CN115815872B - Lead-free antimony-free reinforced solder alloy and preparation method thereof - Google Patents
Lead-free antimony-free reinforced solder alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lead-free and antimony-free reinforced solder alloy and a preparation method thereof, wherein the solder alloy comprises the following components in percentage by weight: bi:2% -5%; ag:3% -5%; cu:0.4% -0.8%; ni:0.001% -0.5%; and the balance Sn. The solder alloy of the invention does not contain lead and antimony, wherein Bi, sn, ag, cu and Ni strengthen the second phase and refine crystal grains to strengthen the high-temperature mechanical property, so that the lead-free and antimony-free strengthened solder can bear higher load and environmental temperature; meanwhile, the lead-free reinforced solder has good plasticity, forming processing capability and wettability, low welding void ratio, small melting point change and longer service life, does not need to change the existing welding process, and has strong substitutability. The preparation method uses Sn-Zr intermediate alloy, sn-Cu-Zr intermediate alloy and ZrH 2 The powder or Cu-Zr intermediate alloy is used for preparing the lead-free reinforced solder alloy, so that the smelting temperature is reduced, the Sn is prevented from being seriously oxidized, other new impurities are not introduced, the quality of products is improved, and the cost is reduced.
Description
Technical Field
The invention belongs to the technical field of electronic assembly, packaging and power semiconductor packaging, and particularly relates to a lead-free and antimony-free reinforced solder alloy and a preparation method thereof.
Background
Along with the wide application of electronic products, the reliability of the electronic products is valued, especially in the fields of aviation, aerospace, military, monitoring, finance, communication and the like, and once the electronic products fail, huge losses are caused. The integrated circuit industry in the electronic packaging field requires smaller and smaller solder joint sizes for carrying electricity, gas, heat and force, higher and higher packaging density, and can be used in higher frequency power cycles, higher vibration levels, high humidity, more severe temperature cycles and higher temperature environments. The conventional SAC305 is a lead-free solder alloy containing 96.5% tin, 3% silver and 0.5% copper. The existing foreign SAC305 reinforced solder alloy has high tensile strength, but sacrifices plasticity and wettability. The wettability of the solder alloy influences the welding void ratio, when the welding void ratio is high, the shearing strength of a welding spot becomes low, and the high-temperature creep life of the welding spot is further influenced, so that the solder alloy not only needs to have high tensile strength, but also needs to have better wettability. Therefore, the mechanical properties of the SAC305 solder alloy do not meet the increasingly demanding requirements of the industry.
Although the conventional sn—pb solder has been widely used because of its low price and excellent wettability, pb and Pb-containing compounds are toxic, and thus, lead-containing electronic products are prohibited by the electronic and electrical equipment (WEEE) directive and the european union restriction of certain harmful substances (RoHS) from 7/1/2006. In addition, in some special application occasions with slower package welding cooling rate, the addition of Sb can cause specific gravity segregation of the SnSb phase to form a thick SnSb phase, and meanwhile, the forming capacity, wettability, thermal expansion coefficient and other performances of the solder can be influenced, and the package reliability of electronic products is influenced, so that the research on novel lead-free and antimony-free solder alloy is urgent.
The reliability of the electronic device is evaluated, and an acceleration test is often adopted in early packaging link verification, and the life is estimated or a weak link is determined in higher-frequency power cycle, higher vibration level, high humidity, more severe temperature cycle and higher temperature environment, wherein the most typical and important acceleration test is the acceleration temperature cycle test. It has been demonstrated that if the loading rate is slow enough for creep deformation to occur, then the creep deformation behavior of lead-free solders at temperatures near or above 0.5 times the melting point plays a very important role. Creep response can be considered as the primary deformation in the use of the weld. Therefore, in solder development, the evaluation of creep property plays a decisive role in solder joint reliability.
Thus, in order to meet the ever-increasing performance requirements for solder alloys and to meet environmental or health-based requirements, there is a need for a lead-free and antimony-free solder alloy with enhanced high creep properties to meet the high reliability of electronic packaging, packaging and power semiconductor packaging.
Disclosure of Invention
In order to overcome the defects of the prior art, the first aim of the invention is to provide a lead-free and antimony-free reinforced solder alloy which does not contain lead, and the welding point formed by welding has longer creep life, does not sacrifice wettability and forming capability, and is suitable for mass production of enterprises.
The second object of the invention is to provide a lead-free and antimony-free reinforced solder alloy and a preparation method thereof.
The first object of the invention can be achieved by adopting the following technical scheme:
the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight:
Bi：2%-5%；
Ag：3%-5%；
Cu：0.4%-0.8%；
Ni：0.001%-0.5%；
Zr：0.001%-0.5%；
and Sn:91.2% -94.598%;
and (Ag-3.5%) 2 +（Bi-3%) 2 ≤0.0002；Zr+Ni<0.5%。
Further, the alloy comprises 0.001-0.1% by weight of Ge.
Further, one or a combination of two or more of Ti, co, in, P, ga, B, au, ta, V, nb, hf, ta, mn, al, zn, si elements is also included, and the content of each element does not exceed the content of Ni.
The second object of the invention can be achieved by adopting the following technical scheme:
a preparation method of a lead-free and antimony-free reinforced solder alloy comprises the following steps:
in the atmosphere, at the temperature of above 650 ℃, sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal, intermediate alloy of Zr and/or ZrH 2 Sequentially adding powder and Bi simple substance metal to smelt;
wherein the intermediate alloy of Zr is one or the combination of two of Sn-Zr and Sn-Cu-Zr intermediate alloys.
Further, the mass percentage of Zr in the Sn-Zr intermediate alloy is 0.01-16.9%; the melting point of the Sn-Zr intermediate alloy is 232-1142 ℃.
A preparation method of a lead-free and antimony-free reinforced solder alloy comprises the following steps:
in a protective atmosphere or vacuum environment, at the temperature of above 885 ℃, sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal, intermediate alloy of Bi simple substance metal and Zr and/or ZrH 2 Adding powder for smelting;
wherein the intermediate alloy of Zr is Cu-Zr intermediate alloy;
the pressure ratio of the protective atmosphere is 0.1-7kPa higher than the atmospheric pressure; the air pressure of the vacuum environment is 0.81-100Pa.
Further, the mass percentage of Zr in the Cu-Zr intermediate alloy is 1-79%.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the traditional SAC305 solder alloy, the lead-free and antimony-free reinforced solder alloy has the advantages of remarkably improved mechanical properties, greatly prolonged creep life at normal temperature and high temperature, lower cost, suitability for industrial mass production and application, excellent replaceability, and suitability for solder requirements in the welding of various electronic components such as PCB assembly, automobile accessory modules, chip modules, power supply modules and the like; the reinforced solder alloy does not contain lead and antimony, so that the damage to the environment and the influence on biological health are reduced, the generation of a coarse SnSb phase by the solder can be thoroughly avoided, and the high-temperature creep life and the packaging reliability of the solder are improved.
2. According to the preparation method of the lead-free reinforced solder alloy, zr is added in the form of the intermediate alloy and the addition sequence of each component is limited, so that the smelting temperature is reduced, funds for purchasing high-temperature smelting equipment, high-temperature smelting power consumption and the like are saved, and the cost is reduced; can be smelted in the atmosphere, avoid serious oxidation of Sn, and simultaneously introduce no other new impurities, thereby improving the quality of products.
Drawings
FIG. 1 is a metallographic structure of example 9 Sn92.249Ag4Cu0.7Bi3Ni0.05Zr0.001.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following in connection with specific embodiments. It will be apparent that the described embodiments are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The service life of the traditional SAC305 brazing filler metal is short under high temperature and high load, so the lead-free and antimony-free reinforced brazing filler metal alloy provided by the invention has higher tensile strength and longer creep life, and the wettability and forming capacity are not sacrificed, so that the lead-free and antimony-free reinforced brazing filler metal alloy is suitable for large-scale production and application of enterprises, and the problem that the service life of the traditional SAC305 brazing filler metal is short under high temperature and high load is solved.
The lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight:
bi:2% -5%; ag:3% -5%; cu:0.4% -0.8%; ni:0.001% -0.5%; zr:0.001% -0.5%; and Sn:91.2% -94.598%; and (Ag-3.5%) 2 +（Bi-3%) 2 ≤0.0002；Zr+Ni<0.5%。
The microscopic mechanisms of creep deformation are mainly 3: dislocation slip, subgrain formation and grain boundary deformation, the main factors to improve creep life are to control dislocation climb rate and grain boundary slip, that is to say to control the atomic diffusion process in the grain and at the grain boundary. For this reason, it is considered that the addition of the second strengthening phase resists creep deformation by hindering dislocation slip, refining grains, enhancing grain boundary strength, and the like.
In the tin alloy, zr and Ni microelements can form Sn with Sn 2 Zr、Ni 3 Sn 4 The high-temperature refractory compound can play a role of non-spontaneous nucleation in the molten liquid, so that the finally solidified crystal grains are fine and the number of the crystal grains is large. The finer the crystal grains are, the more crystal grain boundaries are formed, so that dislocation movement can be effectively blocked, plastic deformation is resisted, and the time for the alloy to break due to creep is further prolonged. At the same time Sn 2 Zr、Ni 3 Sn 4 Can strongly block dislocation movement as a dispersed phase, and Sn 2 Zr、Ni 3 Sn 4 The particle hardness is higher, the stability is better at high temperature, and the reinforcing effect is better. And the strengthening effect of multiple elements is better than that of a single element, so that the invention adds trace elements Zr and Ti to Sn to form an alloy.
Bi is added into the tin alloy, a part of Bi can form solid solution beta-Sn, and a part of Bi crystal structure is formed and pinned in the matrix, so that solute atoms interact with dislocation to block dislocation movement, and the material strength is improved. After Bi is added, bi element and Sn, ag and Cu do not form a high-melting-point second phase, and eutectic, uniform crystallization and other reactions also occur, so that the melting point of each element can be reduced; thus enabling the use of lead-free and antimony-free strengthened solder alloys to replace SAC305 solder alloys at conventional soldering process temperatures; in addition, bi can also improve the overall wettability of the solder and reduce the solder void fraction.
Therefore, the matrix alloy solder is reinforced by adding Bi, ni and Zr, the high-temperature creep life of the welding spot is prolonged, and the service life of the module is prolonged.
As an embodiment of the present invention, 0.001 to 0.1% Ge is further contained in weight percent.
The addition of trace Ge elements can reduce the oxidation of Sn solder alloy in the processes of smelting, casting, forming and welding. When a trace amount of Ge element and Ga are added into the Sn solder alloy 3+ Is concentrated on the surface of Sn solder alloy in a complex oxysalt state, can be oxidized preferentially to form compact oxygenFilm formation for preventing direct oxidation of Sn to Sn 4+ Or the formation of a dense oxide film prevents further oxidation of Sn.
Wherein the chemical composition satisfies the following formula (1):
（Ag-3.5%） 2 +（Bi-3%) 2 ≤0.0002 （1）
in the above formula (1), ag and Bi represent weight percentages of the chemical components of the alloy, respectively.
The addition amount of Ag changes creep property, the creep property of the solder with 3.5% content is best, meanwhile Sn-3.5Ag is eutectic structure, when the silver content of the solder exceeds 3.5% is hypereutectic structure, ag can be caused 3 Sn is coarse, and a brittle intermetallic compound having a size of several tens micrometers is fatal to the reliability of the solder joint, so that excessive use of Ag is required to be avoided. And when the silver content is small, the strength of the solder itself and the brittleness of the solder Cu 3 Sn、Cu 6 Sn 5 The growth inhibition capability of the IMC layer is weakened, and the mechanical property and reliability of the welding spot are affected. The addition of Bi contributes to improved wetting and strength, and the solder joint tensile strength reaches a maximum at 3%, and the use of excessive Bi also makes the solder itself more brittle, and the plasticity becomes worse, making processing more difficult. Therefore, the weight percentage of the chemical components of Ag and Bi satisfies the formula (Ag-3.5%) 2 +（Bi-3%) 2 When the temperature is less than or equal to 0.0002, the creep property, plasticity, wettability, strength and the like of the solder can be optimized.
Wherein the chemical composition satisfies the following formula (2):
Zr+Ni<0.5 % （2）
in the above formula (2), zr and Ni represent weight percentages of the chemical components of the alloy, respectively.
The addition of Zr and Ni can improve the high-temperature creep life of the solder alloy welding spot, and the creep life is increased along with the increase of Zr and Ni in a certain range, but the creep life is reduced after the addition amount exceeds a certain range. Through researches, when the chemical component content of Zr and Ni exceeds a certain range, the wettability and the welding void ratio of the solder alloy are affected, and the high-temperature creep life is further affected. Therefore, in the application scene that the soldering flux cannot be coated, the creep life of the solder can be enhanced only when the weight percentage of the chemical components Zr and Ni satisfies the formula Zr+Ni < 0.5%.
As an embodiment of the present invention, a composition of one or more of Ti, co, in, P, ga, B, au, ta, V, nb, hf, ta, mn, al, zn, si elements is further included, and the content of each element does not exceed the content of Ni.
The Sn matrix is added with Ti, co, in, P, ga, B, au, ta, V, nb, hf, ta, mn, al, zn, si and other elements to form a solid solution, so that the solution strengthening is adopted, the stacking fault is reduced, further, the extension dislocation is easier to form, and the dislocation is difficult to generate the cutting order, the cross sliding and the climbing; meanwhile, the binding force of solute atoms and solvent atoms is stronger, the diffusion activation energy is increased, and the promotion of creep life is facilitated.
The invention relates to a preparation method of a lead-free and antimony-free reinforced solder alloy, which comprises the following steps:
in the atmosphere, at the temperature of above 650 ℃, sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal, intermediate alloy of Zr and/or ZrH 2 Sequentially adding powder and Bi simple substance metal to smelt;
wherein the intermediate alloy of Zr is one or the combination of two of Sn-Zr and Sn-Cu-Zr intermediate alloys.
According to the preparation method, sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal, intermediate alloy of Zr and/or ZrH are used for smelting 2 Sequentially adding the powder and Bi simple substance metals; the smelting can be carried out at the temperature above 650 ℃, the smelting temperature is reduced, the smelting can be carried out in the atmospheric environment, the serious oxidation of Sn can be avoided, other new impurities can not be introduced, the quality of products can be improved, the funds of passing through protective atmosphere, purchasing high-temperature smelting equipment, high-temperature smelting power consumption and the like are saved, and the cost is reduced.
The melting point of Zr element is 1852 ℃, the melting point of Sn is 231.9 ℃, and Sn is seriously oxidized if the metal bond of zirconium crystal is broken by means of high temperature. While vacuum melting may solve the problem of high-temperature oxidation of tin, the melting point of Sn at low pressure is far lower than that of zirconium, so that melting cannot be performed, and Sn-Cu-Zr intermediate alloy and Sn-Zr intermediate alloy are provided for preparing the lead-free and antimony-free reinforced solder alloy.
As one embodiment of the invention, the mass percentage of Zr in the Sn-Zr intermediate alloy is 0.01-16.9%; the melting point of the Sn-Zr intermediate alloy is 232-1142 ℃.
The intermediate alloy of Zr is Sn-Cu-Zr intermediate alloy, because the melting point of the Cu-Zr intermediate alloy is 885-1115 ℃, and 885-1115 ℃ still belongs to high-temperature melting point, smelting is carried out in the atmosphere, and oxidation of Sn, sb and Bi is serious, so that the Cu-Zr intermediate alloy is prepared into Sn-Cu-Zr intermediate alloy, and the melting point temperature of the intermediate alloy is further reduced.
As one embodiment of the invention, the Zr component in the lead-free and antimony-free reinforced solder alloy is ZrH 2 Is added as a raw material.
In the case of adding zirconium atoms chemically, sn itself cannot reduce Zr 4+ Since zirconium is a zirconium monomer, zirconium particles cannot be added by oxidation-reduction reaction, zrH can be added only by pyrolysis reaction 2 At 700 deg.c, it is decomposed into hydrogen and zirconium atoms, and some of the zirconium atoms enter the molten liquid, and upon solidification, form compounds with Sn, ag, cu, bi atoms in the liquid, and decompose to produce gas without introducing impurities. Therefore, the invention uses ZrH 2 As a raw material for Zr in the lead-free and antimony-free reinforced solder alloy.
The invention relates to a preparation method of a lead-free and antimony-free reinforced solder alloy, which comprises the following steps:
in a protective atmosphere or vacuum environment, at the temperature of above 885 ℃, sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal, intermediate alloy of Bi simple substance metal and Zr and/or ZrH 2 Adding powder for smelting;
wherein the intermediate alloy of Zr is Cu-Zr intermediate alloy.
The preparation method of the invention comprises the steps of smelting Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal and ZrInteralloy and/or ZrH 2 Adding powder and Bi simple substance metal, and smelting at the temperature of above 885 ℃; the feeding sequence is not required to be controlled, and the feeding smelting is carried out in a protective atmosphere or a vacuum environment, so that the oxidation of Sn by high-temperature smelting can be avoided, and the smelting at a higher temperature is realized.
The melting point of Zr element is 1852 ℃, the melting point of Sn is 231.9 ℃, the difference between the melting points of Sn and Zr element is large, if the metal bond between zirconium crystals is to be broken, the temperature needs to be raised to the melting point to provide enough energy to break the metal bond, so that Zr atoms are in a short-range ordered and long-range unordered state, the atomic groups in the short-range order are not fixed, but the atomic groups are structural fluctuation which is uniform, instant and unstable in size, and the Zr atoms can be combined with Sn, ag, cu, bi atoms to generate intermetallic compounds in a phase diagram proportion during solidification. However, sn, ag, cu, bi and the like oxidize at high temperatures, and therefore, when the zirconium atom is generated in the raw material zirconium compound, it is necessary to reduce the energy for breaking the chemical bond, that is, to reduce the melting point of the master alloy. On the premise of not carrying other impurities, the Sn, ag, cu, bi which is formed by combining Zr atoms into intermetallic compounds after breaking Zr crystal metal bonds at 1852 ℃ and zirconium atoms is not suitable for being used as intermediate alloy with zirconium because Sn and Bi are seriously oxidized; silver has a melting point of 960.5 ℃, is severely oxidized, belongs to noble metals, and is not suitable for being used as intermediate alloy with zirconium. Therefore, cu-Zr is selected as intermediate alloy, the chemical composition of the intermediate alloy is 1-79% of Zr according to weight percentage, and the melting point of the rest Cu is 885-1115 ℃.
As one embodiment of the invention, the mass percentage of Zr in the Cu-Zr intermediate alloy is 1-79%.
Because the melting point of the Cu-Zr intermediate alloy is 885-1115 ℃, and the melting point of 885-1115 ℃ still belongs to high-temperature melting point, the smelting is carried out in the atmosphere environment, and the oxidation of Sn, sb and Bi is serious, the charging smelting is carried out in the protective atmosphere or the vacuum environment, and the oxidation of other elements is avoided.
As one embodiment of the invention, the pressure of the protective atmosphere is 0.1-7kPa greater than the atmospheric pressure; the air pressure of the vacuum environment is 0.81-100Pa.
The following will further illustrate specific examples.
Example 1
Sequentially adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal and Bi simple substance metal according to the proportion of alloy components, and smelting at 600 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: ag3%, cu0.5%, bi3%, ni0.05%, the balance Sn and unavoidable impurities.
Example 2
Sequentially adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal and Bi simple substance metal according to the proportion of alloy components, and smelting at 600 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: ag5%, cu0.8%, bi2%, ni0.001%, and the balance Sn and unavoidable impurities.
Example 3
Sequentially adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal and Bi simple substance metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: ag4%, cu0.4%, bi5%, ni0.5%, and the balance Sn and unavoidable impurities.
Example 4
Sequentially adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal and Bi simple substance metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: ag4%, cu0.5%, bi3%, ni0.2%, and the balance Sn and unavoidable impurities.
Example 5
Sequentially adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal and Bi simple substance metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: ag3%, cu0.6%, bi4%, ni0.05%, the balance Sn and unavoidable impurities.
Example 6
Sequentially adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal and Bi simple substance metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: 3.5% of Ag3.5%, 0.5% of Cu, 4.5% of Bi, 0.05% of Ni, the balance of Sn and unavoidable impurities.
Example 7
Sequentially adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal and Bi simple substance metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: ag5%, cu0.5%, bi3%, ni0.05%, the balance Sn and unavoidable impurities.
Example 8
And smelting the Sn simple substance metal and the Cu-47.4Zr intermediate alloy according to the alloy component proportion at the temperature of 885 ℃ under the protection of argon gas to prepare the Sn-3.32Cu-3Zr intermediate alloy. Wherein the argon protective atmosphere should be kept 0.01-7kPa greater than the atmospheric pressure.
Sequentially adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, sn-3.32Cu-3Zr intermediate alloy and Bi simple substance metal according to the alloy component proportion, and smelting at the temperature of 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: ag3%, cu0.6%, bi4%, ni0.05%, zr0.5% and the balance Sn and unavoidable impurities.
Example 9
Sequentially adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, sn-1Zr intermediate alloy and Bi simple substance metal according to the alloy component proportion, and smelting at the temperature of 650 ℃ in the atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: ag4%, cu0.7%, bi3%, ni0.05%, zr0.001% and the balance Sn and unavoidable impurities.
Example 10
Adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, cu-47.4Zr intermediate alloy and Bi simple substance metal according to the proportion of alloy components, and smelting at 885 ℃ under the condition that the pressure of argon protective atmosphere is kept to be 0.1-7kPa higher than the atmospheric pressure, thereby preparing the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises, in weight percentage: ag4%, cu0.5%, bi3%, ni0.2%, zr0.2% and the balance Sn and unavoidable impurities.
Example 11
Sequentially adding Sn elemental metal, ni elemental metal, cu elemental metal, ag elemental metal, ge elemental metal and Bi elemental metal according to the alloy component proportion, and smelting at the temperature of 650 ℃ in an atmospheric environment to prepare a lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: ag3%, cu0.5%, bi3%, ni0.05%, ge0.02% and the balance Sn and unavoidable impurities.
Example 12
Adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal, cu-47.4Zr intermediate alloy and Bi simple substance metal according to the alloy component proportion, and smelting at 885 ℃ under the condition that the argon protective atmosphere pressure is kept to be 0.1-7kPa higher than the atmospheric pressure, so as to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises, in percentage by weight: ag5%, cu0.5%, bi3%, ni0.05%, zr0.01%, ge0.1%, and the balance Sn and unavoidable impurities.
Example 13
Sequentially adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal, sn-1Zr intermediate alloy and Bi simple substance metal according to the alloy component proportion, and smelting at the temperature of 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: ag3%, cu0.6%, bi4%, ni0.05%, zr0.5%, ge0.001% and the balance Sn and unavoidable impurities.
Example 14
Sequentially adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal, sn-1Zr intermediate alloy and Bi simple substance metal according to the alloy component proportion, and smelting at the temperature of 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: ag4%, cu0.5%, bi3%, ni0.5%, zr0.5%, ge0.02%, and the balance Sn and unavoidable impurities.
Example 15
Adding Sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal, cu-47.4Zr intermediate alloy and Bi simple substance metal according to the alloy component proportion, and smelting at 885 ℃ under the condition that the argon protective atmosphere pressure is kept to be 0.1-7kPa higher than the atmospheric pressure, so as to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises, in percentage by weight: ag4%, cu0.5%, bi3%, ni0.01%, zr0.1%, ge0.02%, and the balance Sn and unavoidable impurities.
Comparative example 1
A conventional SnAgCu solder alloy comprising, in weight percent: ag3%, cu0.5%, and the balance Sn and unavoidable impurities.
The present invention conducted a series of performance tests on the above lead-free and antimony-free strengthened solder alloy examples and comparative examples, and evaluated the alternatives of the lead-free strengthened solder alloy to SAC305 mainly in terms of melting point, workability, solder void ratio, and creep life, as shown in table 1.
The melting point test mode is a differential scanning calorimeter test using NETZSCH 200F 3. The melting point test range is within the range of 210-230 ℃, and is judged to be replaceable, otherwise, the melting point test range is judged to be non-replaceable.
The workability takes 'unilateral maximum cracking edge' as a judging standard, each solder alloy before rolling has the consistent thickness of 8mm, the width of 50mm and the length of 120mm, the rolling reduction of each rolling pass is 0.5mm, the rolling reduction of 15 times and the rolling reduction of the last rolling pass are 0.25mm, and the uniform thickness after rolling is 0.25mm. And measuring the unilateral maximum cracking edge of the solder alloy strip, classifying the sizes of the cracking edges, wherein the unilateral maximum cracking edge is grade I with the length of 5mm, the unilateral maximum cracking edge is grade II with the length of 5-10mm, and the unilateral maximum cracking edge is grade III with the length of >10 mm. Wherein, the level I is judged to be replaceable, and the levels II and III are judged to be irreplaceable.
Table 1 performance test tables for examples and comparative examples
The solder void ratio is the void ratio tested by using a Sonoscan D9600Z ultrasonic scanning microscope, and the vacuum formic acid reflow soldering process is consistent by adopting a 20mm x 20mm soldering tab made of the lead-free reinforced solder alloy of each example and the comparative example and two 20mm x 20mm DBC plates, wherein the vacuum formic acid reflow oven adopts a unitamp RSS450-160. The welding void ratio is classified, wherein the welding void ratio is I grade with less than 1 percent, II grade with 1 to 10 percent, and III grade with more than 10 percent. Wherein, the level I is judged to be replaceable, and the levels II and III are judged to be irreplaceable.
The creep life was measured by using an electronic creep relaxation tester of RWS30 type manufactured by the middle computer test equipment Co., ltd. Under conditions of 90℃and 15MPa, by manufacturing a solder joint shear test piece according to JISZ3198, an industrial standard of Japan. Wherein, the creep life exceeds 3h and judges as replaceable, and if the creep life does not exceed 3h, the creep life is judged as non-replaceable.
In table 1, the expressions (1), (2) and (x) are expressed alternatively as "v", and the expressions (1), (2) and (x ".
As is clear from Table 1, the lead-free reinforced solder alloy according to formula (1) has a melting point in the range of 210 to 230 ℃ and a single-side maximum crack edge of less than 5mm, and has a melting point and workability.
As is clear from table 1, the lead-free reinforced solder alloy satisfying both the formulas (1) and (2) has a weld void ratio of less than 1% and a weld void ratio substitution.
As shown in table 1, after Bi, ni, zr, ge element is added, the high temperature creep life of the solder alloy is improved, and the improvement is 15 times or more, that is, the improvement is more than 3 hours, and the alloy with the substitution is required to simultaneously conform to the formulas (1) and (2). Among them, the most improved high temperature creep life was 23 times as compared with example 9. As can be seen from table 1, the alloy compositions simultaneously satisfying the formula (1) and the formula (2) have excellent replaceability, and the alloy compositions not satisfying the formula (1), the formula (2), or the alloy compositions satisfying only the formula (1) or the formula (2) have no excellent replaceability.
FIG. 1 is a metallographic structure of example 9 Sn92.249Ag4Cu0.7Bi3Ni0.05Zr0.001, and Ag is apparent from FIG. 1 3 Sn、Bi、Cu 6 Sn 5 Evenly distributed in the alloy, dislocation movement is strongly hindered, the deformation resistance of the solder is improved, the overall wettability of the solder is improved, and the welding void fraction is reduced. At the same time Sn 2 Zr、Ni 3 Sn 4 As a dispersed phase, dislocation movement is strongly hindered, and the particles of the dispersed phase have higher hardness, better stability at high temperature and better strengthening effect. The strengthening effect of multiple elements is better than that of a single element, which is the reason for adding Zr and Ni at the same time. In summary, the lead-free reinforced solder alloy has obviously improved high-temperature mechanical properties, compared with the existing Sn96.5Ag3Cu0.5 solder, the lead-free reinforced solder alloy does not need to greatly change the existing molding processing technology and welding technology when in use, accords with industrial mass production, and can be widely applied to various electronic component welding and semiconductor packaging technologies such as PCBs, automobile accessory modules, chip modules, power modules and the like.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (7)
1. The lead-free and antimony-free reinforced solder alloy is characterized by comprising the following components in percentage by weight:
Bi：2%-5%；
Ag：3%-5%；
Cu：0.4%-0.8%；
Ni：0.001%-0.5%；
Zr：0.001%-0.5%；
and Sn:91.2% -94.598%;
and (Ag-3.5%) 2 +（Bi-3%) 2 ≤0.02%；Zr+Ni<0.5%。
2. The lead-free and antimony-free strengthened solder alloy according to claim 1, further comprising 0.001% -0.1% by weight of Ge.
3. A lead-free and antimony-free strengthened solder alloy according to claim 1 or 2,
one or more than two of Ti, co, in, P, ga, B, au, ta, V, nb, hf, ta, mn, al, zn, si elements are also included, and the content of each element does not exceed the content of Ni.
4. A method of producing a lead-free and antimony-free strengthened solder alloy according to any one of claims 1 to 3, comprising the steps of:
in the atmosphere, at the temperature of above 650 ℃, sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal, intermediate alloy of Zr and/or ZrH 2 Sequentially adding powder and Bi simple substance metal to smelt;
wherein the intermediate alloy of Zr is one or the combination of two of Sn-Zr and Sn-Cu-Zr intermediate alloys.
5. The method for producing a lead-free and antimony-free strengthened solder alloy according to claim 4, wherein,
the mass percentage of Zr in the Sn-Zr intermediate alloy is 0.01% -16.9%; the melting point of the Sn-Zr intermediate alloy is 232-1142 ℃.
6. A method of producing a lead-free and antimony-free strengthened solder alloy according to any one of claims 1 to 3, comprising the steps of:
in a protective atmosphere or vacuum environment, at the temperature of above 885 ℃, sn simple substance metal, ni simple substance metal, cu simple substance metal, ag simple substance metal, ge simple substance metal, intermediate alloy of Bi simple substance metal and Zr and/or ZrH 2 Adding powder for smelting;
wherein the intermediate alloy of Zr is Cu-Zr intermediate alloy;
the pressure ratio of the protective atmosphere is 0.1kPa-7kPa greater than the atmospheric pressure; the air pressure of the vacuum environment is 0.81 Pa-100 Pa.
7. The method for producing a lead-free and antimony-free strengthened solder alloy according to claim 6, wherein,
the mass percentage of Zr in the Cu-Zr intermediate alloy is 1% -79%.
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