CN116921914A - Composite metal composition and preparation method and application thereof - Google Patents
Composite metal composition and preparation method and application thereof Download PDFInfo
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- CN116921914A CN116921914A CN202311071579.6A CN202311071579A CN116921914A CN 116921914 A CN116921914 A CN 116921914A CN 202311071579 A CN202311071579 A CN 202311071579A CN 116921914 A CN116921914 A CN 116921914A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 155
- 239000002184 metal Substances 0.000 title claims abstract description 155
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 66
- 229910000050 copper hydride Inorganic materials 0.000 claims abstract description 50
- 239000003085 diluting agent Substances 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 239000013008 thixotropic agent Substances 0.000 claims description 15
- -1 ester compounds Chemical class 0.000 claims description 10
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 239000002002 slurry Substances 0.000 abstract description 53
- 238000003466 welding Methods 0.000 abstract description 48
- 239000011800 void material Substances 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 15
- 238000005476 soldering Methods 0.000 abstract description 10
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- 230000004907 flux Effects 0.000 abstract description 8
- 239000002923 metal particle Substances 0.000 abstract description 7
- 230000017525 heat dissipation Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 32
- 239000010949 copper Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 3
- FATBGEAMYMYZAF-MDZDMXLPSA-N Elaidamide Chemical compound CCCCCCCC\C=C\CCCCCCCC(N)=O FATBGEAMYMYZAF-MDZDMXLPSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- LTYZGLKKXZXSEC-UHFFFAOYSA-N copper dihydride Chemical compound [CuH2] LTYZGLKKXZXSEC-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
-
- 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
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a composite metal composition, a preparation method and application thereof, and belongs to the technical field of electronic component packaging. The composite metal composition takes the cuprous hydride powder and the metal powder as raw materials, and the cuprous hydride powder can be decomposed into metal Cu and H under the high temperature condition 2 Therefore, the cuprous hydride powder can replace the function of the soldering flux in the existing metal slurry, the oxide layers on the surfaces of metal particles and the surfaces of welded objects in the metal slurry are removed in the welding process, the problem of soldering flux residue caused by using the existing metal slurry is avoided, and the welding void ratio of the interconnection layer is smaller. When the metal paste prepared from the composite metal composition is used as an interconnection layer material of an electronic device, the metal paste has excellent welding quality, small welding void ratio and excellent heat dissipation and reliability.
Description
Technical Field
The invention belongs to the technical field of electronic component packaging, and particularly relates to a composite metal composition, a preparation method and application thereof.
Background
In the service process, the interconnection material of the electronic device is often subjected to severe tests from mechanical vibration, thermal stress, high-density current, power circulation and the like, and as the electronic device becomes more precise and integrated, the requirements on heat dissipation and reliability of the interconnection layer are also higher and higher. The prior art generally prints a metal paste on the surface of the object to be soldered, and forms an interconnection layer between the objects to be soldered by heating.
In the existing metal slurry in the current market, a soldering flux with reducibility is required to be added so that the surface of metal particles in the metal slurry and an oxide layer on the surface of a welded object can be removed in the welding process of the welded object; however, the soldering flux is easy to remain in the interconnection layer after soldering by adopting the method, so that the soldering void rate of the interconnection layer is high, and the heat dissipation performance and the reliability of the interconnection layer are affected.
Aiming at the defects of the metal paste serving as the interconnection layer, the metal paste which does not influence the welding void rate of the interconnection layer and ensures the heat dissipation performance and the reliability of the interconnection layer is found to be the focus of the research in the current electronic component packaging field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a composite metal composition, a preparation method and application thereof, wherein metal slurry prepared from the composite metal composition has excellent welding quality, small welding void ratio and excellent heat dissipation and reliability when being used as an interconnection layer material of an electronic device.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a composite metal composition comprising a metal powder and a copper hydride (CuH) powder; average particle diameter D of the CuH powder 50 30-500nm; the mass ratio of the metal powder to the cuprous hydride powder is (10-50): 1.
The present metal slurry is prepared with Cu, ag, au, sn, pb, bi, in, sb and other metal and its alloy as material and through adding CuH powder to decompose CuH into Cu and H at 60 deg.c 2 H due to CuH decomposition 2 The CuH has reducibility, so that the CuH can replace the function of soldering flux in the metal slurry in the prior art, the oxide layers on the surfaces of metal particles and the surfaces of welded objects in the metal slurry are removed in the welding process, and the problem of soldering flux residue is avoided, so that the welding void ratio of an interconnection layer is smaller; meanwhile, metal Cu generated by CuH decomposition can be diffusion-combined with metal powder in the metal slurry through metallurgical reaction, so that the welding quality is not affected.
The inventors found that the average particle diameter D of the CuH powder 50 The method has great influence on the preparation of metal slurry by the final composite metal composition, and if the particle size of CuH powder is too small (less than 30 nm), agglomeration is easy to occur, so that the CuH powder is not beneficial to being uniformly distributed in a metal slurry system; and the cost of manufacturing the powder particles can be greatly increased; if the particle size of the CuH powder is too large (more than 500 nm), the contact probability of the CuH powder and the metal powder in the metal slurry system is reduced, so that the CuH powder is not beneficial to fully mixing in the metal slurry system, and if the particle size of the CuH powder is too large, the particle size of metal Cu generated by decomposition of the CuH powder is correspondingly increased, so that the fusion and diffusion in the welding process of electronic devices are not beneficial.
The inventor also finds that the mass ratio of the metal powder M to the CuH powder in the composite metal composition can ensure that the metal particle surfaces and the oxide layers on the surfaces of welded objects in the final metal slurry are completely removed only when the mass ratio is in the range, and meanwhile, the welded parts at the upper end cannot be shifted or even the virtual welding is caused; if the mass ratio of the metal powder M to the CuH powder is more than 50:1, the addition amount of the CuH powder is too small, and decomposed H is generated 2 The amount is too small to remove the oxide layer on the surface of the metal particles and the surface of the welded object in the metal slurry; if the mass ratio of the metal powder M to the CuH powder is less than 10:1, the CuH powder is added too much to decompose H 2 Too much can lead to shifting or even cold welding of the upper weldment.
In a preferred embodiment of the composite metal composition of the present invention, the metal powder is at least one of Cu and its alloy, ag and its alloy, au and its alloy, sn and its alloy, pb and its alloy, bi and its alloy, in and its alloy, and Sb and its alloy.
As a preferred embodiment of the composite metal composition of the present invention, the CuH powder has an average particle diameter D 50 130-320nm; the inventors found through a large number of experiments that the average particle diameter D 50 CuH powder in the preferred range may make the weld void ratio of the finally produced metal paste smaller.
As a preferred embodiment of the composite metal composition of the present invention, the mass ratio of the metal powder to the CuH powder is (18-34): 1; the inventor finds through a large number of experiments that the metal powder and the CuH powder in the mass ratio range can ensure that the finally prepared metal slurry has the best welding performance, and the waste of raw materials is avoided.
In a second aspect, the present invention provides a composite metal paste comprising a composite metal composition according to the first aspect.
As a preferred embodiment of the composite metal paste according to the invention, the composite metal paste further comprises the following components: diluents, dispersants and thixotropic agents.
As a more preferable embodiment of the composite metal slurry, the mass percentage of the diluent in the composite metal slurry is 2% -10%; the inventor finds through a large number of experiments that when the mass percentage of the diluent in the whole metal slurry system is 2% -10%, the diluent, cuH powder and metal powder can be uniformly mixed, and a slurry product with moderate viscosity can be prepared; when the addition amount of the diluent is too small (less than 2%), the prepared product has high viscosity, cannot form a slurry product, and is not beneficial to the printing and mounting of the product on a welding surface; when the addition amount of the diluent is too large (more than 10%), the product viscosity is too small, and the product is easy to collapse when printed and attached on a welding surface, so that the welding operation is not facilitated; meanwhile, when the diluent is too much, the diluent volatilizes during welding temperature rise to generate excessive gas, so that the diluent is adhered to the furnace wall and the pipeline of a welding furnace or a sintering furnace to be cleaned poorly, and even a large number of holes are generated in the interconnection layer to influence the performance of the interconnection layer.
As a more preferred embodiment of the composite metal paste of the present invention, the diluent is at least one selected from the group consisting of an alcohol compound, an ether compound, an ester compound, a ketone compound, an aldehyde compound, and a hydrocarbon compound.
As a most preferred embodiment of the composite metal slurry of the present invention, the diluent is at least one selected from butyl ether, hexanone, ethyl acetate, alkane, and n-butanol.
As a more preferable embodiment of the composite metal slurry, the mass percentage of the dispersant in the composite metal slurry is 0.2% -5%; the inventor finds out through a large number of experiments that the dispersing agent with the mass percentage content can lead CuH powder and metal powder to be uniformly dispersed in the whole metal slurry system; when the addition amount of the dispersing agent is too small, the agglomeration of CuH powder and metal powder can be caused; when the addition amount of the dispersing agent is too large, the viscosity of the product is too small, and the product is easy to collapse when being printed and attached on a welding surface, so that the welding operation is not facilitated; and the metal slurry can adhere to the furnace wall of a welding furnace or a sintering furnace and the inside of a pipeline and cannot be cleaned well, and even a large number of holes can be generated in the interconnection layer, so that the performance of the interconnection layer is affected.
As a more preferred embodiment of the composite metal paste of the present invention, the dispersant is selected from at least one of polyamide or acid salt.
As a most preferred embodiment of the composite metal paste of the present invention, the dispersant is selected from at least one of sodium dodecyl sulfate, polyacrylamide and potassium polybutyleate.
As a more preferred embodiment of the composite metal paste, the thixotropic agent in the composite metal paste is 0.4-3% by mass; the inventor finds out through a large number of experiments that the thixotropic agent under the mass percentage content condition can ensure that the printing rheological shaping capability of the composite metal paste is better; when the thixotropic agent is added in an excessive amount, the dynamic rheological property of the sizing agent in the printing process is poor; when the thixotropic agent is added in an excessively small amount, poor static setting ability of the paste after printing is caused.
As a more preferred embodiment of the composite metal paste of the present invention, the thixotropic agent is selected from at least one of modified hydrogenated castor oil, an amide compound, and cellulose hydroxyethyl ether.
As a most preferred embodiment of the composite metal paste according to the invention, the thixotropic agent is selected from at least one of modified hydrogenated castor oil, 9-octadecenamide and cellulose hydroxyethyl ether.
In a third aspect, the present invention provides a method for preparing the composite metal paste, the method comprising the steps of: and uniformly mixing the composite metal composition, a dispersing agent, a diluent and a thixotropic agent in an environment with the temperature not exceeding 25 ℃ by using a planetary mixer to obtain the composite metal slurry.
As a preferred embodiment of the method for producing a composite metal paste of the present invention, the composite metal paste is stored in an environment of 10 ℃ or less for use.
Compared with the prior art, the invention has the beneficial effects that:
the composite metal composition takes CuH powder and metal powder as raw materials, and the CuH can be decomposed into metal Cu and H under the high temperature condition 2 H due to CuH decomposition 2 The CuH can replace the function of soldering flux in the metal paste in the prior art, so that the oxide layers on the surfaces of metal particles and the surfaces of welded objects in the metal paste are removed in the welding process, the problem of soldering flux residue caused by using the existing metal paste is avoided, and the welding void ratio of an interconnection layer is smaller; meanwhile, metal Cu generated by CuH decomposition can be combined with metal powder in the metal slurry through metallurgical reaction diffusion, so that the welding quality is not affected.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
Example 1
The formulation of the composite metal composition of this example is shown in table 1; the formulation of the composite metal paste is shown in table 2.
In the embodiment, the diluent consists of dipropylene glycol butyl ether, hexanone, ethyl acetate and n-heptane, and the mass ratio is dipropylene glycol butylEther: hexanone: ethyl acetate: n-heptane = 3:2:2:1; the dispersing agent consists of sodium dodecyl sulfate, polyacrylamide and potassium polybutylece sulfonate, wherein the mass ratio of the sodium dodecyl sulfate to the polyacrylamide to the potassium polybutylece sulfonate=3:4:2; the thixotropic agent consists of modified hydrogenated castor oil, 9-octadecenamide and cellulose hydroxyethyl ether, wherein the mass ratio of the modified hydrogenated castor oil to the 9-octadecenamide to the cellulose hydroxyethyl ether=2:5:6; the average particle diameter D of the metal powder 50 Is 2 μm.
The preparation method of the composite metal slurry in the embodiment comprises the following steps: uniformly mixing metal powder, cuprous hydride, a dispersing agent, a diluting agent and a thixotropic agent in an environment with the temperature not higher than 25 ℃ by a planetary mixer to obtain the composite metal slurry, and packaging and storing the composite metal slurry in the environment with the temperature lower than 10 ℃ for application after the preparation.
Examples 2 to 12
Examples 2-12 differ from example 1 only in that: the formulation of the composite metal compositions is different, and in particular, as shown in table 1, and the formulations of the composite metal slurries of examples 2-12 are shown in table 2.
The composite metal paste of examples 2-12 was prepared in the same manner as in example 1.
Examples 13 to 14
Examples 13-14 differ from example 1 only in that: the formulation of the composite metal paste was different, and the formulation of the composite metal composites of examples 13-14, as shown in Table 1, was shown in Table 2.
The composite metal slurries of examples 13-14 were prepared in the same manner as in example 1.
Example 15
Example 15 differs from example 1 in that: the composite metal slurry comprises different components and mass ratios of selected diluents, wherein the diluents comprise n-butanol, diethylene glycol butyl ether, isooctane and glutaraldehyde, and the mass ratio is n-butanol, diethylene glycol butyl ether, isooctane, glutaraldehyde=1:3:2:3; the formulation of the composite metal paste was also different, and the formulation of the composite metal composite of example 15 is shown in table 1, as shown in table 2.
The composite metal paste of example 15 was prepared in the same manner as in example 1.
Comparative examples 1 to 4
Comparative examples 1 to 4 differ from example 1 only in that: the formulation of the composite metal composition is different, specifically shown in table 1, and the formulation of the composite metal slurry of comparative examples 1-4 is the same as that of example 1, specifically shown in table 2;
the composite metal slurries of comparative examples 1-4 were prepared in the same manner as in example 1.
Comparative examples 5 to 10
Comparative examples 5 to 10 differ from example 1 only in that: the formulation of the composite metal slurry is different, specifically shown in table 2, and the formulation of the composite metal compositions of comparative examples 5-10 is the same as that of example 1, specifically shown in table 1;
the composite metal slurries of comparative examples 5-10 were prepared in the same manner as in example 1.
Comparative example 11
Comparative example 11A commercially available conventional copper metal paste was used in which the average particle diameter D of copper powder 50 Also 2 μm.
Comparative example 12
Comparative example 12 a commercially available conventional silver metal paste was used in which the average particle diameter D of the silver powder 50 Also 2 μm.
Comparative example 13
Comparative example 13A commercially available conventional Au80Sn20 metal paste was used, in which the average particle diameter D of the Au80Sn20 alloy 50 Also 2 μm.
Comparative example 14
Comparative example 14A commercially available conventional Pb57In40Bi2Sb1 metal paste was used, in which the average particle diameter D of the Pb57In40Bi2Sb1 alloy 50 Also 2 μm.
TABLE 1
TABLE 2
Effect example
Performing a welding void ratio test on the metal pastes of the above examples and comparative examples; the results are shown in Table 3 below.
The welding mode is as follows: the two 5 x 0.5mm silver-plated copper plates are respectively welded by the corresponding process by sandwiching the composite metal paste printed with the example and the comparative example with the thickness of 0.2 mm.
The welding void ratio is detected by X-Ray, and the smaller the welding void ratio is, the better the welding quality is.
TABLE 3 Table 3
The results in Table 3 show that the welding void ratios of the composite metal pastes according to examples 1 to 15 of the present invention are all less than 1%; wherein, the welding void ratio of the composite copper metal slurry in examples 1-9 and examples 13-15 is less than 1%, which is far less than 2.53% of the conventional copper metal slurry sold in comparative example 11; the welding void ratio of the composite silver metal paste in the embodiment 10 of the invention is 0.27%, which is far smaller than 1.28% of the conventional silver metal paste sold in the market of the comparative example 12; the welding void ratio of the composite Au80Sn20 metal paste in the embodiment 11 is 0.18%, which is reduced by nearly 68% compared with the welding void ratio of 0.56% of the conventional Au80Sn20 metal paste sold in the market in the comparative example 13; the welding void ratio of the composite Pb57In40Bi2Sb1 metal paste In example 12 is 0.37%, which is reduced by about 29% compared with the welding void ratio of 0.52% of the conventional Pb57In40Bi2Sb1 metal paste sold In the market In comparative example 14.
In particular, the weld void ratio of the composite metal paste described in examples 1, 4, 5, 8-15 is < 0.6%; comparative example 1 was conducted because of the average particle diameter D of CuH powder in the composite metal composition 50 Less than 30nm, which is unfavorable for the uniform distribution in a metal slurry system, leads to the welding void ratio of the final composite metal slurry being more than 1%, and comparative example 2 is due to the average particle diameter D of CuH powder 50 Too large, the particle size of the metal Cu generated by decomposition is correspondingly increased, which is not beneficial to the fusion diffusion in the welding process of electronic devices, and the welding void ratio of the final composite metal slurry is also more than 1%; comparative example 3 decomposed H because the mass ratio of metal powder to CuH powder was < 10:1, the CuH powder was added too much 2 Too much can lead to the displacement of the welded part at the upper end and even the cold joint, and compared with the method 4, the mass ratio of the metal powder to the CuH powder is more than 50:1, the addition amount of the CuH powder is too little, and decomposed H is generated 2 The amount is too small, the oxide layers on the surfaces of metal particles and the surfaces of welded objects in the metal slurry are not sufficiently removed, and the welding void ratio of the final composite metal slurry is also more than 1%; the addition amount of the diluent in the comparative example 5 is too small, so that a slurry product cannot be formed, and the product is not beneficial to the mounting of the product on a welding surface; in comparative example 6, the addition amount of the diluent is too large, the slurry collapses, the slurry remained on the welding surface is reduced, a large number of voids are generated in the interconnection layer, and the welding void ratio of the final composite metal slurry is also more than 1%; the addition amount of the dispersing agent in the comparative example 7 is too small, and the CuH powder and the metal powder are agglomerated; in comparative example 8, the addition amount of the dispersing agent is too large, the slurry collapses, the slurry remained on the welding surface is reduced, the welding void ratio is increased, and finally, the welding void ratio of the composite metal slurry in comparative examples 7 and 8 is also greater than 1%; comparative example 9 the addition of too little thixotropic agent resulted in poor static setting ability of the paste after printing; the thixotropic agent of comparative example 10 is added in an excessive amount, which results in poor dynamic rheological ability of the paste during printing, and the final welding void ratio of the composite metal paste is also greater than 1%.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A composite metal composition, characterized in that the composite metal composition comprises a metal powder and a cuprous hydride powder; the average particle diameter D of the cuprous hydride powder 50 30-500nm; the mass ratio of the metal powder to the cuprous hydride powder is (10-50): 1.
2. The composite metal composition of claim 1, wherein the metal powder is at least one of Cu and its alloy, ag and its alloy, au and its alloy, sn and its alloy, pb and its alloy, bi and its alloy, in and its alloy, and Sb and its alloy.
3. The composite metal composition of claim 1, wherein the average particle size D50 of the cuprous hydride powder is 130-320nm.
4. The composite metal composition according to claim 1, wherein the mass ratio of the metal powder to the cuprous hydride powder is (18-34): 1.
5. A composite metal paste comprising the composite metal composition of any one of claims 1-4.
6. The composite metal paste according to claim 5, further comprising the following components: diluents, dispersants and thixotropic agents.
7. The composite metal paste according to claim 6, wherein the mass percentage of the diluent in the composite metal paste is 2-10%.
8. The composite metal paste according to claim 6, wherein the mass percentage of the dispersant in the composite metal paste is 0.2% -5%.
9. The composite metal paste according to claim 6, wherein the thixotropic agent is present in the composite metal paste in an amount of 0.4 to 3 mass%.
10. The composite metal paste according to any one of claims 6 to 9, wherein at least one of the following (1) to (3) is used:
(1) The diluent is at least one selected from alcohol compounds, ether compounds, ester compounds, ketone compounds, aldehyde compounds and hydrocarbon compounds;
(2) The dispersing agent is at least one selected from polyamide and acid salt;
(3) The thixotropic agent is at least one selected from modified hydrogenated castor oil, amide compounds and cellulose hydroxyethyl ether.
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| US20150126359A1 (en) * | 2012-05-04 | 2015-05-07 | Imperial Innovations Limited | Process for producing nanoparticles |
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