JP2006167790A - Producing method for solder material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a producing method for a lead-free high-temperature solder material, which is used for soldering in the high-temperature range of 250-300°C, since conventional high-temperature solder materials, which are produced by individually adding a single element to a binary alloy, are insufficient in reliability because of the wide range of variation of their liquidus temperatures. <P>SOLUTION: A 1st metallic component contains Bi and consists of a binary eutectic alloy. A 2nd metallic component has an eutectic point temperature different from that of the 1st metal component and is a binary eutectic alloy of two kinds of metals selected from Bi, Ag, Cu, Ge, and Zn. A 3rd metallic component consists of one or more kinds of metals selected from Pd, Al, Co, and Si. A lead-free high-temperature solder material having a melting point of 250-300°C is produced by adding the 2nd metallic component and next the 3rd metallic component to the 1st metallic component. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a high-temperature solder material that does not contain lead.

  As shown in FIG. 10, in a mounting component that handles a high frequency such as a power amplifier module mounted on an electronic circuit board, a module using a solder material 4 for joining the electrode 2 of the electronic component 1 and the conductor of the module board 3 is used. The component 5 is produced. The module component 5 is mounted on the mother board 6 as shown in FIG. When the module component 5 is mounted on the mother board 6, if the solder material 4 inside the module component 5 is melted and the shape changes, for example, stray capacitance and inductance change, and the high frequency characteristics change. Therefore, a high-temperature solder material (for example, Pb-40% Sn) having a melting temperature of 250 to 300 ° C. is used in the module component 5 so as not to melt when the module component 5 is mounted on the mother board 6.

  However, in recent years, with increasing interest in protecting the global environment, it is feared that environmental problems will occur due to waste, and there is a concern that lead (Pb) may elute from the discarded electronic devices into the soil even in solder materials. Has been. To solve this, a lead-free solder material is required. Among them, as a substitute for the Sn—Pb solder material having a melting temperature of 200 to 250 ° C., the practical use of a solder material not containing lead, such as Sn—Ag and Sn—Cu solder materials, is progressing. .

On the other hand, there is no alternative material for high-temperature solder materials that require high heat resistance, and it is far from practical use. As a high-temperature solder material realizing a melting temperature of 250 to 300 ° C., a material mainly composed of bismuth (Bi) has been proposed (see, for example, Patent Document 1).
JP 2001-353590 A

  However, the conventional high-temperature solder material described in the above-mentioned Patent Document 1 is a binary combination of 90% by weight or more of the first metal element made of Bi, 90% by weight or more of the first metal element and 9.9 parts by weight or less. The third metal element is added to the binary solder material composed of the second metal element that can be crystallized so that the total amount is 0.1 to 3.0% by weight. Has the problem of changing significantly.

  As described above, the high-temperature solder material is used for joining inside the module component, and when the module component is mounted on the mother board, it is heated to 230 to 250 ° C., thus preventing changes in electrical characteristics due to remelting. In order to do so, the melting temperature of the high-temperature solder material must not be 250 ° C. or lower.

  Moreover, since the upper limit temperature is limited by the heat resistance temperature of the electronic component mounted inside the module component, the upper limit value is also regulated for the melting temperature of the high-temperature solder material. If the melting temperature exceeds the lower limit value, the high-temperature solder material inside the module component is melted when mounted on the mother board, and the electrical characteristics are impaired. Further, when the melting temperature exceeds the upper limit value, heating becomes insufficient when mounting the components inside the module components, which may cause poor soldering.

  When the melting temperature of the high-temperature solder material is 300 ° C., a good bonding state cannot be obtained unless the soldering is heated to 310 ° C. or higher of plus 10 ° C. For this reason, the heat resistant temperature of electronic parts is required to be 310 ° C. or higher.

  However, soldering at a high temperature consumes a large amount of energy and is not good in terms of production cost and environmental protection. Also, an electronic component having a high heat-resistant temperature is not good in terms of material cost because the manufacturing cost is high. For this reason, it is desirable to solder at a temperature as low as possible by using an inexpensive component having a low heat-resistant temperature, assuming that the melting temperature of the high-temperature solder is close to 250 ° C. Currently, a high temperature solder material having a melting temperature of 270 to 280 ° C. is generally used with a safety range of 20 to 30 ° C. If the problem that the melting temperature changes greatly is solved, it is safe. The region can be narrowed and soldering can be performed near 250 ° C.

  The present invention solves the above-mentioned conventional problems, and there is no problem that the melting point changes greatly due to variation in the addition rate, and a lead-free high-temperature solder material that can be used for soldering in a high temperature range of 250 to 300 ° C. The purpose is to provide a production method.

  In order to achieve the above object, the method for producing a solder material according to the present invention is different from the first metal component in that the eutectic point temperature is different from Bi, Ag, A second metal component, which is a binary eutectic alloy of two kinds of metals selected from Cu, Ge, and Zn, is added, and a second element made of at least one kind of metal selected from Pd, Al, Co, and Si is added. It is characterized by further adding three metal components.

  With this configuration, the solder material production method of the present invention can produce a solder material that realizes lead-free while maintaining a melting temperature of 250 to 300 ° C.

  As described above, according to the method for producing a solder material of the present invention, synthesis of a high-temperature solder material having a melting point of 250 to 300 ° C. does not include lead, and there is no problem that the melting point changes greatly due to variation in the addition rate. It becomes possible.

  Embodiments of the present invention will be described below with reference to the drawings.

(Embodiment 1)
One of the items to be noted when designing an alloy of solder material is the price of the metal used. Since household electrical and electronic devices are required to be produced at low cost, it is necessary to consider the price of solder materials. By examining a phase diagram of a binary alloy that is generally commercially available, an alloy composition that realizes a eutectic point temperature of 250 to 300 ° C. can be found, but most of them use an expensive metal as a constituent element. The alloy compositions of inexpensive metals include Bi-Ge (eutectic point temperature 271 ° C), Bi-Cu (eutectic point temperature 270 ° C), Bi-Ag (eutectic point temperature 262 ° C), Bi-Zn (eutectic point temperature). It is narrowed to binary alloys containing Bi such as a crystal point temperature of 255 ° C.).

  When a third metal element such as Cu, Ag, Ge, or Bi is added to these Bi-based binary eutectic alloys, the liquidus temperature can be increased and the temperature can be increased. However, when the temperature is increased by this method, the liquidus temperature greatly changes due to variations in the addition rate of the third metal element. As an example, FIG. 1 shows a change in liquidus temperature when Cu is added to Bi-2.5% Ag. In this case, it can be seen that the liquidus temperature greatly changes to 0.82 ° C. when the Cu addition rate changes by 0.1%. For this reason, it is necessary to strictly control the addition rate of the third metal element when producing a material having a desired liquidus temperature. However, in the actual manufacturing process of a metal alloy, since it is manufactured in a large unit of several hundred kg, strict management is difficult. In addition, since metal materials such as Cu and Bi contain about 0.06% of impurity elements such as Sn, Pb, Zn, and Fe, these impurity elements will be contained even after alloying. The composition of the metal alloy may deviate from the design value. When the composition analysis of the finished metal alloy was conducted with several metal alloys having different compositions, a variation of up to 0.2% was confirmed.

  For this reason, stabilization of the liquidus temperature is important for practical application of high-temperature solder. We have accumulated experiments to find that it is effective to stabilize the liquidus line by adding a third eutectic element in a binary eutectic composition rather than adding it alone. FIG. 2 shows the change in liquidus temperature when Ag-39% Cu eutectic is added to Bi-2.5% Ag. When the addition rate of Ag-39% Cu eutectic is changed by 0.1%, the amount of change in liquidus temperature is 0.52 ° C., which is suppressed to 2/3 compared to the case of the above single addition. It becomes possible. In addition, when it is necessary to add a metal element alone, a metal element having a low impurity content such as Al, Pt, Pd, Co, Si, or Au is used. According to this method, a material having an alloy composition close to a desired liquidus temperature can be manufactured.

  Here, a design procedure when the target liquidus temperature is 275 ° C. is shown. Assuming that Bi-2.5% Ag (eutectic point temperature 262 ° C.) is used as the first metal component, Ag-39% Cu (eutectic point temperature 779 ° C.), Ag-18% are used as the second metal component. It is possible to add Ge (eutectic point temperature 651 ° C.), Cu-39% Ge (eutectic point temperature 640 ° C.), etc., but here Ag-39% Cu (eutectic point temperature 779 ° C.) is added. I decided to use it. Table 1 shows changes in the liquidus temperature and the content ratio of each element when Ag-39% Cu is added to Bi-2.5% Ag.

  When the liquidus temperature is set to the target value of 275 ° C., the addition rate of Ag-39% Cu is 2% or 3%, but in order to keep it within a range not exceeding 275 ° C., it is necessary to make it 2%. is there. In this case, the content ratios of Bi, Ag, and Cu are 95.6%, 3.9%, and 0.6%, respectively. However, as described above, management in units of 0.1% is difficult. Therefore, adjusting the fraction in units of 0.5% gives 95.5%, 4%, and 0.5%. The liquidus temperature at this time is approximately 272 ° C., and it is necessary to increase it by 3 ° C. in order to match the target temperature of 275 ° C. Therefore, a small amount of Al having a low impurity content is added as the third metal component in order to increase the liquidus temperature. The change in the liquidus temperature when Al is added is shown in FIG. When 0.1% Al is added, the liquidus temperature changes by 1.3 ° C., so 0.2% Al is added so that the liquidus temperature reaches the target temperature of 275 ° C.

  The metal composition of the material thus designed is Bi-3.9% Ag-0.6% Cu-0.2% Al, and the material is actually manufactured and the liquidus temperature is measured by a differential scanning calorimeter. As a result, a liquidus temperature of 275.7 ° C. was obtained, and it was confirmed that the temperature was sufficiently close to the target temperature of 275 ° C.

  As the first metal component, Bi-1% Ge (eutectic point temperature 271 ° C.), Bi-0.5% Cu (eutectic point temperature 270 ° C.), Bi-96% Zn (eutectic point temperature 255). ° C) or the like. As the second metal component, Bi-0.5% Cu (eutectic point temperature: 270 ° C.), Zn-6% Ge (eutectic point temperature: 398 ° C.), or the like can be added.

  Further, as the third metal component, elements such as Pt, Pd, Co, Si, and Au in addition to Al are suitable for addition because of their low impurity content, but considering the material price, Al Is desirable. Further, when these third metal components are added as fine particles having a diameter of 10 microns or less, crystals are precipitated and hardened using these fine particles as nuclei, so that the metal structure can be densified and the reliability can be improved. .

  Table 2 shows some materials designed with similar procedures.

  Assuming that the target liquidus temperature is 275 ° C., Bi-1% Cu-0.5% Ge-0.08% Pd, Bi-96% Zn-0.5% Ge-0.25% Al, etc. There is. When these materials were prototyped and the liquidus temperature was measured, the difference between the target temperature and the actually measured temperature was within 1.2 ° C., which was sufficient for the target temperature.

  Materials with different target liquidus temperatures were designed and prototyped using the same procedure. For these materials, the difference between the target temperature and the actually measured temperature was all within 1.0 ° C., and there was no practical problem.

  According to such a configuration, the first metal component including Bi and including a binary eutectic alloy has a eutectic point temperature different from that of the first metal component, and is selected from Bi, Ag, Cu, Ge, and Zn. Solder characterized by adding a second metal component which is a binary eutectic alloy of various kinds of metals, and further adding a third metal component made of at least one kind of metal selected from Pd, Al, Co and Si According to the material production method, it is possible to produce a high-temperature solder material having a melting point of 250 to 300 ° C. without containing harmful lead and without the problem that the melting point changes greatly due to variation in the addition rate.

  FIG. 4 is a view showing a soldered article using the solder material produced in the present invention.

  In FIG. 4, the electrode 8 of the electronic component 7 and the module substrate 9 are joined using a solder material 10. The module component 11 having such a structure becomes an electric or electronic device by being mounted and assembled on the mother board 6 in a separate process. At that time, when the solder material 10 inside the module component 11 melts and changes its shape, the high frequency characteristics change. Therefore, the solder material 10 is composed of Ag 0.1 to 8.0 wt%, Cu 0.1 to 3.0 wt%. At least two elements selected from Ge 0.1 to 2.0 wt%, Zn 0.1 to 6.0 wt%, Pd 0.01 to 0.5 wt%, Al 0.01 to 1.0 wt% %, Co 0.01 to 0.5% by weight, Si 0.01 to 0.5% by weight of at least one element selected from the composition consisting of Bi and the balance of Bi, without containing harmful lead, This is a high-temperature solder material having a melting point of 250 to 300 ° C., which does not have a problem that the melting point changes greatly due to variation in the addition rate.

  FIG. 5 is an enlarged view of a portion where the electrode 8 of the electronic component and the electrode 12 of the module substrate 9 are joined by the solder material 10. In the soldered article, the electrode 8 of the electronic component is subjected to Au flash treatment on the Ni base, and the Sn content is 0.5% by weight or less excluding inevitable impurities. Moreover, the electrode 12 of a module board | substrate is Cu, and Sn content rate is 0.5 weight% or less except the unavoidable impurity like the electrode of an electronic component. Therefore, the constituent elements of the joint portion between the solder material 10 and the electrode 12 are composed of seven types of Bi, Ag, Cu, Al, Au, Ni, and Sn, and the Sn content is 0.5 weight excluding inevitable impurities. % Or less. When a high-temperature storage test was conducted at 150 ° C. for 500 hours, the measured joint strength value after the test was 84% of the initial value and maintained 80% or more of the reference value. Even if a Sn-58% Bi low melting point compound having a eutectic point temperature of 138 ° C. is produced in the part, the influence on reliability is considered to be small. In addition, when the Sn content of the joined body is 1.0% by weight and 1.5% by weight excluding inevitable impurities, the measured bonding strength values after the test are 76% and 71%, respectively. Since it is less than 80% of the value, it has a great influence on the reliability and is considered unusable.

  FIG. 6 is an enlarged view in the case where the Sn plating process generally used for the electrode 13 of the electronic component is performed. In this case, the constituent elements of the high-temperature solder material after joining are five types of Bi, Ag, Cu, Al, and Sn, and Sn-58% Bi compound 14 having a eutectic point temperature at 138 ° C. is generated. As a result, the bonding reliability is lowered.

  FIG. 7 is a view showing a soldered article using the solder material produced in the present invention.

  In FIG. 7, the flat lead 15 has a structure joined to the metal foil 17 by a solder material 16 inside a semiconductor mounting component that is loaded with a high voltage and a high current such as a power transistor and generates a large amount of heat. The power transistor 18 produced in this manner is mounted on the mother board 19 in a separate process and used, thereby becoming an electric or electronic device. At this time, the solder material 16 contains Bi and contains 0.1 to 8.0% by weight of Ag and 0.1 to 3.0% by weight of Cu so that the solder material 16 inside the power transistor does not melt and the electrical connection is not broken. %, Ge 0.1-2.0 wt%, Zn 0.1-6.0 wt%, at least two elements selected from Pd 0.01-0.5 wt%, Al 0.01-1.0 By making the composition composed of at least one element selected from wt%, Co 0.01 to 0.5 wt%, Si 0.01 to 0.5 wt%, and the balance of Bi, harmful lead It is a high-temperature solder material having a melting point of 250 to 300 ° C. without including a problem that the melting point changes greatly due to variation in the addition rate.

  FIG. 8 is an enlarged view of a part where the flat lead 15 of the electronic component and the electrode 20 of the mother board 19 are joined by the solder material 21. In the soldered article, the flat lead 15 of the electronic component is subjected to Au flash treatment on the Ni base, and the Sn content is 0.5% by weight or less excluding inevitable impurities. Further, the electrode 20 of the mother substrate is Cu, and the Sn content is 0.5% by weight or less excluding inevitable impurities as in the case of the electrode of the electronic component. Therefore, the constituent elements of the high-temperature solder material after joining are composed of seven kinds of Bi, Ag, Cu, Al, Au, Ni and Sn, and the Sn content is 0.5% by weight or less excluding inevitable impurities. . When a high-temperature storage test was performed at 150 ° C. for 500 hours, the measured joint strength after the test was 82% of the initial value and maintained 80% or more of the reference value. Even if a Sn-58% Bi low melting point compound having a eutectic point temperature of 138 ° C. is formed at the junction of the above, it is considered that the influence on the reliability is small. In addition, when the Sn content of the bonded body is 1.0 wt% and 1.5 wt% excluding inevitable impurities, the measured bonding strength after the test is 73% and 69%, which is the standard. Since it is less than 80% of the value, it has a great influence on the reliability and is considered unusable.

  FIG. 9 is an enlarged view in the case where the Sn plating process generally used for the flat lead 22 is performed. In this case, the constituent elements of the high-temperature solder material after joining are five types of Bi, Ag, Cu, Al, and Sn, and Sn-58% Bi compound 23 having a eutectic point temperature at 138 ° C. is generated. As a result, the bonding reliability is lowered.

  Therefore, in the soldered article using the solder material produced in the present invention, the Sn content of the joined body is 0.5% by weight or less excluding inevitable impurities, so that the high-temperature solder material after joining Even if a Sn-58% Bi compound is generated inside, it is possible to maintain the bonding reliability.

  The solder material production method of the present invention can synthesize a high-temperature solder material that does not contain lead and has a melting point of 250 to 300 ° C., and applies this solder material as a soldering material for mother boards and module parts of electric and electronic devices. can do.

The figure which shows the change of liquidus temperature at the time of adding Cu to Bi-2.5% Ag The figure which shows the change of liquidus temperature at the time of adding Ag-39% Cu eutectic to Bi-2.5% Ag in Embodiment 1 of this invention. The figure which shows the change of the liquidus temperature at the time of adding Al The figure which shows the soldering article using the solder material produced by this invention Enlarged view of the soldered article joint Enlarged view of the joint when the electrode is Sn plated The figure which shows the soldering article using the solder material produced by this invention Enlarged view of the soldered article joint Enlarged view of the joint when the electrode is Sn plated Diagram showing mounting parts using conventional high-temperature solder

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electronic component 2 Electrode component 3 Module substrate 4 Solder material 5 Module component 6 Mother substrate 7 Electronic component 8 Electronic component electrode 9 Module substrate 10 Solder material 11 Module component 12 Module substrate electrode 13 Electronic component with Sn plating 14 Sn-58% Bi compound 15 Flat lead 16 Solder material 17 Metal foil 18 Wart transistor 19 Mother board 20 Mother board electrode 21 Solder material 22 Sn plated flat lead 23 Sn-58% Bi compound

Claims (3)

The first metal component made of a binary eutectic alloy containing Bi is different from the first metal component in that the eutectic point temperature is different, and the binary by two kinds of metals selected from Bi, Ag, Cu, Ge, and Zn. A second metal component that is an eutectic alloy is added, a third metal component that is made of at least one metal selected from Pd, Al, Co, and Si is further added, and a solder material that has a melting point of 250 to 300 ° C. A method for producing a solder material, characterized by producing. The first metal component is Bi—Ag, the second metal component is selected from Ag—Cu, Ag—Ge, and Cu—Ge, and the third metal component is Al. The method for producing a solder material according to claim 1. The first metal component is Bi—Ge or Bi—Zn, the second metal component is Bi—Cu or Zn—Ge, and the third metal component is at least one selected from Pd, Al, Co, and Si. The method for producing a solder material according to claim 1, wherein the above is selected.

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