CN113579557A - SnBi material alloy, and preparation method and application thereof - Google Patents
SnBi material alloy, and preparation method and application thereof Download PDFInfo
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- CN113579557A CN113579557A CN202110926536.6A CN202110926536A CN113579557A CN 113579557 A CN113579557 A CN 113579557A CN 202110926536 A CN202110926536 A CN 202110926536A CN 113579557 A CN113579557 A CN 113579557A
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- 229910052802 copper Inorganic materials 0.000 claims description 15
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- 229910020988 Sn—Ag Inorganic materials 0.000 claims description 5
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- 238000007711 solidification Methods 0.000 abstract description 27
- 230000008023 solidification Effects 0.000 abstract description 27
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Classifications
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- 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
- B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
- B23K35/282—Zn as the principal constituent
-
- 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
- B23K35/40—Making wire or rods for soldering or welding
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
The invention provides a SnBi material alloy and a preparation method and application thereof, wherein the SnBi material alloy comprises Sn, Bi and Sb elements; wherein the Bi element and the Sb element account for y percent and x percent respectively in the SnBi material alloy, the balance is Sn and a small amount of inevitable impurities, x is more than or equal to 0 and less than or equal to 10, y is more than or equal to 30 and less than or equal to 45, and y is-0.0117 x2+1.1176x +32+ c, c is a correction factor, and-1 is less than or equal to c is less than or equal to 1. The thermal expansion coefficient of the alloy during solidification is regulated and controlled by utilizing the characteristic of cold contraction and thermal expansion of the Bi element, so that the problem of shrinkage of the solder alloy during solidification is solved, the SnBi material alloy has little or no shrinkage during solidification, and the performance is excellent.
Description
Technical Field
The invention relates to the technical field of through hole filling materials, in particular to a SnBi material alloy and a preparation method and application thereof.
Background
Integrated circuits are an integral part of all electronic products. The rapid development of electronic products in the direction of light weight, thinness, shortness, miniaturization and high functionality requires the volume of integrated circuits to be more miniaturized, and three-dimensional integrated circuits have become a necessary trend of development. In view of the development process of three-dimensional integrated circuits, through-via technology has gradually become an inevitable solution for three-dimensional integrated circuit interconnection as the through-via wafer packaging technology is continuously developed towards high yield.
The through hole technology can enable the stacking density of chips in the three-dimensional direction to be maximum, the interconnection line between the chips to be shortest and the overall dimension to be minimum, can effectively realize the 3D chip stacking, can manufacture the chips with more complex structures, stronger performance and more cost efficiency, and becomes the most attractive technology in the current electronic packaging technology.
The filling of the through holes is a key of the through hole technology and is a link with high difficulty, the filling effect of the through holes is directly related to the problems of reliability, yield and the like of the integrated technology, and the high reliability and yield are very important for the practicability of the three-dimensional integrated circuit. Conventional filling methods typically use electroplated copper to fill the via. The aperture of the through-hole is typically several microns to tens of microns, and the depth may reach tens to hundreds of microns. Due to its high aspect ratio structure, the copper electroplating process generally requires several to tens of hours, the filling efficiency is low, and the electrolyte and additives are toxic and also pollute the environment. The existing process for quickly filling the through hole by using the solder alloy can improve the filling speed of the through hole and the production efficiency. However, the shrinkage of the solder alloy during the solidification process can seriously affect the filling quality, generate filling defects and affect the popularization of a new process.
Disclosure of Invention
In order to solve the defects in the prior art, the invention mainly aims to provide the SnBi material alloy and the preparation method and the application thereof, the SnBi material alloy utilizes the characteristic of Bi element cold contraction and thermal expansion to regulate and control the thermal expansion coefficient of the alloy during solidification, and solves the problem of shrinkage of the solder alloy during solidification, so that the SnBi material alloy has little shrinkage or no shrinkage during solidification and has excellent performance.
In order to achieve the above object, according to a first aspect of the present invention, there is provided an SnBi-based material alloy.
The SnBi material alloy comprises Sn, Bi and Sb elements; wherein the mass percentages of the Sb element and the Bi element in the SnBi material alloy are respectively x percent and y percent, the rest is Sn and a small amount of inevitable impurities, x is more than or equal to 0 and less than or equal to 10, y is more than or equal to 30 and less than or equal to 45, and y is-0.0117 x2+1.1176x +32+ c, c is a correction factor, and-1 is less than or equal to c is less than or equal to 1.
Further, the mass percentages of the Sb element and the Bi element in the SnBi material alloy are respectively x% and y%, wherein x is more than or equal to 0 and less than or equal to 9, and y is more than or equal to 30 and less than or equal to 40;
preferably, -0.1. ltoreq. c.ltoreq.0.1; c is more than or equal to 0 and less than or equal to 0.05.
Further, the SnBi-based material alloy further includes at least one of Ag, Cu, Co, Ti, Ni, and In elements.
Further, when the SnBi material alloy contains Ag, Cu, Co, Ti, Ni, and In elements, the respective contents thereof by mass percent are: 0.1-3% of Ag, 0.01-2.5% of Cu, 0.01-0.1% of Co, 0.01-0.1% of Ti, 0.03-0.9% of Ni and 0.01-1% of In.
In order to achieve the above object, according to a second aspect of the present invention, there is provided a method for producing an SnBi-based material alloy.
The preparation method of the SnBi material alloy comprises the following steps:
according to a certain alloy proportion, melting and mixing metal simple substances or alloys of all elements to obtain the SnBi material alloy; wherein, Sn element and Bi element are introduced in the form of metal simple substance during melting, and Sb element is introduced in the form of Bi-Sb alloy.
Furthermore, Ag, Cu, Co, Ti and Ni elements are introduced in a mode of Sn-Ag, Sn-Cu, Sn-Co, Sn-Ti and Sn-Ni alloy during melting.
Further, In element is introduced In a metal simple substance mode during melting.
Furthermore, the alloy is prepared by a vacuum melting method; wherein the smelting furnace is vacuumized to 1 x 10-1～1×10-2Pa and filling protective gas.
Further, the melting temperature of melting and mixing the metal simple substances or the alloy of each element is 200-500 ℃, and the temperature is kept for 10-20 min.
In order to achieve the above object, according to a third aspect of the present invention, there is provided a use of an SnBi-based material alloy.
The SnBi material alloy prepared by the preparation method is used as a filling material for through holes of integrated circuit chips.
The SnBi material alloy is a low-melting-point welding material, and has fine crystal grains.
In the SnBi material alloy, the property of the Bi element of shrinking and expanding can regulate and control the thermal expansion coefficient of the alloy during solidification, and the problem of shrinkage of the solder alloy during solidification is solved.
The Sb element is added into the alloy, so that the microstructure of the brazing filler metal can be refined, the conductivity and the wettability of the brazing filler metal are improved, and meanwhile, the addition of the Sb element is beneficial to improving the electrode potential of an alloy matrix, so that the corrosion resistance of the alloy is improved.
The noble metal Ag can improve the mechanical strength of the alloy by adding the Ag element; in addition, Ag can improve the wettability and weldability of the alloy, high-temperature creep, thermal cycle reliability and other performances.
The trace Cu element can promote the wetting spreading capability of the alloy.
A certain amount of Co element is added into the alloy, so that the microstructure of the brazing filler metal can be refined, the supercooling degree is reduced, the growth of intermetallic compounds is consistent, and the drop impact resistance is improved.
Ti alloy elements form a compact oxidation film on the surface of the brazing filler metal through the comprehensive action of the elements, so that the oxidation of the brazing filler metal is prevented, and the oxidation resistance and the pore-filling wettability of the alloy are improved.
The strength and toughness of the alloy can be further improved by adding Ni element and In element simultaneously.
In the present invention, the Sn-Bi alloy can improve the electrical properties of the alloy by controlling the addition ratio and distribution state of the Sn element and other elements.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
fig. 1 shows the filling effect of the SnBi material alloy prepared in the embodiment of the present invention as the via filling material for the ic chip.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
According to a specific embodiment of the present invention, there is provided an SnBi-based material alloy which is simple in preparation process and excellent in performance, and which is a low melting point alloy.
The SnBi material alloy can be applied to an integrated circuit chip and used as a through hole filling material of the integrated circuit chip.
The SnBi material alloy comprises Sn, Bi and Sb elements; wherein the Bi element and the Sb element account for y percent and x percent respectively in the SnBi material alloy, the balance is Sn and a small amount of inevitable impurities, x is more than or equal to 0 and less than or equal to 10, y is more than or equal to 30 and less than or equal to 45, and y is-0.0117 x2+1.1176x +32+ c, c is a correction factor, and-1 is less than or equal to c is less than or equal to 1.
In the above-described embodiment, the SnBi material alloy may or may not include Sb element, and is formed as a lead-free SnBi material alloy; and the relational expression of the mass percentage of the Bi element no matter whether the Sb element is added or not
y＝-0.0117x2+1.1176x +32+ c holds.
In the embodiment of the invention, the Bi element and the Sb element account for y percent and x percent respectively in the SnBi material alloy, wherein x is more than or equal to 0 and less than or equal to 9, and y is more than or equal to 30 and less than or equal to 40.
In the embodiment of the invention, -0.1 ≦ c ≦ 0.1.
As a more preferred embodiment of the present invention, 0. ltoreq. c.ltoreq.0.05.
The SnBi material alloy of the present invention further includes at least one of Ag, Cu, Co, Ti, Ni, and In elements, and may be selected as necessary.
When the SnBi material alloy contains Ag, the content of the Ag element is 0.1-3% by mass.
In the embodiment of the present invention, the mass percentage of the Ag element may be 0.1 to 2%, and more preferably 1 to 2%.
When the SnBi material alloy contains Cu, the content of Cu is 0.01-2.5% by mass.
In the embodiment of the present invention, the mass percentage of the Cu element may be 0.01 to 2%, and more preferably 0.02 to 1%.
When the SnBi material alloy contains Co element, the content of Co element is 0.01-0.1% by mass percent.
In the embodiment of the present invention, the mass percentage of the Co element may be 0.01 to 0.08%, and more preferably 0.03 to 0.05%.
When the SnBi material alloy contains Ti, the content of Ti is 0.01-0.1% by mass.
In the embodiment of the present invention, the mass percentage of the Ti element may be 0.01 to 0.08%, and more preferably 0.03 to 0.05%.
When the SnBi-based material alloy contains Ni, the mass percentage of the Ni element may be 0.03 to 0.9%.
In the embodiment of the present invention, the mass percentage of the Ni element may be 0.05 to 0.5%, and more preferably 0.3 to 0.5%.
When the SnBi-based material alloy contains an In element, the In element content is 0.01 to 1% by mass.
In the embodiment of the present invention, the In element may be 0.1 to 0.8% by mass, and more preferably 0.3 to 0.5% by mass.
According to another specific embodiment of the invention, a preparation method of the lead-free SnBi-based material alloy is provided.
The preparation method of the lead-free SnBi material alloy comprises the following steps:
adding Sn and Bi metal simple substances into a smelting furnace according to the required alloy proportion, covering an anti-oxidation flux on the surface in the smelting process, heating to the melting temperature of 200-500 ℃, properly preserving the temperature for 10-20 min, removing surface oxidation slag, and pouring into a mold to prepare the lead-free SnBi material alloy.
In the preparation method, when at least one of Ag, Cu, Co, Ti and Ni elements needs to be added, Sn-Ag, Sn-Co, Sn-Ti, Sn-Cu or Sn-Ni alloy is prepared by respectively utilizing a vacuum melting method, then Sn, Bi metal simple substances and the prepared alloy are added into a melting furnace according to the required alloy proportion, an anti-oxidation flux covers the surface in the melting process, the melting temperature is heated to 200-500 ℃, the temperature is properly preserved for 10-20 min, surface oxidation slag is removed, and the alloy is poured into a mold to prepare the lead-free SnBi series material alloy.
When In element needs to be added, the Sn, Bi and In metal simple substances are directly added into a smelting furnace according to the required alloy proportion, an anti-oxidation flux is covered on the surface In the smelting process, the temperature is heated to 200-500 ℃, the temperature is properly preserved for 10-20 min, surface oxidation slag is removed, and the alloy is poured into a mold to prepare the lead-free SnBi series material alloy.
When In element and at least one of Ag, Cu, Co, Ti and Ni element are required to be added simultaneously, the prepared alloy and Sn, Bi and In metal simple substances are added into a smelting furnace according to the required alloy proportion, an anti-oxidation flux is covered on the surface In the smelting process, the smelting temperature is 200-500 ℃, the temperature is properly preserved for 10-20 min, surface oxidation slag is removed, and the alloy is poured into a mold to prepare the lead-free SnBi series material alloy.
According to another specific embodiment of the invention, the invention further provides a preparation method of the SnBi material alloy.
The preparation method of the SnBi material alloy comprises the following steps:
(1) preparing a Bi-Sb alloy by using a vacuum melting method;
(2) adding the prepared Bi-Sb alloy and Sn and Bi metal simple substances into a smelting furnace according to the required alloy proportion, covering an anti-oxidation flux on the surface in the smelting process, heating to the melting temperature of 200-500 ℃, properly preserving the heat for 10-20 min, removing surface oxidation slag, and pouring into a mold to prepare the SnBi material alloy.
In the preparation method, when at least one of Ag, Cu, Co, Ti and Ni elements needs to be added, Sn-Ag, Sn-Co, Sn-Ti, Sn-Cu or Sn-Ni alloys are respectively prepared by a vacuum melting method, then the prepared alloy, Bi-Sb alloy and Sn and Bi metal simple substances are added into a melting furnace according to the required alloy proportion, an anti-oxidation flux covers the surface in the melting process, the melting temperature is heated to 200-500 ℃, the proper heat preservation is carried out for 10-20 min, surface oxidation slag is removed, and the alloy is poured into a mold to prepare the SnBi material alloy.
When In element needs to be added, directly adding the Bi-Sb alloy and the Sn, Bi and In metal simple substances into a smelting furnace according to the required alloy proportion, covering an anti-oxidation flux on the surface In the smelting process, heating to the melting temperature of 200-500 ℃, properly preserving the heat for 10-20 min, removing surface oxidation slag, and pouring into a mold to prepare the SnBi series material alloy.
When In element and at least one of Ag, Cu, Co, Ti and Ni element are required to be added simultaneously, the prepared alloy, Bi-Sb alloy and Sn, Bi and In metal simple substances are added into a smelting furnace according to the required alloy proportion, the surface is covered with an anti-oxidation flux In the smelting process, the alloy is heated to the melting temperature, the temperature is properly preserved, surface oxidation slag is removed, and the alloy is poured into a mold to prepare the SnBi series material alloy.
In the embodiment of the invention, the vacuum melting method specifically comprises the following steps: adding metal simple substances Bi and Sb, or Sn and Ag, or Sn and Co, or Sn and Ti, or Sn and Cu, or Sn and Ni into a vacuum melting furnace according to a certain alloy proportion, respectively, and vacuumizing to 1 x 10-1～1×10-2Pa, filling protective gas, respectively heating the alloy to a melting temperature, simultaneously electromagnetically stirring, and then carrying out vacuum casting to respectively prepare Bi-Sb, Sn-Ag, Sn-Co, Sn-Ti, Sn-Cu and Sn-Ni alloys.
Hereinafter, the SnBi-based material alloy and the method for preparing the same according to the present invention will be described in detail by way of specific examples.
Example 1
An Sn-Bi material alloy powder comprising, in mass percent: 35% of Bi, 2.5% of Sb and the balance of Sn and inevitable impurities, wherein the alloy has a density of 7.96 (g/cm) in a liquid state (231 ℃ C.)3) The density after solidification (135 ℃ C.) was also 7.96 (g/cm)3). The alloy has no shrinkage during solidification. The method for preparing the SnBi material alloy comprises the following steps:
1) metals Bi and Sb with the purity of 99.99 wt.% are mixed according to the mass ratio of 80: 20, adding the alloy into a vacuum smelting furnace, and vacuumizing to 1 multiplied by 10-1Pa, filling nitrogen; heating the alloy to 650-700 ℃ for melting, and performing electromagnetic stirring to make the alloy components uniform, and then performing vacuum casting to prepare a Bi-Sb20 alloy;
2) and adding the prepared Bi-Sb20 alloy and metals Sn and Bi into a smelting furnace according to the alloy proportion, covering rosin on the surface of the alloy in the smelting process, heating the alloy to 350 ℃, preserving the temperature for 10min, removing surface oxidation slag, and pouring the alloy into a mold to prepare the SnBi35Sb2.5 alloy.
Fig. 1 shows the filling effect of the snbi35sb2.5 alloy prepared in this example 1 as the filling material for the through holes of the integrated circuit chip, as shown in fig. 1, the filling quality is good, and there is no filling defect.
Example 2
An Sn-Bi material alloy powder comprising, in mass percent: 40% of Bi, 7.5% of Sb and the balance of Sn and inevitable impurities, wherein the alloy has a density of 8.03 (g/cm) in a liquid state (300 ℃ C.)3) The density after solidification (135 ℃ C.) was also 8.03 (g/cm)3). The alloy has no shrinkage during solidification.
The method for preparing the SnBi-based material alloy was the same as that of example 1 except that the surface of the alloy was covered with LiCl-KCL molten salt.
Example 3
An Sn-Bi material alloy powder comprising, in mass%: 33% of Bi, 1.5% of Sb, 2% of Ag, and the balance of Sn and inevitable impurities, wherein the alloy has a density of 7.98 (g/cm) in a liquid state (205 ℃ C.)3) The density after solidification (135 ℃ C.) was also 7.99 (g/cm)3). The method for preparing the alloy comprises the following steps:
1) metals Bi and Sb with the purity of 99.99 wt.% are mixed according to the mass ratio of 80: 20, adding the alloy into a vacuum smelting furnace, and vacuumizing to 1 multiplied by 10-2Pa, filling nitrogen, heating to 650-700 ℃ for melting, electromagnetically stirring to make the alloy components uniform, and then carrying out vacuum casting to prepare a Bi-Sb20 alloy;
2) adding Sn and Ag with the purity of 99.99 wt.% into a vacuum smelting furnace according to a certain alloy proportion, and vacuumizing to 1 x 10-2Pa, filling nitrogen; heating the alloy to 800-900 ℃ for melting, and performing electromagnetic stirring to make the alloy components uniform, and then performing vacuum casting to prepare Sn-Ag20 alloy;
3) adding the prepared Bi-Sb20 and Sn-Ag20 alloy and metal Sn and Bi into a smelting furnace according to the alloy proportion, covering rosin on the surface of the alloy, heating the alloy to 400 ℃, preserving the temperature for 15min, removing surface oxidation slag, and pouring the alloy into a mold to prepare the SnBi33Sb1.5Ag2 alloy.
Example 4
An Sn-Bi material alloy powder comprising, in mass%: 37% of Bi, 5% of Sb, 0.01% of Co, 0.02% of Ti, 0.03% of Cu and 0.4% of Ni, wherein the alloy has a density of 8.0 (g/cm) at 265 ℃ in a liquid state3) The density after solidification (135 ℃ C.) was also 8.01 (g/cm)3) The balance of Sn and inevitable impurities.
The method for preparing the SnBi material alloy is the same as the preparation method in the embodiment 3, and the difference is that Sn-Co5, Sn-Ti20, Sn-Cu20 and Sn-Ni5 alloys are respectively prepared according to certain alloy proportion; wherein the melting temperature is 900-1000 ℃, 1550-1650 ℃, 750-820 ℃ and 900-1100 ℃ respectively; then adding the prepared Bi-Sb20, Sn-Co5, Sn-Ti20, Sn-Cu20 and Sn-Ni5 alloy and metal Sn and Bi into a smelting furnace according to the alloy proportion, covering KCL-LiCl molten salt on the alloy surface, heating the alloy to 450 ℃, preserving the temperature for 15min, removing surface oxidation slag, and pouring into a mold to prepare the SnBi37Sb5Co0.01Ti0.02Cu0.03Ni0.4 alloy.
Example 5
An Sn-Bi material alloy powder comprising, in mass%: 32% of Bi, 0.1% of Co, 0.1% of Ti, 0.03% of Cu, 0.07% of Ni, 0.1% of Ag, and the balance of Sn and inevitable impurities, wherein the alloy has a density of 7.92(g/cm3) at 186 ℃ in a liquid state and a density of 7.92(g/cm3) after solidification at 139 ℃. The method for preparing the lead-free solder alloy comprises the following steps:
1) adding 99.99 wt.% metal Sn and Co, Sn and Ti, Sn and Cu, Sn and Ni, Sn and Ag into a vacuum smelting furnace according to a certain alloy proportion, respectively, and vacuumizing to 1 x 10-2Pa, filling nitrogen; then respectively heating the alloy to 900-1000 ℃, 1550-1650 ℃, 750-820 ℃, 900-1100 ℃ and 800-900 ℃ for melting, simultaneously electromagnetically stirring to make the alloy components uniform, and then carrying out vacuum casting to respectively prepare Sn-Co10, Sn-Ti20, Sn-Cu20, Sn-Ni5 and Sn-Ag20 alloys;
2) adding the prepared Sn-Co10, Sn-Ti20, Sn-Cu20, Sn-N5i and Sn-Ag20 alloy and metal Sn and Bi into a smelting furnace according to the alloy proportion, covering an anti-oxidation solvent (oil bath) on the alloy surface, heating the alloy to 450 ℃, preserving the temperature for 20min, removing surface oxidation slag, and pouring into a mold to prepare the SnBi32Co0.1Ti0.1Cu0.03Ni0.07Ag0.1 lead-free solder alloy.
Example 6
An Sn-Bi material alloy powder comprising, in mass%: 32% of Bi, 0.03% of In, and the balance Sn and inevitable impurities, and the alloy has a density of 7.92 (g/cm) In a liquid state (186 ℃)3) The density after solidification (139 ℃ C.) was also 7.92 (g/cm)3). The method for preparing the lead-free solder alloy comprises the following steps:
melting Sn, Bi and In with the purity of 99.99 wt.% In a smelting furnace according to the alloy ratio. Covering an anti-oxidation solvent (oil bath) on the surface of the alloy, heating the alloy to 250 ℃, preserving the heat for 20min, removing surface oxidation slag, and pouring into a mold to prepare the SnBi32In0.03 lead-free solder alloy.
Example 7
An Sn-Bi material alloy powder comprising, in mass%: bi 32%, and the balance Sn and inevitable impurities, and the alloy has a density of 7.92 (g/cm) (186 ℃ C.) in a liquid state3) The density after solidification (139 ℃ C.) was also 7.92 (g/cm)3). The method for preparing the lead-free solder alloy comprises the following steps:
metals Sn and Bi with the purity of 99.99 wt.% are melted in a smelting furnace according to the alloy ratio. Covering the surface of the alloy with an anti-oxidation solvent (oil bath), heating the alloy to 250 ℃, preserving the heat for 20min, removing surface oxidation slag, and pouring the alloy into a mold to prepare the SnBi32 lead-free solder alloy.
The densities of the solder alloys of examples 1-7 before and after solidification are summarized below and are detailed in Table 1.
TABLE 1 summary of densities before and after solidification of Sn-Bi based material alloys in examples 1 to 7
Note: in table 1, the balance of the components of the Sn — Bi material alloy is Sn and unavoidable impurities in mass%.
The properties of the SnBi material alloy prepared by the preparation method of the present invention will be further described by comparative examples.
Comparative example 1
A via-filling material alloy, the lead-free solder alloy comprising, in mass percent: 96.5% of Sn, 3% of Ag and 0.5% of Cu, wherein the alloy has a density of 7.05 (g/cm) at a temperature of 220 ℃ in a liquid state3) The density after solidification (216.06 ℃ C.) was also 7.3 (g/cm)3)。
Comparative example 2
A via-filling material alloy, the lead-free solder alloy powder comprising, in mass percent: 57% of Bi, 1.0% of Ag and the balance of Sn, wherein the density of the alloy in a liquid state (190 ℃) is 8.76 (g/cm)3) The density after solidification (138.05 ℃ C.) was also 8.54 (g/cm)3)。
The densities of the via hole filler alloys of comparative examples 1-2 before and after solidification are summarized below and are detailed in table 2.
TABLE 2 summary of densities before and after solidification of the via-filling alloy of comparative examples 1-2
Note: in table 2, the balance of the components in the alloy for via-hole filling material is Sn and inevitable impurities in mass%.
As can be seen from comparison between tables 1 and 2, in examples 1 to 7 of the present invention, compared to comparative examples 1 to 2, the density of the SnBi material alloy in the liquid state is almost the same as the density after solidification, and even if there is fluctuation, the density is within the error range, so that the SnBi material alloy in the present invention utilizes the property of Bi element to contract and expand with heat to regulate the thermal expansion coefficient of the alloy during solidification, thereby solving the problem of shrinkage of the solder alloy during solidification.
Furthermore, the electrical properties of the SnBi material alloy can be improved by adjusting the addition ratio of the Sn element to other elements.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. An SnBi-based material alloy, characterized in that the SnBi-based material alloy comprises Sn, Bi and Sb elements; wherein the mass percentages of the Sb element and the Bi element in the SnBi material alloy are respectively x percent and y percent, the rest is Sn and a small amount of inevitable impurities, x is more than or equal to 0 and less than or equal to 10, y is more than or equal to 30 and less than or equal to 45, and y is-0.0117 x2+1.1176x +32+ c, c is a correction factor, and-1 is less than or equal to c is less than or equal to 1.
2. The SnBi-based material alloy according to claim 1, wherein the Sb element and the Bi element account for x% and y% in the SnBi-based material alloy, respectively, and 0. ltoreq. x.ltoreq.9, 30. ltoreq. y.ltoreq.40;
preferably, -0.1. ltoreq. c.ltoreq.0.1; c is more than or equal to 0 and less than or equal to 0.05.
3. The SnBi-based material alloy according to claim 1 or 2, further comprising at least one of Ag, Cu, Co, Ti, Ni, and In elements.
4. The SnBi-based material alloy according to claim 3, wherein when the SnBi-based material alloy contains Ag, Cu, Co, Ti, Ni, In, the respective contents thereof are, In mass percent: 0.1-3% of Ag, 0.01-2.5% of Cu, 0.01-0.1% of Co, 0.01-0.1% of Ti, 0.03-0.9% of Ni and 0.01-1% of In.
5. The SnBi-based material alloy according to any one of claims 1 to 4, which comprises the steps of:
according to a certain alloy proportion, melting and mixing metal simple substances or alloys of all elements to obtain the SnBi material alloy; wherein, Sn element and Bi element are introduced in the form of metal simple substance during melting, and Sb element is introduced in the form of Bi-Sb alloy.
6. The SnBi system material alloy preparation method according to claim 5, wherein the Ag, Cu, Co, Ti, Ni elements are introduced in a form of Sn-Ag, Sn-Cu, Sn-Co, Sn-Ti, Sn-Ni alloy when melted.
7. The SnBi-based material alloy according to claim 5 or 6, wherein the In element is introduced as a simple metal substance at the time of melting.
8. The SnBi material alloy preparation method according to claim 5 or 6, wherein the alloy is prepared by vacuum melting; wherein the smelting furnace is vacuumized to 1 x 10-1～1×10-2Pa and filling protective gas.
9. The SnBi material alloy according to claim 6, wherein the melting temperature of the single metal or alloy of each element is 200 to 500 ℃ and the temperature is maintained for 10 to 20 min.
10. Use of the SnBi-based material alloy prepared by the preparation method according to any one of claims 5 to 9 as a via filling material for an integrated circuit chip.
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