capacity, it is not necessary to change the cooling rate in the alloy lead free high temperature solder in accordance with the present invention, and soldering is carried out under conventional cooling conditions. This is because the high temperature lead-free solder alloy according to the present invention can present excellent connection reliability while suppressing the generation of a low melting point phase, even when slow cooling is performed at 0.8 ° C / sec The cooling rate is ideal between 1 and 10 ° C / sec.
    [0072]. The high temperature lead-free solder alloy according to the present invention exhibits its effects particularly in cases where a semiconductor element, as described above, operates at an elevated temperature of approximately 250 to 280 ° C when welding to a heat sink . As a matter of course, the high temperature lead-free solder alloy according to the present invention does not generate a low melting point phase and can exhibit sufficiently high connection reliability, even when used in a solder joint, which has a required heat resistance temperature up to 250 ° C.
    [0073]. The solder alloy according to the present invention, made from a high purity material or a low alpha material is a low alpha solder alloy. Errors can be prevented
    Petition 870160039147, of 7/26/2016, p. 27/49
    20/32 of software with the use of this on the periphery of a memory.
    EXAMPLES [0074]. The solder alloys with 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 / second to simulate the formation of each solder joint after blasting. The cooling rate is controlled by a thermocouple that detects the oven temperature of the DSC. To be more specific, the cooling rate of 1 ° C / second is a value obtained when a solder alloy has been completely melted at 430 ° C, then cooled to 180 ° C at a temperature reduction rate of 1 ° C / second.
    [0075]. A DSC curve of the cooled solder alloy was obtained by increasing the temperature to 5 ° C / min in air using the DSC (model: Q2000), manufactured by TA Instruments Japan Inc., from the resulting DSC curve , the solid temperature, the liquid temperature, the liquid phase rate and the solid phase rate. The results are compiled in Tables 1 and 2.
    [0076]. Figure 2 is a graph showing the DSC curve of a weld alloy in Comparative Example 1. Figure 3 is a graph showing the DSC curve of a weld alloy in Example 14. These DSC curves are obtained through increasing the temperature of the solidified solder alloys at a cooling rate of 1 ° C / sec. at 5 ° C / min.
    [0077]. In the DSC curve illustrated in Figure 2, the temperature at the beginning of the endotherm of the first endothermic peak is the solid temperature and the temperature at the end of the endotherm of the last endothermic peak is the liquid temperature. However, in a case where there is only a single endothermic peak, as illustrated in Figure 3, the temperature at the beginning of the endothermic peak endotherm is the solid temperature and the temperature at the end of the endothermic peak endotherm is the liquid temperature.
    Petition 870160039147, of 7/26/2016, p. 28/49
    21/32 [0078]. As seen in Figure 2, in the solder alloy of Comparative Example 1, where the alloy composition is out of the scope of the invention, two endothermic peaks were observed, and the solid temperature shown was 227 ° C. On the other hand, as is clear from Figure 3, in the solder alloy of Example 14, where the alloy composition is within the scope of the invention, a single endothermic peak was observed, and the illustrated solid temperature was 323 ° Ç.
    [0079]. In the alloy compositions illustrated in Comparative Examples except Comparative Examples 4, 5 and 10, an endothermic peak was observed at a temperature below 280 ° C.
    [0080]. The methods for calculating the liquid phase rate and the solid phase rate will be described in detail, using the DSC curve of Comparative Example 1, as shown in Figure 4 as an example.
    [0081]. The liquid phase rate at 280 ° C was determined as follows: First, as shown in Figure 4, a baseline 8 was taken, and the Vo area (Vo = Vi + V2) surrounded by the baseline 8 and 9, a DSC curve was determined. The dividing line 10 was determined, then it was drawn at 280 ° C and the area Vi surrounded by the dividing line 10, the DSC curve 9 at 280 ° C or less the baseline and 8. Finally, the phase rate liquid (percentage) at 280 ° C, was calculated by the equation (Vi / Vo) x 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 Figure 3 , the Vi area is 0 and therefore the liquid phase rate at 280 ° C is 0%.
    [0082]. The solid phase rate at 280 ° C was determined as follows: The area V2 surrounded by the dividing line 10, the DSC curve 9 at 280 ° C or more and the baseline 8 shown in Figure 4 were determined. liquid phase rate at 280 ° C, was then calculated using the equation (V2 / Vo) x 100 to obtain the solid phase rate. On the other hand,
    Petition 870160039147, of 7/26/2016, p. 29/49
    22/32 in a case where no endothermic peak was observed at a temperature of 280 ° C or more, as shown in Figure 3, V2 is equal to Vo, so that the solid phase rate at 280 ° C is equal to 100 %. The results of the measurements are illustrated in Tables 1 and 2.
    [0083]. In addition, a solder alloy, each having an alloy composition illustrated in Tables 1 and 2, was shaped to prepare a specimen with a predetermined shape. The methods of measuring tensile strength and elongation at break are described below.
    [0084]. A specimen has the shape illustrated in Figure 5. Its parallel part has dimensions of 8 mm in diameter (φ) and 30 mm in length. The specimen was obtained by melting each solder alloy at the liquid temperature of each composition of + 100 ° C, casting the solder alloy cast in a split mold made to work according to the dimensions described above, cooling the solder alloy melted with air until the temperature dropped to room temperature, and removal of the cooled solder alloy from the split mold. A thermocouple was connected to the casting part of the split mold and the temperature evolution during solidification was measured. As a result, the cooling rate was approximately 1 to 3 ° C / second. A tensile test was carried out in a thermostatic chamber at 250 ° C in air, at a speed of 0.09 mm / min using an Autograph 5966 manufactured by Instron.
    [0085]. The tensile strength and elongation at break were calculated from the load and the deviation values read in a load cell of the tensile tester. According to the present invention, in the case of a solder alloy, a tensile strength of 5 MPa or more was found, and an elongation at break of 5% or more, the solder alloy was considered to have sufficient mechanical properties to avoid easy fracture even at high temperature when used for a weld joint.
    Petition 870160039147, of 7/26/2016, p. 30/49
    23/32
    Elongation at break [%] M 1 367 1 407 1 ** 1 727 1 124.0 | 867 1 Si 35.3 | 39J 1 O* jd 53J 1 O* CO 1 826 I 112.3 | O3 63.3 | CN 134.9 | δ 120.5 | 265 1 272.0 | 209.1 Tensile strength [Mpa] CN • d CN COPOO CNCN CN CN o • the CN IO 5 CN POO CN8 ' CO8 ' 8 ' 3 ‘ CNCO •O POO 8 O 8 ' CN hello O8 IO CN CO CN8 ' • oó | B j f EM IO $ 9 'o * O8 O8 O8 O8 sO* O8 sO* O8 O8 O8 O8 O8 O8 O8 O8 O8 IO $ 9 'o * O8 O8 O8 O8 O8 COCN CN CN CN O* 1 «11 ε IO O o O o O o O o O* O o O* O o O o O o O o O o O o O o O o O o IO O o O o O o O o O o O' CO O CO Liquid temperature, pq 360.3 358.9 357.0 359.5 jO CO 348.2 358.8 359.8 358.9 356.5 358.5 373.6 359.0 356.2 358.6 375.2 354.7 CN 356.7 356.38 CO 356.4 351.4 352.3Solid temperature [° q 228.4 300.2 297.7 300.8 338.2 227.6 298.5 228.6 304.6 • d 303.9 327.8 301.3 323.6 301.0 328.6 324.7 CO8 322.2 § 299.3 301.0 299.5 227.6 CN 221.6 Composition of Iga [%] 5 r ή Ώ Z 5th Φ u Ό £ δ > £CN o ' > 5 CO o2 CO o Z O o í8O the U 8Oδ δ o δ 0.005 tk 0.003 0.003 1 = 0.005 8O 3O CN O Φ Ik δ o 8O 0.046 O' 3 0.003 δ o ειο'ο O o 8O O CO CO o - δ o 0.085 910Ό δ o 8O the o 8O O' δ o 0.003 O IO•O¢ 0 IO•O•O¢ 0•O¢ 0 •O IO •O •O -O -O -O -O -O IO < ¢ 0 ¢ 0 LO ¢ 0 8 IO ¢ 0 LO ¢ 0 IO ¢ 0 8 ¢ 0 IO ¢ 0 8 IO IO LO IO IO IO IO IO IO CO £ IO CO CO CO COIO CO CO CO CO CO CO 8 CO CO CO 8 • CO IO CO • CO • CO CO CO CO CO δ δ 5> 8 8 8 8 B B B B B B B B B B B B B B B B B B B B B B| Example 1 | | Example 2 | | Example 3 | | Example 4 | | Example 5 | | Example 6 | | Example 7 | | Example 8 | | Example | | Example 101 | Example 11 | | Example 121 | Example 131 | Example 141 | Example 15 | Example 161 | Example 171 | Example 181 | Example 19 | Example 201 | Example 211 | Example 221 | Example 23 | Example 241 | Example 251 Example 26
    24/32
    Elongation at break [%] 159.6 | CN8 1 102.6 | 125.6 Tensile strength [Mpa] IO8 IOCN -O IO O8 | «J f E O8 • CN CN O8 O8 O8 1 «11 ε O o 5 O o O o O o Liquid temperature, pq 358.0 356.5 385.9 358.7 360.0 Solid temperature [° q 304.4 225.6 300.3324.2 Composition of Iga [%] 5rήΏ Z 5thΦ u 0.049 Ό 910'0£ 19600'0 δO > 0.005 £> 52Zíthe Uδδtk1 =Φ Ik3 δ o 900'0 0.004 O o 0.003 O •O •O •O -O •O < IO LO IO IO IO s CO CO CO CO • CO 5> s s s s s| Example 271 | Example 281 | Example 291 | Example 301 Example 31
    Petition 870160039147, of 7/26/2016, p. 32/49
    25/32
    Elongation at break pq Ό Ό o Ό O. *O 1 CH8 140.8 | CN3 «L CN CS 0.3 0.3 • 8, 8 _8 - □ ac 3 dogs POO cq dog «H CO CN CO cs CN CO cs CN Ό δ CH CO cs cs CN ΙΌ CO cs có CN XLO CO f «1 1 E O8 O8 Lf) cs' o. Lf) cs' o. «L o. O. O8 3CS s ΌCS CS O8 O8 cr> O 1 M J E O o O o Lf) O Lf) o 3 O o «L CO CH CN 5 O o O o CN the CO Dotquldo temperature rq 360.4 358.4 § 1 1 358.0 375.0 fH8 362.9 356.9 CH cs 375.3 CS3 X cs I ° i AND1 ' 326.0 225.7 224.0 Ό'•OSl 225.5 333.5 OThe 228.4 226.9 CH§ 338.9 X Ό 8 fH O.8trQ.1 5 O Q O * § O0.002 8000'0 0.0007 Ώ Z§ O 0.002 % Lf)§ O 0.0023 ΰ8th O_8O £0.012 δ3O >0.012 ç8O 5 O Ώ o The0.044 28th0.016 Oδ o δδ o δ0.004 The_0.002 1 =0.003 § 0IL0.003§< § O 8O 8O 600'0 3rd 0.046 O Ό Ό Ό Ό Ό CO Lf) LO LO LOL CO LOL LOL í * Lf) Lf) Lf) Lf) Lf) 8 Lf) CO LO CO 8 CO CO ΏV » CO CO CO CO CO3 LO CO LO CO COCO CO c V » 2 2 2 2 2 2 2 2 2 2 2 2 2| Example 32 | | Example 33 | | Example 34 | £ 3.I 8Δ Q.I | Example 37 | ExampleCompcralivo1 ExampleCompcraHvo2 ExampleCompcraHvo3 ExampleCompcraHvo4 ExampleCompcraHvo5 ExampleCompcraHvo6 ExampleCompcraHvo7
    Petition 870160039147, of 7/26/2016, p. 33/49
    26/32
    Elongation at break pq 3 CO O. CN 3 • 8, 8 _8 - □ ac in «L CN "H3 l> f «1 1 E 97.6 96.3 O8 98.5 f M j E XCN CO O o ΙΌ Dotquldo temperature rq «L CN3 359.6 CH o. 362.3 I ° t | AND1 ' 227.9 228.5 302.8 229.1 ANDO.8 trQ.1 Au f ή Λ Z Mo ΰ O_ £ H δ > ç 5 The 2 Mn O δ δ The_ 1 = 0.004 0IL 0.006< 0.002 2 Ass Lf) Ό K LO í * CO LO CO CO ΛV » Lf) CO CO CO LO CO c V » bal. bal. bal. bal.ExampleCompcraHvo8 ExampleCompcraHvo9 ExampleCompcraHvo10 Example CompcraHvo11
    Petition 870160039147, of 7/26/2016, p. 34/49
    27132 [0086]. Each of Examples 1 to 37 where the alloy composition is within the scope of the invention showed a solid phase rate of 98% or more, a liquid temperature of up to 376 ° C, a tensile strength at 250 ° C 5 MPa or more, and an elongation at break of 5% or more. On the other hand, each of the Comparative Examples 1 to 11, in which Al, Fe and Ti are not contained or Al, Fe and Ti are contained in quantities outside the ranges of the present invention, only an elongation at break with value was found less than 4%. For example, each of the Comparative Examples 3, 4, 5, 10 and 11 has a solid phase rate at 250 ° C of 98% or more, thus satisfying the required heat resistance, but exhibits an elongation at break at 250 ° C of less than 3%, therefore, not meeting the mechanical ductility. However, in Examples 2, 4, 5, 6, 7, 9, 11, 12, 13, 15, 16, 18 and 37 where Al, Fe or 11 is added in a specific amount, the mechanical ductility improves considerably.
    [0087]. Comparative Examples 1 to 5 where Al, Fe or Ti are not contained, each has an elongation at break of up to 3%, although some of them demonstrate high tensile strength. Comparative Examples 6 to 11 where the contents of Al, Fe and Ti are outside the ranges of the present invention, each has a low elongation at break value, although some of them demonstrate high tensile strength.
    [0088]. Figures 6 (a) to 6 (d) are each a micrograph of a sample fracture surface that was used by an optical microscope; Figure 6 (a) is a micrograph in Example 7, Figure 6 (b) a micrograph in Example 10, Figure 6 (c) a micrograph in Example 14 and Figure 6 (d) a micrograph in Comparative Example 3. The micrographs shown in Figures 6 (a) to 6 (d) are taken at 20x magnification.
    [0089]. Figures 7 (a) to 7 (d) are each a micrograph of a sample fracture surface that was used by an electron microscope; Figure 7 (a) is a micrograph in Example 7, Figure 7 (b) a micrograph in Example 10, Figure 7 (c) a micrograph in Example 14 and a
    Petition 870160039147, of 7/26/2016, p. 35/49
    28/32
    Figure 7 (d) a micrograph in Comparative Example 3. The micrographs shown in Figures 7 (a) to 7 (d) are taken at 200x magnification.
    [0090]. As shown in Figures 6 (a) to 6 (d), it was revealed that the granular regions surrounded by cracks seen on the fracture surface in Figures 6 (a) to 6 (c) are clearly smaller in size than those in Figure 6 (d). It has also been revealed that the phases of intermetallic compounds such as Ag3Sn and Cu3Sn are finely dispersed in a SbSn phase in Figures 7 (a) to 7 (c), whereas a SbSn phase and the thick phases of intermetallic compounds such as Ag3Sn and Cu3Sn form a lamellar structure in Figure 7 (d).
    [0091]. In the high temperature lead-free solder alloy according to the present invention, the Ag3Sn, Cu6Sn5, Cu3Sn and similar phases are finely dispersed in the SbSn phase as shown in Figures 7 (a) to 7 (c) to increase the area granular crystal boundaries, thereby reducing the stress concentration. Therefore, the granular regions surrounded by the cracks observed on the fracture surface, as shown in Figures 6 (a) to 6 (c) are considered to be smaller in size than the granular regions surrounded by the cracks observed on the fracture surface, as illustrated in Figure 6 (d).
    [0092]. The high temperature lead-free solder alloy according to the present invention can thus reduce the concentration of stresses due to deformation, while suppressing the fracture of each granular boundary and, consequently, is considered to show excellent tensile strength and elongation at break.
    [0093]. In addition, each solder alloy in accordance with the present invention was used to form a solder joint over a heatsink and the state of the common interface between the solder alloy and the heatsink was examined.
    Petition 870160039147, of 7/26/2016, p. 36/49
    29/32
    Layer thicknessBMI [mm] O the CO 2.3 Solid phase rate [° C] 0'001 0'001 0'001 Liquid phase rate [° C] 0.0 0.0 0.0 Liquid temperature [° C] 358.4 358.6 358.7 Solid temperature [° C] 326.0 326.0 327.0 Alloy composition [%] z O 0.03 0.07 < 0.02 0.02 0.02 Ass O O O O)< O O O Sb CO CO CO Sn bal. bal. bal.Example 38 Example 39 Example 40
    Petition 870160039147, of 7/26/2016, p. 37/49
    30/32 [0094]. Each of Examples 38, 39 and 40 where the alloy composition is within the scope of the present invention has a solid phase rate of 100% and a liquid temperature of up to 376 ° C, and has good heat resistance. In addition, once the Al content is within the scope of the present invention, mechanical strength and ductility are also obviously met. In addition, a layer of intermetallic compound (IMC) formed at the interface of the joint with the heat sink is thinner in Examples 39 and 40 than in Example 38 where Ni is not contained. It is known that the reliability of the joint reduces at the joint interface between the solder alloy and the heat sink, if the layer of intermetallic compounds formed in the vicinity of the common interface is very thick. In other words, by adding more Ni to a solder alloy obtained by incorporating Al, Ti and Fe from a Sn-Sb-Ag-Cu alloy within the scope of the present invention, the layer of intermetallic compounds can be prevented to have an increased thickness, thus further improving the reliability of the joint.
    [0095]. Figures 8 (a) to 8 (c) are each a micrograph of a cross-sectional surface of an interface between a high temperature lead-free solder alloy of the present invention and a Cu heatsink as was taken by an electron microscope. The Cu heatsink has a size of 30 x 20 x 2 mm and is made of Cu. A Si chip has a size of 5 x 5 x 0.5 mm and the electrode portions of the joint are lightly bathed with Ni / Au.
    [0096]. Reflux blast soldering was performed by applying an appropriate flux to the central portion of a Cu heatsink, placing the solder alloy with a weight of approximately 10 mg in the assembly flux and a Si chip in it. The joint conditions are as follows: A H 2 vacuum soldering device manufactured by Shinko Seiki Co., Ltd .; rate of temperature rise: 1.8
    Petition 870160039147, of 7/26/2016, p. 38/49
    31/32 [° C / sec.]; peak temperature: 367 [° C]; melting time of the solder alloy: 80 seconds; and cooling rate: 1.7 [° C / sec.].
    [0097]. Figure 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% AI) and a Cu heatsink; Figure 8 (b) is an electron micrograph of a cross-sectional surface of a joint interface between a solder alloy in the Example (Sn-37% Sb-6% Cu-15% Ag-0.02% AI-0 , 03% Ni) and a Cu heatsink; and Figure 8 (c) is an electron micrograph of a cross-sectional surface of a joint interface between a solder alloy in the Example (Sn-37% Sb-6% Cu-15% Ag-0.02% AI- 0.07% Ni) and a Cu heatsink.
    [0098]. As shown in Figures 8 (a) to 8 (c), the solder joint in Example 38 forms a CuSb intermetallic composite phase with a thickness of approximately 4 (pm) at the Cu heatsink joint interface. The solder joints using the solder alloys described in Examples 39 and 40 have a BMI thickness of 3.5 (pm) and 2.3 (pm), respectively. Figures 8 (a) to 8 (c) reveal that the liquid phase of the Cu electrode ingredients is suppressed from the Cu heatsinks in the weld alloys and the layers made of various intermetallic compounds formed at the joint interfaces are thin.
    [0099]. From the above, the high temperature lead-free solder alloy according to the present invention has excellent tensile and elongation resistance in a high temperature environment of 250 ° C. Therefore, the high temperature lead-free solder alloy according to the present invention can reduce the thermal stress applied to a solder joint, which can be caused by the thermal stress due to a difference in the thermal expansion coefficient between each substrate and a associated component. As described above, in the high temperature lead-free solder alloy according to the present invention, the solder joint does not cause fracture in relation to a semiconductor element
    Petition 870160039147, of 7/26/2016, p. 39/49
    32/32 capable of operating at high temperature. The high temperature lead-free solder alloy according to the present invention can also be used without any problem, even in an environment where the solder alloy can be exposed to high temperatures.
    权利要求:
    Claims (4)
    [1]
    1. High temperature LEAD WITHOUT ALLOY characterized by consisting of an alloy composition, consisting of: 35 to 40% by weight of Sb, 8 to 25% by weight of Ag, 5 to 10% by weight of Cu, as well as at least one material selected from a group consisting of 0.003 to 1.0% by weight of Al, 0.01 to 0.2% by weight of Fe and 0.005 to 0.4% by weight of Ti, and a balance of Sn, which further consists of at least one material selected from a group consisting of P, Ge and Ga in a total amount of 0.002 to 0.1% by weight, which further consists of at least one material selected from a group consisting of Ni, Co and Mn in a total amount of 0.01 to 0.5% by weight, which further consists of at least one material selected from a group consisting of Zn and Bi in a total amount of 0.005 to 0.5 % by weight, which still consists of at least one material selected from a group consisting of Au, Ce, In, Mo, Nb, Pd, Pt, V, Ca, Mg and Zr, in a total amount of 0.0005 to 1% by weight.
    [2]
    2 WELDING PASTE characterized by including the high temperature lead-free solder alloy as defined by claim 1.
    [3]
    3 PREMOLDED WELDING characterized by including the high temperature lead-free solder alloy as defined by claim 1.
    [4]
    4 WELD JOINT characterized by being formed by the high temperature lead-free solder alloy as defined by claim 1.
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    公开号 | 公开日
    BR112015002414A2|2018-02-06|
    US9796053B2|2017-10-24|
    CN104520062B|2016-01-06|
    WO2014024715A1|2014-02-13|
    EP2883649A4|2016-03-09|
    US20150217410A1|2015-08-06|
    TW201411652A|2014-03-16|
    EP2883649A1|2015-06-17|
    KR20150024441A|2015-03-06|
    EP2883649B1|2017-04-19|
    TWI587316B|2017-06-11|
    CN104520062A|2015-04-15|
    ES2632605T3|2017-09-14|
    KR101561894B1|2015-10-20|
    JP5585746B2|2014-09-10|
    MY154606A|2015-07-01|
    DK2883649T3|2017-06-19|
    JPWO2014024715A1|2016-07-25|
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    法律状态:
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-02-26| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2019-08-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-10-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/07/2013, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/07/2013, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012178846|2012-08-10|
    JP2012-178846|2012-08-10|
    PCT/JP2013/070473|WO2014024715A1|2012-08-10|2013-07-29|High-temperature lead-free solder alloy|
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