EP2101951A1 - Pb-free solder alloy - Google Patents

Pb-free solder alloy

Info

Publication number
EP2101951A1
EP2101951A1 EP07860735A EP07860735A EP2101951A1 EP 2101951 A1 EP2101951 A1 EP 2101951A1 EP 07860735 A EP07860735 A EP 07860735A EP 07860735 A EP07860735 A EP 07860735A EP 2101951 A1 EP2101951 A1 EP 2101951A1
Authority
EP
European Patent Office
Prior art keywords
specimen
experiment
solder alloy
free solder
manufactured
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07860735A
Other languages
German (de)
French (fr)
Other versions
EP2101951A4 (en
Inventor
Dong-Nyung Lee
Sang-Beom Kim
Kyoo-Sik Kang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Iljin Copper Foil Co Ltd
Original Assignee
Iljin Copper Foil Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Iljin Copper Foil Co Ltd filed Critical Iljin Copper Foil Co Ltd
Publication of EP2101951A1 publication Critical patent/EP2101951A1/en
Publication of EP2101951A4 publication Critical patent/EP2101951A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead

Definitions

  • the present invention relates to a solder alloy not containing lead (hereinafter, referred to as a Pb-free solder alloy), and more particularly, to a Pb-free solder alloy that generates no whiskers by including beryllium (Be) or boron (B)
  • Soldering is a technique of joining two or more members together by using a solder having a melting point of 450 ° C or less. In soldering, only the solder is melted and a base material is not melted.
  • a conventional solder, used in soldering, is an alloy of lead (Pb) and tin (Sn)
  • Pb-Sn solders mostly comprise 63% by weight of tin and have a eutectic composition of tin and Pb, and a melting point of 183 ° C , which does not thermally destroy electronic parts.
  • the Pb-Sn solders have excellent wetability for the electrodes of ball grid arrays (BGAs) or the lands of printed circuit boards (PCBs) and thus reduce the number of soldering failures.
  • Pb-free solders containing no lead are recently in use
  • a compound obtained by adding Ag, Cu, Zn, In, Ni, Cr, Fe, Co, Ge, P, or Ga to a Sn-Ag based material, a Sn-Cu based material, a Sn-Bi based material, a Sn-Zn based material, or an alloy of each of the aforementioned materials is the main representative of Pb-free solder alloys
  • a Sn-3Ag-0 5Cu compound from among Pb-free solders obtained by adding Cu to a Sn-Ag based material is good in terms of solderabihty, a joint strength, and high-resistant fatigability, and is thus currently used in soldering for many electronic apparatuses
  • the Sn-3Ag-0.5Cu compound is also used as a solder alloy for forming bumps and balls of BGAs.
  • whiskers are prone to be formed on the surface of the solder
  • the whiskers are denoted by crystals that grow from the surface of the solder when the solder is joined with a different material and their components are diffused with each other These whiskers are sensitive to heat and moisture When these whiskers are formed on the surface of a solder alloy, an electrical short occurs within a circuit. Therefore, the durabilities of a BGA package and a flip-chip package are reduced.
  • FIGS. 1A through 1 D are scanning electron microscope (SEM) pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, according to a first experiment;
  • SEM scanning electron microscope
  • 2A through 2D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a second experiment; FIGS.
  • 3A through 3D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a third experiment; FIGS.
  • FIGS. 4A through 4D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fourth experiment; FIGS.
  • 5A through 5D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fifth experiment; FIGS.
  • 6A through 6D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a sixth experiment; FIGS.
  • FIGS 8A through 8D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a seventh experiment,
  • FIGS 8A through 8D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to an eighth experiment,
  • FIGS 9A through 9D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a ninth experiment,
  • FIGS. 10A through 10D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a tenth experiment,
  • FIGS 11 A through 11 D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to an eleventh experiment,
  • FIGS 12A through 12D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a twelfth experiment,
  • FIGS 13A through 13D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a first comparative experiment,
  • FIGS 14A through 14D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a second comparative experiment;
  • FIGS. 15A through 15D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a third comparative experiment;
  • FIGS. 16A through 16D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fourth comparative experiment;
  • FIGS. 16A through 16D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fourth comparative experiment;
  • 17A through 17D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fifth comparative experiment; and
  • FIGS. 18A through 18D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a sixth comparative experiment.
  • a Pb-free solder alloy comprising tin (Sn) as a first element and one of boron (B) or beryllium (Be) as a second element.
  • the second element of the Pb-free solder alloy may be 0.001 to 0.4 % by weight of Be and the rest of the Pb-free solder alloy may be comprised of the first element and inevitable impurities.
  • the second element of the Pb-free solder alloy may be 0.003 to 0.5 % by weight 5 of B and the rest of the Pb-free solder alloy may be comprised of the first element and inevitable impurities.
  • the Pb-free solder alloy may further include copper (Cu) as a third element.
  • the third element may be 0.1 to 5.0% by weight.
  • the second element of the Pb-free solder alloy may be 0.001 to 0.4 % by weight it) of Be and the rest of the Pb-free solder alloy may be comprised of the first element, the third element, and inevitable impurities.
  • the second element of the Pb-free solder alloy may be 0.003 to 0.5 % by weight of B and the rest of the Pb-free solder alloy may be comprised of the first element, the third element, and inevitable impurities.
  • the Pb-free solder alloy may further comprise silver (Ag) as a fourth element.
  • the second element of the Pb-free solder alloy may be 0.001 to 0.4 % by weight of Be and the rest of the Pb-free solder alloy may be comprised of one of a group of the first and fourth elements and inevitable impurities and a group of the first, third, and fourth elements and inevitable impurities.
  • the second element of the Pb-free solder alloy may be 0.003 to 0.5 % by weight of B and the rest of the Pb-free solder alloy may be comprised of one of a group of the first and fourth elements and inevitable impurities and a group of the first, third, and fourth elements and inevitable impurities. 5 ADVANTAGEOUS EFFECTS
  • a Pb-free solder alloy capable of preventing generation of whiskers can be provided.
  • the inventors of the present invention paid attention to the fact that when a Pb-Sn solder is bonded to a pad formed of Cu, Cu is diffused faster than Sn on a bonding5 surface between the solder and the Cu pad.
  • the inventors of the present invention thought that a compressive stress applied by the intermetallic compound to the Sn of the solder can be removed by whiskers, 5 which are single crystals having beard formations, growing from the surface of the solder where Sn is spread
  • a Pb-free solder alloy according to the present invention is a Sn-based multi-element alloy that contains Sn as the main ions Accordingly, the Pb-free solder alloy according to the present invention may contain at least 80% by weight of Sn.
  • the main object of the present invention is to prevent generation of whiskers within a Pb-free solder alloy
  • the inventors of the present invention paid attention to Be or B as a material that can prevent the formation of a compressive stress within Sn crystals by preventing Sn and Cu from being diffused when a Sn-based solder and a Cu pad are bonded together
  • the Pb-free solder 0 alloy according to the present invention contains Sn as a first element and Be or B as a second element
  • the Pb-free solder alloy according to the present invention is referred to as a Sn-based alloy
  • the Pb-free solder alloy according to the present invention may contain 0 001 to 5 0 4 % by weight of Be or 0.003 to 0.5 % by weight of B
  • a sufficient amount of Be or B, as the second element, is inserted into an interstitial site in the Sn 1 which is the first element, as compared with a case where the Pb-free solder alloy according to the present invention contains less than 0 001 % by weight of Be or less than 0 003 % by weight of B
  • the0 effect of preventing growth of an intermetallic compound between Sn and Cu is high, and as described later, whiskers may not be generated even under harsh conditions such as a thermal shock test, a thermo-hydrostatic test, etc
  • the Pb-free solder alloy according to the present invention contains more than 0 4 % by weight of Be or more than 0.5 % by weight of B, the Be or B inserted into the interstitial site in the5 Sn is saturated, thereby causing an increase in the manufacturing costs and a degradation of economical efficiency.
  • the Pb-free solder alloy may further contain Cu as a third element. In this case,
  • Pb-free solder alloy may increase, as compared with when the Cu content is less than
  • the Pb-free solder alloy may further include silver (Ag) as a fourth element.
  • silver Ag
  • the thermal shock tolerance of the Pb-free solder alloy may significantly increase, as compared with when the Ag content is less than 1.0% by weight, and the drop tolerance thereof may improve, as compared with when the Ag content exceeds 3.0% by weight.
  • Such a Pb-free solder may be manufactured in various forms, such as, a ball, a cream, a bar, a wire, etc.
  • a Pb-free solder alloy is a Sn-Be-Cu ternary alloy.
  • a Be-Cu alloy was first manufactured, Sn was melted in a melting pot, and the Be-Cu alloy was melted in the melting pot, thereby producing a melt. After the temperature of the melt was kept for a certain period of time between 600 0 C and 650 " C 1 the melt was tapped from the melting pot and cast into a bar-shaped Sn-Be-Cu solder alloy specimen.
  • the unit of the numbers shown in Table 1 is % by weight, and the numbers are the contents of the elements inserted into the melt. Besides the elements stated in Table 1 , very small amounts of impurities, such as phosphorus (P), nickel (Ni), and cobalt (Co), may be further included in the melt.
  • impurities such as phosphorus (P), nickel (Ni), and cobalt (Co)
  • the column “right after the manufacture” indicates whether whiskers were generated on the experimental specimens just after being manufactured
  • the column “thermal shock” indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens which underwent thermal shock tests in which a specimen is maintained between -55 0 C and 80 V 1000 times for 20 minutes per one time
  • the column “thermo-hydrostatic test” indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens which underwent thermo-hydrostatic tests in which a specimen is maintained for 1000 hours at a humidity of 90% and a temperature of 80 0 C
  • the column “leaving undisturbed at a normal temperature” indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens which were left for 12 months at a normal temperature.
  • "Undetected”, as shown in the below tables including Table 1 indicates that no whiskers were generated in the manufactured experimental specimens
  • "Detected” indicates that whiskers were generated in the manufactured experimental specimens.
  • FIGS. 1A through 1 D are scanning electron microscope (SEM) pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, according to a first experiment.
  • SEM scanning electron microscope
  • 2A through 2D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a second experiment.
  • FIGS. 3A through 3D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a third experiment.
  • FIGS. 4A through 4D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fourth experiment.
  • FIGS. 5A through 5D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fifth experiment.
  • the detected whiskers have lengths of 3.4 ⁇ m on average, and the number of whiskers per unit area (m ⁇ f) is 3
  • whiskers were generated after harsh conditions in the first experiment, the lengths of the whiskers are significantly less than those in comparative experiments that are to be described later, and the number of whiskers per unit area is small.
  • the Sn-Be-Cu ternary alloy according to the first embodiment provides good effects compared with conventional ones.
  • no whiskers were detected in the second through fifth experiments where the content of Be is at least 0.001% by weight
  • a Sn-Be-Cu ternary alloy including at least 0.001 % by weight of Be is preferable (Second embodiment)
  • a Pb-free solder alloy according to the second embodiment is a Sn-Be-Cu-Ag quaternary alloy.
  • a Be-Cu alloy was first manufactured, Sn was melted in a melting pot, and the Be-Cu alloy and silver (Ag) were melted in the melting pot, thereby producing a melt. After the temperature of the melt was kept for a certain period of time between a temperature of 600 ° C to 650 ° C , the melt was tapped from the melting pot and cast into a bar-shaped Sn-Be-Cu-Ag solder alloy specimen. The bar-shaped Sn-Be-Cu-Ag solder alloy specimen was processed as in the first embodiment so as to manufacture experimental specimens.
  • Table 2 shows the contents of Sn, Be, Cu, and Ag in the experimental specimens manufactured according to the second embodiment.
  • the unit of the numbers shown in Table 2 is % by weight, and the numbers are the contents of the elements inserted into the melt.
  • very small amounts of impurities, such as P, Ni, and Co, may be further included in the melt.
  • Table 2 also indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens right after being manufactured, after a thermal shock test, after a thermo-hydrostatic test, and after being left undisturbed at a normal temperature, under the same conditions as those in Table 1.
  • FIGS. 6A through 6D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a sixth experiment
  • FIGS 7A through 7D are SEM pictures of a surface of a specimen that has just
  • FIGS 8A through 8D are SEM pictures of a surface of a specimen that has just been i o manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to an eighth experiment
  • FIGS 9A through 9D are SEM pictures of a surface of a specimen that has just
  • the bar-shaped Sn-B-Cu solder alloy specimen was processed as in the first embodiment so as to manufacture experimental specimens 5
  • the following Table 3 shows the contents of Sn, B, and Cu in the experimental specimens manufactured according to the third embodiment
  • the unit of the numbers shown in Table 3 is % by weight, and the numbers are the contents of the elements inserted into the melt.
  • very small amounts of impurities, such as P, Ni, and Co, may be further included in the melt.
  • Table 3 also indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens right after being manufactured, after a thermal shock test, after a thermo-hydrostatic test, and after being left undisturbed at a normal temperature, under the same conditions as those in Table 1
  • FIGS. 10A through 10D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a tenth experiment.
  • FIGS. 10A through 10D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a tenth experiment.
  • FIGS. 10A through 10D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a
  • 1 1A through 11 D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to an eleventh experiment.
  • FIGS. 1 1A through 11 D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to an eleventh experiment.
  • 12A through 12D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a twelfth experiment.
  • Table 3 and FIGS. 10A through 12D no whiskers were generated on a surface of the Sn-B-Cu ternary alloy according to the third embodiment just after being manufactured.
  • whiskers were generated on the surface of the Sn-B-Cu ternary alloy that underwent a thermal shock test, the surface thereof that underwent a thermo-hydrostatic test, and the surface thereof that was left undisturbed at a normal temperature.
  • the detected whiskers have lengths of 3.0 ⁇ m on average, and the number of whiskers per unit area (m ⁇ f) is 5.
  • the Sn-Be-Cu ternary alloy according to the third embodiment provides good effects compared with conventional ones.
  • Pb-free solder alloys according to the comparative experiments are a Sn-Cu binary alloy and a Sn-Ag-Cu ternary alloy.
  • a Sn-Cu ingot and a Sn-Ag-Cu ingot by Samhwa Non-ferrous Metal Ind. Co., Ltd were used in the comparative experiments.
  • Experimental specimens were manufactured using the Sn-Cu ingot and the Sn-Ag-Cu ingot according to the same method as in the first embodiment.
  • the unit of the contents shown in Table 4 is % by weight.
  • Table 4 also indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens right after being manufactured, after a thermal shock test, after a thermo-hydrostatic test, and after being left undisturbed at a normal temperature, under the same conditions as those in Tables 1 through 3.
  • FIGS. 13A through 13D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the 5 same conditions as those of the first experiment, according to a first comparative experiment.
  • FIGS. 14A through 14D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the i o specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a second comparative experiment.
  • FIGS. 15A through 15D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a i s surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a third comparative experiment.
  • FIGS. 16A through 16D are SEM pictures of a surface of a specimen that has just0 been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fourth comparative experiment. 5 FIGS.
  • 17A through 17D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fifth comparative0 experiment.
  • FIGS. 17A through 17D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fifth comparative0 experiment.
  • 18A through 18D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a sixth comparative experiment.
  • whiskers were generated on the surfaces of all of the Sn-based solder alloys including neither Be nor B.
  • whiskers were generated on the surface of the manufactured specimen that underwent a thermal shock test, the surface thereof that underwent a thermo-hydrostatic test, and the surface thereof that was left undisturbed at a normal temperature.
  • Table 5 shows the mean of the lengths of the generated whiskers and the number of whiskers per unit area.
  • the solder alloys of the first and tenth experiments have whiskers that are significantly short and the number of which is significantly small, as compared with the Sn-Cu solder alloys of the first through third comparative experiments and the Sn-Ag-Cu solder alloys of the fourth through sixth comparative experiments.
  • a solder alloy according to the present invention can be prevented from having whiskers even when being under bad conditions. While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by one of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
  • solder alloy according to the present invention can be used in soldering wires of various machines and electronic apparatuses.

Abstract

The present invention is provided to prevent the generation of whiskers via a lead (Pb)-free solder alloy. To achieve this objective, the present invention provides a Pb-free solder alloy including tin (Sn) as a first element and either boron (B) or beryllium (Be) as a second element.

Description

Pb-FREE SOLDER ALLOY
TECHNICAL FIELD The present invention relates to a solder alloy not containing lead (hereinafter, referred to as a Pb-free solder alloy), and more particularly, to a Pb-free solder alloy that generates no whiskers by including beryllium (Be) or boron (B)
BACKGROUND ART Soldering is a technique of joining two or more members together by using a solder having a melting point of 450°C or less. In soldering, only the solder is melted and a base material is not melted.
A conventional solder, used in soldering, is an alloy of lead (Pb) and tin (Sn) Such Pb-Sn solders mostly comprise 63% by weight of tin and have a eutectic composition of tin and Pb, and a melting point of 183°C , which does not thermally destroy electronic parts. In addition, the Pb-Sn solders have excellent wetability for the electrodes of ball grid arrays (BGAs) or the lands of printed circuit boards (PCBs) and thus reduce the number of soldering failures.
However, when electronic apparatuses using such Pb-Sn solders are disused, the Pb contained in these solders pollutes the environment With the reinforcement of a restriction on the use of Pb, the Pb-Sn solders are becoming difficult to be used
Accordingly, Pb-free solders containing no lead are recently in use A compound obtained by adding Ag, Cu, Zn, In, Ni, Cr, Fe, Co, Ge, P, or Ga to a Sn-Ag based material, a Sn-Cu based material, a Sn-Bi based material, a Sn-Zn based material, or an alloy of each of the aforementioned materials is the main representative of Pb-free solder alloys
A Sn-3Ag-0 5Cu compound from among Pb-free solders obtained by adding Cu to a Sn-Ag based material is good in terms of solderabihty, a joint strength, and high-resistant fatigability, and is thus currently used in soldering for many electronic apparatuses The Sn-3Ag-0.5Cu compound is also used as a solder alloy for forming bumps and balls of BGAs.
However, when a Sn-Ag-Cu based Pb-free alloy is used as a solder for a long period of time, whiskers are prone to be formed on the surface of the solder The whiskers are denoted by crystals that grow from the surface of the solder when the solder is joined with a different material and their components are diffused with each other These whiskers are sensitive to heat and moisture When these whiskers are formed on the surface of a solder alloy, an electrical short occurs within a circuit. Therefore, the durabilities of a BGA package and a flip-chip package are reduced.
DESCRIPTION OF THE DRAWINGS FIGS. 1A through 1 D are scanning electron microscope (SEM) pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, according to a first experiment; FIGS. 2A through 2D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a second experiment; FIGS. 3A through 3D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a third experiment; FIGS. 4A through 4D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fourth experiment; FIGS. 5A through 5D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fifth experiment; FIGS. 6A through 6D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a sixth experiment; FIGS. 7A through 7D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a seventh experiment, FIGS 8A through 8D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to an eighth experiment,
FIGS 9A through 9D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a ninth experiment,
FIGS. 10A through 10D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a tenth experiment,
FIGS 11 A through 11 D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to an eleventh experiment,
FIGS 12A through 12D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a twelfth experiment,
FIGS 13A through 13D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a first comparative experiment,
FIGS 14A through 14D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a second comparative experiment;
FIGS. 15A through 15D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a third comparative experiment;
FIGS. 16A through 16D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fourth comparative experiment; FIGS. 17A through 17D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fifth comparative experiment; and
FIGS. 18A through 18D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a sixth comparative experiment.
DETAILED DESCRIPTION OF THE INVENTION
TECHNICAL PROBLEM The present invention provides a Pb-free solder alloy that does not include lead
(Pb) and also can prevent generation of whiskers.
TECHNICAL SOLUTION
According to an aspect of the present invention, there is provided a Pb-free solder alloy comprising tin (Sn) as a first element and one of boron (B) or beryllium (Be) as a second element. The second element of the Pb-free solder alloy may be 0.001 to 0.4 % by weight of Be and the rest of the Pb-free solder alloy may be comprised of the first element and inevitable impurities.
The second element of the Pb-free solder alloy may be 0.003 to 0.5 % by weight 5 of B and the rest of the Pb-free solder alloy may be comprised of the first element and inevitable impurities.
The Pb-free solder alloy may further include copper (Cu) as a third element.
The third element may be 0.1 to 5.0% by weight.
The second element of the Pb-free solder alloy may be 0.001 to 0.4 % by weight it) of Be and the rest of the Pb-free solder alloy may be comprised of the first element, the third element, and inevitable impurities.
The second element of the Pb-free solder alloy may be 0.003 to 0.5 % by weight of B and the rest of the Pb-free solder alloy may be comprised of the first element, the third element, and inevitable impurities. is The Pb-free solder alloy may further comprise silver (Ag) as a fourth element.
The second element of the Pb-free solder alloy may be 0.001 to 0.4 % by weight of Be and the rest of the Pb-free solder alloy may be comprised of one of a group of the first and fourth elements and inevitable impurities and a group of the first, third, and fourth elements and inevitable impurities. 0 The second element of the Pb-free solder alloy may be 0.003 to 0.5 % by weight of B and the rest of the Pb-free solder alloy may be comprised of one of a group of the first and fourth elements and inevitable impurities and a group of the first, third, and fourth elements and inevitable impurities. 5 ADVANTAGEOUS EFFECTS
According to the present invention as described above, a Pb-free solder alloy capable of preventing generation of whiskers can be provided.
BEST MODE 0 As described above, a conventional Sn-Ag-Cu-based Pb-free solder has a disadvantage of generating whiskers on the surface thereof. However, the cause of the generation of the whiskers is not yet clearly revealed.
The inventors of the present invention paid attention to the fact that when a Pb-Sn solder is bonded to a pad formed of Cu, Cu is diffused faster than Sn on a bonding5 surface between the solder and the Cu pad.
In other words, since copper (Cu) is diffused faster than tin (Sn), which is a main component of the solder, between the solder and the Cu pad, the Cu is diffused in the direction of a grain boundary of the solder Thereafter, an intermetallic compound with a Cu6Sn5 composition is formed in the solder
The inventors of the present invention thought that a compressive stress applied by the intermetallic compound to the Sn of the solder can be removed by whiskers, 5 which are single crystals having beard formations, growing from the surface of the solder where Sn is spread
Accordingly, the inventors of the present invention tried to reduce the number of generations of a compressive stress within the Sn by preventing intermetallic diffusion via the insertion of a metal whose atoms are small into an interstitial site within the i o crystal structure of the Sn, consequently preventing the generation of whiskers Beryllium (Be) or boron (B) may be used as the metal with small atoms A Pb-free solder alloy according to the present invention is a Sn-based multi-element alloy that contains Sn as the main ions Accordingly, the Pb-free solder alloy according to the present invention may contain at least 80% by weight of Sn. i s As described above, the main object of the present invention is to prevent generation of whiskers within a Pb-free solder alloy Particularly, the inventors of the present invention paid attention to Be or B as a material that can prevent the formation of a compressive stress within Sn crystals by preventing Sn and Cu from being diffused when a Sn-based solder and a Cu pad are bonded together Thus, the Pb-free solder 0 alloy according to the present invention contains Sn as a first element and Be or B as a second element Hence, at least 80% by weight of Sn is contained in the Pb-free solder alloy according to the present invention, and thus the Pb-free solder alloy according to the present invention is referred to as a Sn-based alloy
The Pb-free solder alloy according to the present invention may contain 0 001 to 5 0 4 % by weight of Be or 0.003 to 0.5 % by weight of B
In this case, a sufficient amount of Be or B, as the second element, is inserted into an interstitial site in the Sn1 which is the first element, as compared with a case where the Pb-free solder alloy according to the present invention contains less than 0 001 % by weight of Be or less than 0 003 % by weight of B Thus, as described above, the0 effect of preventing growth of an intermetallic compound between Sn and Cu is high, and as described later, whiskers may not be generated even under harsh conditions such as a thermal shock test, a thermo-hydrostatic test, etc Also, when the Pb-free solder alloy according to the present invention contains more than 0 4 % by weight of Be or more than 0.5 % by weight of B, the Be or B inserted into the interstitial site in the5 Sn is saturated, thereby causing an increase in the manufacturing costs and a degradation of economical efficiency. The Pb-free solder alloy may further contain Cu as a third element. In this case,
0.1 to 5.0% by weight of Cu may be included. Thus, the mechanical strength of the
Pb-free solder alloy may increase, as compared with when the Cu content is less than
0.1 % by weight, and the wetability thereof may improve, as compared with when the Cu content exceeds 5.0% by weight.
The Pb-free solder alloy may further include silver (Ag) as a fourth element. Here,
1.0 to 3.0% by weight of Ag may be included. In this case, the thermal shock tolerance of the Pb-free solder alloy may significantly increase, as compared with when the Ag content is less than 1.0% by weight, and the drop tolerance thereof may improve, as compared with when the Ag content exceeds 3.0% by weight.
Such a Pb-free solder may be manufactured in various forms, such as, a ball, a cream, a bar, a wire, etc.
MODE OF THE INVENTION The present invention will now be described more fully with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. The following experiments are not to be construed as limiting the invention but are described to provide a thorough understanding of the present invention.
(First embodiment)
A Pb-free solder alloy, according to the first embodiment, is a Sn-Be-Cu ternary alloy.
In the first embodiment, a Be-Cu alloy was first manufactured, Sn was melted in a melting pot, and the Be-Cu alloy was melted in the melting pot, thereby producing a melt. After the temperature of the melt was kept for a certain period of time between 600 0C and 650 "C 1 the melt was tapped from the melting pot and cast into a bar-shaped Sn-Be-Cu solder alloy specimen.
After the surface of a JIS 2 type Cu base with a comb shape was polished, a flux EC-19S-8 by Tamura-Kaken Corporation_was coated on the polished surface of the Cu base. Thereafter, the prepared Sn-Be-Cu solder alloy specimen was melted in a fused silica tube by a predetermined amount, and the Cu base was digested in the resultant fused silica tube for 3 seconds so as to perform dip soldering. Next, the dip-soldered substrate was dipped in ethyl acetate, and then residues of the flux were removed through ultrasonic cleaning, thereby manufacturing experimental specimens. The following Table 1 shows the contents of Sn, Be, and Cu in the experimental specimens manufactured according to the first embodiment. The unit of the numbers shown in Table 1 is % by weight, and the numbers are the contents of the elements inserted into the melt. Besides the elements stated in Table 1 , very small amounts of impurities, such as phosphorus (P), nickel (Ni), and cobalt (Co), may be further included in the melt.
In Table 1 , the column "right after the manufacture" indicates whether whiskers were generated on the experimental specimens just after being manufactured, the column "thermal shock" indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens which underwent thermal shock tests in which a specimen is maintained between -55 0C and 80 V 1000 times for 20 minutes per one time, the column "thermo-hydrostatic test" indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens which underwent thermo-hydrostatic tests in which a specimen is maintained for 1000 hours at a humidity of 90% and a temperature of 800C , and the column "leaving undisturbed at a normal temperature" indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens which were left for 12 months at a normal temperature. "Undetected", as shown in the below tables including Table 1 , indicates that no whiskers were generated in the manufactured experimental specimens, and "Detected" indicates that whiskers were generated in the manufactured experimental specimens.
[Table 1]
leaving
Thermo-hy
Right after Thermal undisturbed
Experiment Sn Be Cu drostatic manufacture] shock at normal test temperature
First experiment 99.9833 0.0005 0.0162 Undetected I Detected Detected Detected
Second
99.967 0.001 0.032 Undetected [Undetected Undetected Undetected experiment
Third experiment 99.484 0.020 0.496 Undetected Undetected Undetected Undetected
Fourth experiment 94.804 0.200 4.996 Undetected Undetected Undetected Undetected
Fifth experiment 94.604 0.400 4.996 Undetected Undetected Undetected Undetected
FIGS. 1A through 1 D are scanning electron microscope (SEM) pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, according to a first experiment. FIGS. 2A through 2D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a second experiment.
FIGS. 3A through 3D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a third experiment.
FIGS. 4A through 4D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fourth experiment.
FIGS. 5A through 5D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fifth experiment.
As can be seen in Table 1 and FIGS. 1A through 5D, no whiskers were generated on a surface of the Sn-Be-Cu ternary alloy according to the first embodiment just after being manufactured. However, in the first experiment where the content of beryllium (Be) is less than 0.001 % by weight, whiskers were generated on the surface of the Sn-Be-Cu ternary alloy that underwent a thermal shock test, the surface thereof that underwent a thermo-hydrostatic test, and the surface thereof that was left undisturbed at a normal temperature.
In the first experiment, the detected whiskers have lengths of 3.4 μm on average, and the number of whiskers per unit area (mπf) is 3 Although whiskers were generated after harsh conditions in the first experiment, the lengths of the whiskers are significantly less than those in comparative experiments that are to be described later, and the number of whiskers per unit area is small. Accordingly, the Sn-Be-Cu ternary alloy according to the first embodiment provides good effects compared with conventional ones. In Table 1 , no whiskers were detected in the second through fifth experiments where the content of Be is at least 0.001% by weight Thus, a Sn-Be-Cu ternary alloy including at least 0.001 % by weight of Be is preferable (Second embodiment)
A Pb-free solder alloy according to the second embodiment is a Sn-Be-Cu-Ag quaternary alloy. In the second embodiment, a Be-Cu alloy was first manufactured, Sn was melted in a melting pot, and the Be-Cu alloy and silver (Ag) were melted in the melting pot, thereby producing a melt. After the temperature of the melt was kept for a certain period of time between a temperature of 600 °C to 650 °C , the melt was tapped from the melting pot and cast into a bar-shaped Sn-Be-Cu-Ag solder alloy specimen. The bar-shaped Sn-Be-Cu-Ag solder alloy specimen was processed as in the first embodiment so as to manufacture experimental specimens.
The following Table 2 shows the contents of Sn, Be, Cu, and Ag in the experimental specimens manufactured according to the second embodiment. The unit of the numbers shown in Table 2 is % by weight, and the numbers are the contents of the elements inserted into the melt. Besides the elements stated in Table 2, very small amounts of impurities, such as P, Ni, and Co, may be further included in the melt. Table 2 also indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens right after being manufactured, after a thermal shock test, after a thermo-hydrostatic test, and after being left undisturbed at a normal temperature, under the same conditions as those in Table 1.
[Table 2] leaving
Right after Thermal Thermo-hydr undisturbed at
Experiment Sn Ag Cu Be manufacture shock ostatic test normal temperature
Sixth
98.900 1.000 0.097 0.003 Undetected Undetected Undetected Undetected experiment
Seventh 98.300 1.000 0.679 0.021 Undetected Undetected Undetected Undetected experiment
Eighth
96.900 3.000 0.097 0.003 Undetected Undetected Undetected Undetected experiment
Ninth
94.00 3.00 2.88 0.12 Undetected Undetected Undetected Undetected experiment
FIGS. 6A through 6D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a sixth experiment
FIGS 7A through 7D are SEM pictures of a surface of a specimen that has just
5 been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a seventh experiment, FIGS 8A through 8D are SEM pictures of a surface of a specimen that has just been i o manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to an eighth experiment
FIGS 9A through 9D are SEM pictures of a surface of a specimen that has just
15 been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a ninth experiment
As can be seen in Table 2 and FIGS 6A through 9D, no whiskers were generated0 on a surface of the Sn-Be-Cu ternary alloy according to the second embodiment just after being manufactured, a surface thereof that underwent a thermal shock test, a surface thereof that underwent a thermo-hydrostatic test, and a surface thereof that was left undisturbed at a normal temperature. 5 (Third embodiment)
A Pb-free solder alloy according to the third embodiment is a Sn-B-Cu ternary alloy
In the third embodiment, Sn was melted in a melting pot, and boron (B) and copper (Cu) were then melted in the resultant melting pot, thereby producing a melt0 After the temperature of the melt was kept for a certain period of time between a temperature of 600 0C to 650 °C , the melt was tapped from the melting pot and cast into a bar-shaped Sn-B-Cu solder alloy specimen
The bar-shaped Sn-B-Cu solder alloy specimen was processed as in the first embodiment so as to manufacture experimental specimens 5 The following Table 3 shows the contents of Sn, B, and Cu in the experimental specimens manufactured according to the third embodiment The unit of the numbers shown in Table 3 is % by weight, and the numbers are the contents of the elements inserted into the melt. Besides the elements stated in Table 3, very small amounts of impurities, such as P, Ni, and Co, may be further included in the melt.
Table 3 also indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens right after being manufactured, after a thermal shock test, after a thermo-hydrostatic test, and after being left undisturbed at a normal temperature, under the same conditions as those in Table 1
[Table 3L leaving undisturbed
Right after Thermal Thermo-hydr
Experiment Sn B Cu at normal manufacture shock ostatic test temperature
Tenth
99.989 0.001 0.010 Undetected Detected Detected Detected experiment
Eleventh
99.987 0.003 0.010 Undetected Undetected Undetected Undetected experiment
Twelfth
98.5 0.5 1.0 Undetected Undetected Undetected Undetected experiment
FIGS. 10A through 10D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a tenth experiment. FIGS. 1 1A through 11 D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to an eleventh experiment. FIGS. 12A through 12D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a twelfth experiment. As can be seen in Table 3 and FIGS. 10A through 12D, no whiskers were generated on a surface of the Sn-B-Cu ternary alloy according to the third embodiment just after being manufactured. However, in the tenth experiment where the content of B is less than 0.003% by weight, whiskers were generated on the surface of the Sn-B-Cu ternary alloy that underwent a thermal shock test, the surface thereof that underwent a thermo-hydrostatic test, and the surface thereof that was left undisturbed at a normal temperature.
In the tenth experiment, the detected whiskers have lengths of 3.0 μm on average, and the number of whiskers per unit area (mπf) is 5.
Although whiskers were generated after harsh conditions in the tenth experiment, the lengths of the whiskers are significantly less than those in comparative experiments that are to be described later, and the number of whiskers per unit area is small. Accordingly, the Sn-Be-Cu ternary alloy according to the third embodiment provides good effects compared with conventional ones.
In Table 3, no whiskers were detected in the eleventh and twelfth experiments where the content of B is at least 0.003% by weight. Thus, a Sn-Be-Cu ternary alloy including at least 0.003% by weight of B is preferable.
(Comparative experiments)
Pb-free solder alloys according to the comparative experiments are a Sn-Cu binary alloy and a Sn-Ag-Cu ternary alloy. A Sn-Cu ingot and a Sn-Ag-Cu ingot by Samhwa Non-ferrous Metal Ind. Co., Ltd were used in the comparative experiments. Experimental specimens were manufactured using the Sn-Cu ingot and the Sn-Ag-Cu ingot according to the same method as in the first embodiment. The unit of the contents shown in Table 4 is % by weight.
Table 4 also indicates whether whiskers were generated on the surfaces of the manufactured experimental specimens right after being manufactured, after a thermal shock test, after a thermo-hydrostatic test, and after being left undisturbed at a normal temperature, under the same conditions as those in Tables 1 through 3.
[Table 4]
Leaving
Comparative Right after Thermal Thermo-hydro undisturbed at
Sn Ag Cu experiment manufacture shock static test normal temperature
First comparative
99.9 0.0 0.1 Undetected Detected Detected Detected experiment
Second comparative
99.3 0.0 0.7 Undetected Detected Detected Detected experiment ._|
Third comparative
95.0 0.0 5.0 Undetected Detected Detected Detected experiment Fourth comparative
98.9 1.0 0.5 Undetected Detected Detected Detected experiment
Fifth comparative
98.0 3.0 0.5 Undetected Detected Detected Detected experiment
Sixth comparative
94.0 3.0 1.0 Undetected Detected Detected Detected experiment
FIGS. 13A through 13D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the 5 same conditions as those of the first experiment, according to a first comparative experiment.
FIGS. 14A through 14D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the i o specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a second comparative experiment.
FIGS. 15A through 15D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a i s surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a third comparative experiment.
FIGS. 16A through 16D are SEM pictures of a surface of a specimen that has just0 been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fourth comparative experiment. 5 FIGS. 17A through 17D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a fifth comparative0 experiment. FIGS. 18A through 18D are SEM pictures of a surface of a specimen that has just been manufactured, a surface of the specimen subjected to a thermal shock test, a surface of the specimen subjected to a thermo-hydrostatic test, and a surface of the specimen that was left undisturbed at a normal temperature, respectively, under the same conditions as those of the first experiment, according to a sixth comparative experiment.
As can be seen from Table 4 and FIGS. 13A through 18D, whiskers were generated on the surfaces of all of the Sn-based solder alloys including neither Be nor B. In the first and tenth experiments and the first through sixth comparative experiments, whiskers were generated on the surface of the manufactured specimen that underwent a thermal shock test, the surface thereof that underwent a thermo-hydrostatic test, and the surface thereof that was left undisturbed at a normal temperature. Table 5 shows the mean of the lengths of the generated whiskers and the number of whiskers per unit area.
JTable δ]
Average whisker length j Number of whiskers per unit area
First experiment 3.4 /a 3/πutf
Tenth experiment 3.0 /M
First through third
14.4 /a 11 /mm" comparative experiments
Fourth through sixth
11.8 /an 14/mm" j comparative experiments
As can be seen from Table 5, the solder alloys of the first and tenth experiments have whiskers that are significantly short and the number of which is significantly small, as compared with the Sn-Cu solder alloys of the first through third comparative experiments and the Sn-Ag-Cu solder alloys of the fourth through sixth comparative experiments.
Accordingly, even when an extremely small amount of Be1 namely, less than 0.001 % by weight of Be, is added to Sn or even when an extremely small amount of B, namely, less than 0.003% by weight of B, is added to Sn, an effect of preventing the generation of whiskers is significantly high, as compared with comparative examples in which neither Be nor B is added.
As described above, a solder alloy according to the present invention can be prevented from having whiskers even when being under bad conditions. While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by one of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
The solder alloy according to the present invention can be used in soldering wires of various machines and electronic apparatuses.

Claims

1. A Pb-free solder alloy comprising: tin (Sn) as a first element; and one of boron (B) or beryllium (Be) as a second element.
2. The Pb-free solder alloy of claim 1 , wherein the second element of the Pb-free solder alloy is 0.001 to 0.4 % by weight of Be and the rest of the Pb-free solder alloy is comprised of the first element and inevitable impurities.
3. The Pb-free solder alloy of claim 1 , wherein the second element of the
Pb-free solder alloy is 0.003 to 0.5 % by weight of B and the rest of the Pb-free solder alloy is comprised of the first element and inevitable impurities.
4. The Pb-free solder alloy of claim 1 , further comprising copper (Cu) as a third element.
5. The Pb-free solder alloy of claim 4, wherein the third element is 0.1 to 5.0% by weight.
6. The Pb-free solder alloy of claim 4 or 5, wherein the second element of the Pb-free solder alloy is 0.001 to 0.4 % by weight of Be and the rest of the Pb-free solder alloy is comprised of the first element, the third element, and inevitable impurities.
7. The Pb-free solder alloy of claim 4 or 5, wherein the second element of the Pb-free solder alloy is 0.003 to 0.5 % by weight of B and the rest of the Pb-free solder alloy is comprised of the first element, the third element, and inevitable impurities.
8. The Pb-free solder alloy of claim 1 or 4, further comprising silver (Ag) as a fourth element.
9. The Pb-free solder alloy of claim 8, wherein the second element of the Pb-free solder alloy is 0.001 to 0.4 % by weight of Be and the rest of the Pb-free solder alloy is comprised of one of a group of the first and fourth elements and inevitable impurities and a group of the first, third, and fourth elements and inevitable impurities.
10. The Pb-free solder alloy of claim 8, wherein the second element of the Pb-free solder alloy is 0.003 to 0.5 % by weight of B and the rest of the Pb-free solder alloy is comprised of one of a group of the first and fourth elements and inevitable impurities and a group of the first, third, and fourth elements and inevitable impurities.
EP07860735A 2006-12-29 2007-12-28 Pb-free solder alloy Withdrawn EP2101951A4 (en)

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KR20060138548 2006-12-29
KR1020070139767A KR101042031B1 (en) 2006-12-29 2007-12-28 Pb-free solder alloy
PCT/KR2007/006951 WO2008082191A1 (en) 2006-12-29 2007-12-28 Pb-free solder alloy

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EP2101951A1 true EP2101951A1 (en) 2009-09-23
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US20100092335A1 (en) 2006-12-29 2010-04-15 Iljin Copper Foil Co., Ltd. Pb-free solder alloy
JP5245568B2 (en) * 2008-06-23 2013-07-24 新日鉄住金マテリアルズ株式会社 Electronic member having lead-free solder alloy, solder ball and solder bump
CN103056543B (en) * 2013-01-18 2015-03-25 江苏师范大学 Lead-free nanometer solder containing Yb, A1 and B
CN105149809B (en) * 2015-10-10 2017-09-26 南京青锐风新材料科技有限公司 It is a kind of suitable for antioxidant of SnAgCu or SnCu solders and preparation method thereof
CN105834612B (en) * 2016-05-04 2018-02-23 中南大学 A kind of high-dimensional stability Sn Ag Cu solders suitable for Electronic Packaging
CN105834611B (en) * 2016-05-04 2018-02-13 中南大学 A kind of high conductance high reliability Ce Sn Ag Cu solders suitable for Electronic Packaging
CN107877031A (en) * 2017-11-27 2018-04-06 东莞市千岛金属锡品有限公司 A kind of lead-free low-temperature solder and preparation method thereof

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JP2010514931A (en) 2010-05-06
TWI366497B (en) 2012-06-21
KR20100132470A (en) 2010-12-17
KR101165426B1 (en) 2012-07-12
TW200927358A (en) 2009-07-01
KR101042031B1 (en) 2011-06-16
WO2008082191A1 (en) 2008-07-10
CN101588889A (en) 2009-11-25
EP2101951A4 (en) 2010-01-27
KR20080063176A (en) 2008-07-03
JP5210323B2 (en) 2013-06-12

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