KR20170011662A - Bonding material with exothermic and amorphous characteristics and manufacturing method thereof - Google Patents

Bonding material with exothermic and amorphous characteristics and manufacturing method thereof Download PDF

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KR20170011662A
KR20170011662A KR1020150104651A KR20150104651A KR20170011662A KR 20170011662 A KR20170011662 A KR 20170011662A KR 1020150104651 A KR1020150104651 A KR 1020150104651A KR 20150104651 A KR20150104651 A KR 20150104651A KR 20170011662 A KR20170011662 A KR 20170011662A
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South Korea
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metal
plating
amorphous
exothermic
bonding
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KR1020150104651A
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Korean (ko)
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KR101818963B1 (en
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정재필
이준형
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덕산하이메탈(주)
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Priority to KR1020150104651A priority Critical patent/KR101818963B1/en
Priority to PCT/KR2016/004269 priority patent/WO2016171525A1/en
Priority to PCT/KR2016/008063 priority patent/WO2017014605A1/en
Publication of KR20170011662A publication Critical patent/KR20170011662A/en
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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
    • B23K35/40—Making wire or rods for soldering or welding
    • 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
    • B23K35/0233—Sheets, foils
    • B23K35/0238—Sheets, foils layered
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/26—Electroplating: Baths therefor from solutions of cadmium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/34—Electroplating: Baths therefor from solutions of lead
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/42—Electroplating: Baths therefor from solutions of light metals
    • C25D3/44—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Automation & Control Theory (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a method for manufacturing a bonded material comprising a metal element, comprising the steps of: preparing an aqueous alloy plating solution containing two or more metal salts including a first metal salt and a second metal salt exhibiting an exothermic reaction during an electrode and an alloy; Forming an electrolytic plating circuit by immersing the electrolytic plating circuit in the aqueous alkaline plating solution so as to form an electrolytic plating circuit; And applying a reduced potential or current to the electrode, and forming at least two or more amorphous metal plating films on the substrate by the standard reduction potential difference of the metal salts And a method of manufacturing a bonded material having heat and amorphous properties.
According to the present invention, potentials (voltages) are alternately applied through a power source capable of supplying a potential in a state where a base material is immersed in a plating bath containing two or more metal salts, thereby forming a complex multi-layer easily in a short time through a low- The thickness of each layer can be controlled by controlling the time and current density of each potential cycle, and the number of composite layers can be easily controlled by the number of potential cycles.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a bonding material having heat and amorphous properties and a method of manufacturing the same,

The present invention relates to a bonded material having exothermic and amorphous properties and a method of manufacturing the same. More particularly, the present invention relates to a bonded material having a characteristic of melting at a low temperature using an exothermic reaction occurring in a process of changing a metal from amorphous to crystalline The present invention relates to a method for producing a bonded material having an exothermic and amorphous characteristics as an intermediate and a method for bonding the bonded material at a temperature lower than the conventional brazing and soling temperature using a bonding material having such heat and amorphous properties.

Techniques related to the method of forming a multilayer thin film layer have been proposed in Patent Registration No. 0560296 and Patent Registration No. 0932694. [

Hereinafter, a method of manufacturing a multilayer metal thin film and a multilayer thin film coating apparatus and method disclosed in the patent registration Nos. 0560296 and 0932694 are described briefly.

1 is a view showing a method of manufacturing a multilayer metal thin film in Patent Registration No. 0560296 (hereinafter referred to as "Prior Art 1"). As shown in FIG. 1, in the method of manufacturing a multilayered metal thin film of the prior art 1, in the method of manufacturing a thin metal film, titanium films 22 and 25 oriented in the <002> direction by ionized physical vapor deposition To about 149 A thick; Depositing titanium nitride films (23, 26) oriented in the <111> direction on the titanium films (22, 25); And depositing an aluminum film 24 oriented in the <111> direction on the laminated film of the titanium / titanium nitride films 22, 23, 25 and 26.

However, since the method of manufacturing the multilayered metal thin film according to the prior art 1 is deposited by using physical vapor deposition (PVD), metal organic chemical vapor deposition (MOCVD), or IPVD, But it had to be implemented through a machine.

A method for depositing a metal layer on a substrate of Patent Registration No. 0932694 (hereinafter, referred to as 'Prior Art 2') includes: a pretreatment step of performing plasma cleaning or ion beam cleaning on the surface of the product; A first thin film layer forming step of forming a first thin film layer by performing one of evaporation deposition, sputtering and reactive sputtering on the surface of the pretreated product; A second thin film layer forming step of forming a second thin film layer on the surface of the first thin film layer by performing one of sputtering, reactive sputtering, plasma penetration, and ion beam penetration; And repeating the first thin film layer forming step and the second thin film layer forming step.

However, the method of depositing the metal layer on the substrate according to the prior art 2 also has disadvantages in that the multilayer thin film is formed by vapor deposition, so that the cost is increased and the vapor deposition machine is expensive.

In addition, in the case of a PVD process including sputtering, a vacuum apparatus is necessary because a vacuum process is performed, and a chemical thin film forming process including a CVD process must also be carried out in a vacuum, and since the process temperature is high, You can give. In the case of the ALD method, the source material is limited and the growth rate of the layer is slow. Printing methods including the roll printing method are difficult to control the thickness of the layer and take a long time to form a multilayer.

Korean Patent No. 10-0415984

An object of the present invention is to solve the problems of the prior art as described above and to produce thin layers of different metal layers alternately so that an exothermic reaction due to a change from an amorphous state to a crystalline state can take place.

This is because a metal material is immersed in a plating bath containing two or more metal salts and a potential (voltage) is applied through a power supply to manufacture a metal multilayer Plated film. In addition, a bonding material having such exothermic and amorphous properties provides desirable conditions for the preparation of a plating solution.

Another object of the present invention is to provide a plating method and a plating method capable of controlling the plating thickness of each layer so that an exothermic reaction can occur by controlling the time and current density of each potential, A method of manufacturing a bonded material having heat and amorphous characteristics, and a preferable manufacturing condition.

In addition, a bonding material having an exothermic and amorphous characteristics produced by electroplating or electroless plating in which different kinds of metal layers are alternately laminated in layers has a tendency to increase as the thickness of individual metal layers in the multilayer plating becomes thinner to the nanometer level Characteristics are displayed. Also, since the surface area between the plating layers is widened and becomes unstable and can be melted by an exothermic reaction due to a change from amorphous to crystalline at a temperature lower than the melting point of a conventional bulk material, a low temperature bonding method using the same as a bonding medium is provided.

Another object of the present invention is to provide a solder paste which is difficult to apply on the curved surface or the vertical surface of the material to be bonded and which can be applied without being affected by curved surface or vertical surface by using a multilayered plating film, It is an object of the present invention to provide a low-temperature bonding method of a material to be bonded using a multi-layered plating film which can be used separately as a material to be bonded independently of the material to be bonded and used as a low-temperature bonding material when the film is peeled off and used as a foil.

According to an aspect of the present invention, there is provided a method of manufacturing an electrolytic plating circuit, comprising: preparing an aqueous alloy plating solution containing two or more metal salts including a first metal salt and a second metal salt; A voltage between +2 V and -4.5 V or a corresponding current value based on a 25 DEG C standard hydrogen electrode is input to a control unit for controlling the electrolytic plating circuit according to the reduction potential value of the metal salt to be plated Applying a reducing potential or current to the electrode, and forming at least two layers of amorphous metal plating films on the mother substrate by a standard reduction potential difference of the metal salts, wherein when the multilayer amorphous metal plating film is changed to crystalline And is produced by a method of producing a bonded material having an exothermic and amorphous properties.

The range of the reduction potential of the metal salt may be a voltage between +1.83 V and -1.67 V or a corresponding current value based on a standard hydrogen electrode at 25 캜.

The water-based alloy plating solution may include a first metal salt, a second metal salt, an acid and a base, and an additive in a water-based plating solution.

The first and second metal salts are selected from the group consisting of Sn, Cu, Zn, Ni, Al, Ti, V, Cr, Mn, Fe, Co, Ga, Ge, As, Zr, Nb, Mo, Tc, Ru, And at least one metal salt selected from the group consisting of Cd, In, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, Bi and Po metal salts.

The first and second metal salts may be selected from two or more metal salts of the elements showing the difference in the standard reduction potential.

The acid may be selected from sulfuric acid, hydrochloric acid, methanesulfonic acid (MSA), nitric acid, boric acid, acetic acid, organic sulfuric acid, citric acid, formic acid, ascorbic acid, hydrofluoric acid, phosphoric acid, amino acid and hypochlorous acid.

The additive may be selected from among polyoxyethylene lauryl ether (POELE), a plating flatting agent (smoothing agent), an accelerator, an inhibitor, a defoaming agent, a polishing agent and an oxidation inhibitor.

The step of applying the reducing potential or the current to the electrode may alternately cause a first voltage section in which the first metal and the second metal are simultaneously coated and a second voltage section in which the second metal is plated alternately.

When the metal plating film is laminated on two films, the sum of the two film thicknesses can be realized in a thickness ranging from 0.1 nm to 5 占 퐉.

The metal plating film may have a total thickness ranging from 0.6 nm to 300 탆.

The bonding material having the exothermic and amorphous properties may be a bonding material for low temperature bonding, which bonds the base material and the material to be bonded by an exothermic reaction caused by a change in crystal phase from amorphous to crystalline.

The present invention also provides a bonded material having exothermic and amorphous characteristics including at least two amorphous metal plating films containing at least two metal elements exhibiting an exothermic reaction upon alloying.

Wherein the metal element is selected from the group consisting of Sn, Cu, Zn, Ni, Al, Ti, V, Cr, Mn, Fe, Co, Ga, Ge, As, Zr, Nb, Mo, Ru, Rh, Pd, Ag, And may be at least one metal element selected from the group consisting of Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au,

When the metal element is in a metal salt state, two or more metal elements showing a difference in standard reduction potential may be selected and used.

When the metal plating film is laminated on two films, the sum of the two film thicknesses can be realized in a thickness ranging from 0.1 nm to 5 占 퐉.

The multi-layered metal plating film may have a total thickness ranging from 0.6 nm to 300 탆.

The metal plating film may have a structure in which six or more layers are stacked.

The amorphous metal plating film may be used as a bonding material at a temperature lower than the melting point of the entire bulk composition constituting the plating layer.

The bonding material having the exothermic and amorphous characteristics may be a material for low-temperature bonding which bonds the base material and the material to be bonded by an exothermic reaction caused by a change in crystal phase from amorphous to crystalline.

According to the present invention, in producing a bonded material having heat and amorphous characteristics, potentials (voltages) are alternately applied through a power source while the base material is immersed in a plating bath containing two or more metal salts, The thickness of each layer can be controlled so that an exothermic reaction due to a change from an amorphous state to a crystalline state can be achieved by controlling the current density or time of each potential cycle, It is possible to control the number of multiple layers.

In addition, when bonding the material to be bonded using the bonding material having heat and amorphous characteristics according to the present invention at a low temperature, the surface of the bonding material can be exposed to a flux, an inert gas, a reducing gas atmosphere, And plated film materials can be used as a bonding medium by plating not only noble metals but also common metals (eg, various metals such as copper, tin, zinc, and nickel). The amorphous characteristics of the bonding medium in which the thickness of the individual plated metal layers made of different metals are made to the nanometer level are exhibited. The amorphous phase is unstable and an exothermic reaction occurs during the phase change to the crystalline phase. Further, the surface area between the laminated plated layers becomes wider and becomes more unstable and melts by an exothermic reaction at a temperature lower than the melting point of the conventional bulk material.

In order to produce nano-metal powder, expensive noble metal powders, such as gold and silver, which are easily oxidized and easily oxidized due to their large contact area with oxygen in the atmosphere, are used . On the other hand, the cost of the bonding medium, which is the bonding material having the exothermic and amorphous characteristics prepared by the present invention, is much lower than that of the nano powder.

In addition, unlike the nano powder which is likely to be oxidized during the manufacturing process, the bonding material mixture material having the exothermic and amorphous characteristics produced by the present invention is not only a precious metal but also a metal, There is no concern (the outermost layer forms only a natural oxide film in the atmosphere).

In addition, unlike the conventional nano powder having a risk of explosion or fire due to rapid oxidation and heat generation of the nano powder, the multilayered plating film is easy to handle and has a safe effect.

The present invention is also advantageous in that it can be easily mass produced using a plating method unlike a method in which a multilayer is formed by physical vapor deposition (PVD) or chemical vapor deposition (CVD) such as sputtering in vacuum have.

Further, in the present invention, when a roll-shaped plating electrode is used, the bonding material having heat and amorphous characteristics can be peeled off to form a separate foil-like bonding material, have.

In addition, the present invention has an effect of controlling the thickness of a bonding material having exothermic and amorphous characteristics so that an exothermic reaction can be arbitrarily changed from amorphous to crystalline by controlling the composition of the plating liquid and the pulse and plating time.

In addition, in the present invention, the bonding material having the exothermic and amorphous characteristics prepared to have the exothermic characteristic due to the change from the amorphous to the crystalline state can significantly lower the bonding temperature as compared with the conventional bulk bonding medium, (For example, a bulk material of a Sn-Ag type brazing material which is widely used for bonding copper in the electronic industry has a lowest melting point (eutectic temperature) of about 221 ° C, and Sn-3.5wt% Ag solder The Sn-Ag based multilayer plating film alternately stacked with Sn prepared by the present invention has a lower melting point, and when it is used as a bonding medium, the Sn- ° C, or copper, which is the material to be bonded, can be bonded even at a temperature lower than the melting point of the bonding material according to the lamination condition of the bonding material having exothermic and amorphous characteristics).

In addition, in the conventional method, a noble metal powder having a nanometer-scale size is generally used as a kind of noble metal powder, and the melting point of the noble metal powder is lowered to perform low-temperature bonding. In the present invention, different kinds of plating layers are alternately layered at a nanometer- There is an effect that can be. If different types of metal layers are used as the bonding medium, the two metal layers are spread and melted to form an alloy, so that the strength of the joints is more improved than that of one kind of metal.

In addition, the bonded material having the exothermic and amorphous characteristics produced by the present invention has a temperature of not higher than 52.3% (Ni-Cu multilayer thin film) or more of 87.1% (Cu-Ag type multilayer thin film) (Brazing and soldering) is possible by using the bonding material having the heat and amorphous characteristics according to the present invention even in this temperature range where the conventional bulk type bonding medium is not melted. Also, the bonding temperature at this time can be bonded even at the melting point of the first plating layer and the melting point of the second plating layer or below. (Example 4) As one embodiment of the bonding temperature, the bonding material having Ni- At a temperature of 600 ° C to 1000 ° C, which is the lowest melting point of the first and second plated layers, which is 1083 ° C or lower.

Of course, when the medium of the present invention is used, the upper limit of the junction temperature is effective to the melting point of the existing bonding medium or the melting point of the material to be bonded, which is higher than 87.1%.

Further, the bonding material having the exothermic and amorphous characteristics produced by alternately laminating different types of metal layers in the form of layers and electrolytic plating or electroless plating has an amorphous characteristic as the individual laminated metal layers are thinned, and the increase in surface area between the respective metal layers , And each of the plating layers constituting the bonding material having the exothermic and amorphous characteristics exhibits an exothermic reaction easily at the time of heating at a low temperature. In this case, melting is performed at a temperature lower than the melting point of the conventional bulk material, and this melting phenomenon has no relation to the stacking order of the respective plating layers constituting the bonding material having the heat generation and amorphous characteristics.

The bonding material can be bonded at a low temperature. Therefore, low-temperature soldering or low-temperature brazing is enabled.

1 is a schematic view showing a method of manufacturing a multilayered metal thin film according to the prior art 1;
2 is a block diagram showing a method of manufacturing a bonded material having exothermic and amorphous characteristics according to the present invention.
3 is a schematic view of an apparatus for manufacturing a bonded material having exothermic and amorphous properties for implementing a method of manufacturing a bonded material having exothermic and amorphous characteristics according to the present invention.
4 is a cross-sectional view illustrating a bonded material having exothermic and amorphous characteristics manufactured by a method of manufacturing a bonded material having exothermic and amorphous characteristics according to the present invention.
5 is a block diagram illustrating a reduced potential measurement method for implementing a method of manufacturing a bonded material having exothermic and amorphous characteristics of the present invention.
Fig. 6 is a photograph of a current, a potential and a plating power supply apparatus in which the alloy of the first section is plated.
FIG. 7 is a photograph of a current, a potential, a repetition rate setting, and a plating power supply device in which the second section of pure metal is plated.
8 is a graph showing the formation of a bonding material having heat and amorphous characteristics according to the content of metal salt and the difference in reduction potential in the plating solution according to the present invention.
FIGS. 9A to 9H are cross-sectional photographs of a bonding material having heat and amorphous characteristics when the first metal salt, the second metal salt, and the reduction potential are different in the plating solution according to the present invention. FIG.
10 is a graph showing the formation of a bonding material having heat and amorphous characteristics according to the content of metal salt and the difference in reduction potential in the plating solution according to the present invention.
11 is a scanning electron microscope (SEM) photograph showing a cross section of a Sn-Cu multilayer plated film formed by a method of manufacturing a bonded material having exothermic and amorphous characteristics of the present invention.
12 is a scanning electron microscope (SEM) photograph showing a cross-section of a Sn-Cu multilayered plating film produced by thickening an individual plating layer laminated by a method of manufacturing a bonded material having exothermic and amorphous characteristics of the present invention.
13 is a scanning electron microscope (SEM) photograph showing a cross section of a Zn-Ni multi-layered plated film formed by a method of manufacturing a bonded material having exothermic and amorphous characteristics of the present invention.
14 is a cross-sectional view of a bonded material having exothermic and amorphous characteristics in which a first plating layer, a second plating layer, and a third plating layer are alternately laminated when a third metal salt is added to the metal salt according to the present invention.
FIG. 15 is a graph showing the conditions under which a metal is oxidized and reduced in order to explain a method of bonding at a low temperature using a bonding material having the exothermic and amorphous characteristics of the present invention.
FIG. 16 is a graph showing the thermal characteristics of a bonded material having Ni-Cu thermal and amorphous characteristics manufactured by the present invention measured by DTA (Differential Thermal Analysis). FIG.
17 is a photograph showing the low-temperature bonding of 304 stainless steel for 10 minutes at 600 ° C, 700 ° C, 800 ° C, and 1000 ° C using a bonding material having Ni-Cu thermal and amorphous characteristics prepared in the present invention as a bonding medium.
FIG. 18 is a photograph of the fracture surface obtained by low temperature bonding of 304 stainless steel at 900 ° C for 10 minutes using a bonding material having Ni-Cu thermal and amorphous characteristics prepared in the present invention as a bonding medium.
FIG. 19 is a graph showing DSC (Differential scanning calorimetry) measurement of thermal properties of a bonded material having Sn-Cu thermal and amorphous characteristics manufactured according to the present invention during heating.
FIG. 20 is a photograph of a bonding material having Sn-Cu thermal and amorphous characteristics prepared according to the present invention on a copper substrate. FIG.
FIG. 21 is a graph showing the results of measurement of a copper plate for 10 minutes at 160.degree. C., 170.degree. C. and 210.degree. C. in a vacuum of 10 -3 torr using a bonding material having Sn-Cu thermal and amorphous characteristics prepared in the present invention as a bonding medium. This is a low-temperature bonded image.
22 is a graph showing the thermal characteristics of the bonded material having the Cu-Ag heat generating and amorphous characteristics manufactured by the present invention measured by DTA.
FIG. 23 is a graph showing the relationship between the thickness of the first and second plating metal layers (left) before and after the heating of the bonded material having the Sn-Cu thermal and amorphous characteristics according to the present invention, It is a photograph of a (right) figure.
FIG. 24 is a graph showing the relationship between the first and second plating layers (left) in a plated state before heating of the bonded material having the Ni-Cu thermal and amorphous characteristics according to the present invention, and the first and second plating layers (Right).
25 is a graph showing the amorphous characteristics (left) of the bonded material having the exothermic and amorphous characteristics Sn-Cu produced by the present invention as a result of XRD analysis of the bonded material having the exothermic and amorphous characteristics, And a crystalline state (right) as a result of phase analysis by XRD of a state in which the first and second plating layers disappear due to diffusion after heating.
26 is an electron micrograph (SEM) photograph showing a cross section of a multi-layered metal material produced by thickening the sum of the thicknesses of the two plated layers to 5 μm.
27 is a heating graph in which a multilayer metal material is manufactured such that the sum of the thicknesses of the two plating layers is 5 탆 thick and the thermal characteristics are measured using a differential scanning calorimeter (DSC).
28 is an optical microscope photograph showing an actual cross-section of a joint of a multi-layered metal material prepared by thickening the sum of the thicknesses of the two plated layers to 5 탆 and joining them.
FIG. 29 is an optical microscope photograph showing the copper electrode cross section made by laminating six layers of multilayer film metal materials at a low temperature.
30 is an optical microscope photograph showing an end face portion of a Sn-Cu-based metal plating thin film produced by lengthening the plating time of the multilayer metal material to have a total plating thickness of 300 mu m.

The terms or words used in the present specification and claims are intended to mean that the inventive concept of the present invention is in accordance with the technical idea of the present invention based on the principle that the inventor can appropriately define the concept of the term in order to explain its invention in the best way Should be interpreted as a concept.

Throughout the specification, when an element is referred to as "comprising &quot;, it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise. Also, the term " part "in the description means a unit for processing at least one function or operation, which may be implemented by hardware or software or a combination of hardware and software.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method of manufacturing a bonded material having exothermic and amorphous characteristics with exothermic characteristics using the plating method according to the present invention will be described in detail with reference to the drawings.

FIG. 2 is a block diagram showing a method of manufacturing a bonded material having exothermic and amorphous characteristics according to the present invention. FIG. 3 is a graph showing the exothermic and amorphous characteristics And FIG. 4 is a cross-sectional view illustrating a bonded material having exothermic and amorphous characteristics manufactured by a method of manufacturing a bonded material having exothermic and amorphous characteristics according to the present invention, and FIG. FIG. 5 is a block diagram illustrating a reduction potential measurement method for implementing a method of manufacturing a bonded material having exothermic and amorphous characteristics according to the present invention.

Referring to these drawings, a method of manufacturing a bonded material having exothermic and amorphous characteristics using the plating method of the present invention comprises immersing electrodes 12, 13, and 14 in an aqueous alloy plating liquid 15 containing two or more metal salts, A voltage is applied to the electrodes 12, 13 and 14 so that the first plating layer 33 (the first metal alloy containing the second metal) 33 and the second plating layer 34 are alternately plated, A method of fabricating the electrode and the water-based alloy plating solution (S100), an electrolytic plating circuit forming step (S110), a reducing potential or a current applying step (S120), a voltage or an equivalent current, An input step (S130) and a multilayer plating step (S140).

In the present invention, the metal salt in the plating solution is ionized, and in order to deposit on the cathode using electric current, a voltage higher than the reduction potential of each element must be applied. In the case of a plating solution in which two or more metal salts are present, there is a difference in standard reduction potential between the two elements, and a voltage range in which the type of metal to be precipitated varies. When these voltage sections are alternately applied, metal layers of different kinds are alternately deposited. The voltage section may be represented by a first section in which both the first metal and the second metal are plated and a second section in which only the second metal is plated.

As described above, in the present invention, the alternately deposited plating layers have a laminated structure in which thin films having a wide surface are piled up in a regular order. At this time, if the thickness of the individual metal layer in the multi-layered plating layer is reduced to the nanometer scale, the characteristics are significantly different from those of the bulk metal. Specifically, each of the plated layers laminated at a nanometer level has an amorphous characteristic and becomes unstable due to an increase in the surface area between the respective metal layers, and each of the plated layers laminated easily shows an exothermic reaction when it is heated at a low temperature. This allows the alloy to be easily melted to form an alloy even at a temperature lower than the melting point in the bulk material state. Therefore, it is generally possible to perform the bonding process performed at a high temperature at a low temperature.

Here, the apparatus 10 for producing a bonded material having exothermic and amorphous characteristics for implementing a method of manufacturing a bonded material having heat and amorphous characteristics using the plating method of the present invention comprises a container 11, a reference electrode 12, A negative electrode 14, a magnet 16 for stirring, and a PC 20 as a control unit.

The vessel (11) is a plating bath in which an opened top is closed with a stopper (11a) and a stirring magnet (16) is installed on an inner bottom.

As the reference electrode 12, a saturated calomel electrode was used. A 10 mm X 0 mm platinum (Pt) electrode was used as the anode 13 and a 10 mm X 0 mm copper electrode was used as the cathode 14 electrode. Different types of conductive metals can be used for the anode and cathode depending on the plating conditions and the size can be adjusted. The power supply can use both a constant current and a constant voltage.

The stirring magnet 16 is disposed on the bottom surface of the container 11 to stir the plating liquid stored in the container 11 and drive magnet (not shown) is provided on the drive shaft at the lower end of the container 11 (Not shown in the drawing) is driven, the driving magnet is operated by the principle of interlocking the stirring magnet 16 disposed on the bottom surface of the container 11 by the magnetic force.

The PC 20 as the control unit is provided with software such as a power supply capable of adjusting voltage and current waveforms and a waveform adjustment program, and is capable of controlling voltage and current waveforms through input and manipulation. The PC 20 is provided with a positive electrode 17 of a power source to be electrically connected to the positive electrode 13 through a wire and a reference electrode 18 of a power source to be electrically connected to the reference electrode 12 through a wire, And a negative electrode 19 of a power source is provided so as to be electrically connected to the negative electrode 14 through electric wires.

The electrode and aqueous alloy plating solution preparation step (S100) is a step of preparing and manufacturing an electrode and an aqueous alloy plating solution (15), respectively. At this time, the electrode includes a reference electrode 12, an anode 13, and a cathode 14. The plating solution 15 includes the first metal salt and the second metal salt, and may include an acid and an additive.

The first and second metal salts may be at least one selected from the group consisting of Sn, Cu, Zn, Ni, Al, Ti, V, Cr, Mn, Fe, Co, Gallium, Ge, As, Zr, Nb, Mo, (Rh), Pd, Ag, Cd, In, Sb, Tell, Hf, Ta, W, Metals such as rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), thallium (Tl), lead (Pb) and bismuth (Bi) Two or more metal salts of the elements that differ in the range of the reduction potential of 0.029 V to 1.0496 V may be selected and used. The concentration ratio of the first and second metal salts in the plating solution is preferably selected in the range of 2: 1 to 100: 1. In this embodiment, Cu, Sn, Pb, Bi, Ag, Ni, and Zn, which have the highest utilization, are selected and multilayer plating is performed.

In the case of acid, it is ionized and electricity such as hydrochloric acid, sulfuric acid, methanesulfonic acid (MSA), nitric acid, boric acid, acetic acid, organic sulfuric acid, citric acid, formic acid, ascorbic acid, hydrofluoric acid, phosphoric acid, amino acid, hypochlorous acid Sulfuric acid, which is easy to obtain at low cost, is used in the examples.

In the case of additives, the surface of the plated film is made uniform, and a leveling agent (smoothing agent), an accelerator and an inhibitor may be added. In addition, various additives such as a defoaming agent, a polishing agent, a particle refining agent and the like may be used in some cases. In the examples, polyoxyethylene lauryl ether (POELE) was used as an additive in the flattening agent, but it is possible to form a multilayer film without using it.

The electrolytic plating circuit forming step S110 is a step of forming the electrolytic plating circuit by immersing the reference electrode 12, the anode 13, and the cathode 14 in the water-based alloy plating solution 15 and then connecting the power source. That is, the electron movement sequence of the circuit in the electrolytic plating circuit forming step S110 is performed in a process of moving through the anode 13, the power source, and the cathode 14.

The reduction potential or current application step (S120) is a step of inputting and applying a reduced potential (voltage) or current through the software of the PC 20 which is a control unit.

In this case, the pulse voltage and the current may be represented by a first section in which both the first metal and the second metal are plated and a second section in which only the second metal is plated, in performing the reduction potential or current application step (S120).

The thickness condition input step S130 of the plated thin film is a step of inputting a voltage or a corresponding current, time and cycle number corresponding to the plating thickness having a desired heat generating characteristic for the first plating layer 33 and the second plating layer 34, Through the software of FIG.

 That is, in the step of inputting the thickness condition of the plated thin film (S130), by adjusting the voltage or the corresponding current and time value between +2 V and -4.5 V on the standard hydrogen electrode at 25 ° C according to the thickness condition, It is possible to control the thickness of the plating having the exothermic characteristic. Preferably, in the present invention, the thickness of the plating layer having the exothermic characteristics of the first and second regions can be controlled by adjusting the voltage or the corresponding current and time between + 1.83V and -1.67V with respect to the standard hydrogen electrode.

More preferably, the plating can be performed by adjusting the voltage between + 1.83V and -1.67V or the corresponding current and time based on the standard hydrogen electrode. When the reduction potential is lower than -1.67 V (for example, Li, Na, Ca, etc.), it is difficult to produce by the plating method of the present invention, and it is difficult to manufacture. When the potential is + 1.83 V or more, .

The multilayer plating step S140 is a step of obtaining a bonded material having exothermic and amorphous characteristics through sequential plating of the first plating layer 33 and the second plating layer 34. [ The metal salt in the plating solution is ionized, and in order to be reduced and deposited on the cathode, a voltage higher than the reduction potential of each element should be applied. By using this principle, a layer in which one metal precipitates and a layer in which two or all of the metals are precipitated alternately appear. The number of alternating plating layers is unstable because the surface area between the plating layers is wider as the number of layers is increased. However, the current density at plating should not exceed the limit current density.

The bonding material having heat generation and amorphous properties is preferably a combination of the thicknesses of the first plating layer 33 and the second plating layer 34 so that the first metal layer 33 and the second metal layer 34 can exhibit heat generation characteristics May be formed with a thickness ranging from 0.1 nm to 5 mu m.

In addition, in the bonding material having the exothermic and amorphous characteristics, each of the amorphous metal plating films such as the first plating layer 33 and the second plating layer 34 preferably has a laminated structure of at least six layers. When each of these amorphous metal plating films is less than 6 layers, the endothermic reaction occurs more than the exothermic reaction at the time of bonding, and the crystalline phase of the amorphous bonding material is not changed to the crystalline state, so that the bonding strength of the bonding portion is lowered and the bonding reliability is lowered It is not preferable.

Furthermore, the number of multiple layers can easily be controlled by the number of dislocation cycles in the multi-layer plating step (S140).

The reduction potential difference between the first metal salt and the second metal salt was measured to determine the reduction potential of the first plating layer 33 and the second plating layer 34 of the present invention for the production of a bonding material having alternating plated and exothermic properties A potential or current application step (S120) may be performed.

At this time, the step of measuring the reduction potential difference of the metal salt may include a step S200 of preparing an alloy plating liquid, an electrode preparing step S210, an electrolytic plating circuit forming step S220, a power applying step S230, And measuring the reduction potential and current of the metal to be plated. The reason for measuring the reduction potential of the metal salt is to give a voltage higher than the potential at which these metals are reduced so as to form the first plating layer and the second plating layer to be.

Here, the alloy plating liquid manufacturing step S200, the electrode preparing step S210, the electrolytic plating circuit forming step S220, and the power applying step S230 are steps of forming the bonding material having the exothermic and amorphous properties, The electrode and the aqueous alloy plating solution preparing step S100, the electrolytic plating circuit forming step S110, and the reducing potential or current applying step S120, detailed description thereof will be omitted.

If the reduction potential is known, a method of manufacturing a bonded material having an exothermic and amorphous characteristics can be performed immediately. Meanwhile, the polarization curve measuring step (S240) and the reducing potential of the metal to be plated and the current measuring step (S250) may be performed only once but not once again. Furthermore, a method for measuring the reduction potential difference is to measure a Tafel curve (a constant voltage per unit time is changed, and a current density at that time is represented by a hysteresis curve, and a section where a change in slope is represented by a reduction potential).

As a result, the bonded materials having the exothermic and amorphous characteristics produced by the method for producing a bonded material having the exothermic and amorphous characteristics of the present invention can easily form a laminate up to a nanometer thickness so as to have heat generation characteristics, To tens of thousands or more.

Meanwhile, the bonding material 30 having the exothermic and amorphous characteristics manufactured by the method for producing a bonding material having the heat and amorphous characteristics according to the present invention is characterized in that the conductive material 30 having the insulating tape 32 closed at the edge thereof The first plating layer 33 and the second plating layer 34 are sequentially stacked on the substrate 31. [ Here, the first plating layer 33 is a first zone plated layer including a first metal and a second metal, and the second plating layer 34 is a second zone plated layer made of a second metal.

The bonding material having the exothermic and amorphous characteristics can be realized by alternately stacking several layers of different plating layers from several layers to several tens of layers or more, thereby further improving the bonding property.

On the other hand, the low-temperature bonding of the base material forming the bonding material having the exothermic and amorphous characteristics is carried out in a vacuum, an inert gas, or a reducing gas atmosphere, which is an atmosphere that does not cause oxidation of the bonding surface. .

The bonding material having the above exothermic and amorphous characteristics may be a multilayer plated film on the surface of the base material, a multilayer foil sheet in the form of a multilayer thin film foil sheet, a crushed particle form in the multilayer foil sheet, A paste form prepared by mixing powders or balls in which a bonded material is formed, pulverized particles of a multilayered foil sheet, or powders in which a bonding material having heat and amorphous properties are mixed with a liquid, And can be used as a bonding medium.

The liquid in the paste form can be used as a solvent, for example, alcohols, phenols, ethers, acetone, aliphatic hydrocarbons having 5 to 18 carbon atoms, aromatic hydrocarbons such as kerosene, diesel, toluene, xylene, Among them, alcohols, ethers, or acetones having preferably some solubility in water may be used.

The base material (material to be bonded) may be selected from the group consisting of metals, ceramics, and high molecular materials.

The base material (bonding material) forming the bonding material having the exothermic and amorphous characteristics according to the present invention has a heat generation characteristic and can be bonded at a lower temperature than a conventional bonding medium in bulk form.

Preferably, the bonding material having the exothermic and amorphous characteristics is a bonding material for low temperature bonding which bonds the base material and the material to be bonded by an exothermic reaction caused by a change in crystal phase from amorphous to crystalline. That is, the bonding material having the exothermic and amorphous characteristics is formed in the form of a multi-layered plated film including a metal element exhibiting an exothermic reaction during alloying, and is formed by an exothermic reaction due to a change in crystal phase from amorphous to crystalline when the base material and the material to be bonded are bonded Since the base material and the bonding material are bonded to each other, bonding can be easily and stably performed at a low temperature. Further, the bonded material changed from the amorphous state to the crystalline state exhibits excellent bonding strength by firmly and stably bonding the base material and the material to be bonded.

The present invention also provides a bonded material having exothermic and amorphous characteristics including a metal element exhibiting an exothermic reaction upon alloying and including at least two layers of amorphous metal plating films.

Here, the bonding material having the exothermic and amorphous characteristics has a structure in which the amorphous metal plating film has a laminated structure of six or more layers, and is used as a bonding material at a temperature lower than the melting point of the entire bulk composition constituting the plating layer of the amorphous metal plating film Preferably, the bonding material is a material for low-temperature bonding which bonds the base material and the material to be bonded by an exothermic reaction caused by a change in crystal phase from amorphous to crystalline.

The metal element may be at least one selected from the group consisting of Sn, Cu, Zn, Ni, Al, Ti, V, Cr, Mn, Fe, Co, Ga, Ge, As, Zr, Nb, Mo, Ru, Rh, Pd, Ag, At least one metal element selected from the group consisting of In, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb and Bi may be used. , And two or more metal elements showing a difference in standard reduction potential may be selected and used.

On the other hand, when the metal plating film is laminated on two films, the sum of the two film thicknesses is preferably in the range of 0.1 nm to 5 μm, and the total thickness is preferably in the range of 0.6 nm to 300 μm It is preferable that it is formed to have a thickness.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG.

FIG. 6 is a photograph showing a current, a potential and a plating power supply apparatus in which a first section of alloy is plated, and FIG. 7 is a graph showing the current, potential, A recorded picture is disclosed.

FIG. 8 is a table showing the formation of a bonding material having heat and amorphous characteristics according to a content ratio of a metal salt and a difference in reduction potential in a plating solution according to the present invention. FIGS. 9A to 9H show the plating solution according to the present invention Sectional view of a bonded material having heat and amorphous characteristics when the types of the first metal salt and the second metal salt and the reduction potential value are different from each other is shown in FIG. A range graph showing the formation of a bonding material having heat generation and amorphous characteristics depending on the reduction potential difference is shown.

11 shows a scanning electron microscope (SEM) photograph showing a cross-section of a Sn-Cu multilayered plated film formed by a method of manufacturing a bonded material having exothermic and amorphous characteristics of the present invention, and Fig. 12 shows the heat and amorphous characteristics (SEM) photograph showing a cross-section of a Sn-Cu multi-layered plated film produced by thickening an individual plated layer stacked by a method of manufacturing a bonded material having the exothermic and amorphous characteristics of the present invention, (SEM) photograph showing a cross-section of a Zn-Ni multi-layered plated film formed by a method for producing a material is disclosed. Fig. 14 is a cross-sectional view showing a cross section of the first plated layer and the second plated layer when the third metal salt is added to the metal salt according to the present invention Sectional view of a bonded material having exothermic and amorphous characteristics in which a plated layer and a third plated layer are alternately laminated.

FIG. 15 is a graph showing the conditions under which the metal is oxidized and reduced in order to explain a method of bonding at a low temperature using a bonding material having the exothermic and amorphous characteristics of the present invention.

FIG. 16 is a graph showing the thermal characteristics of a bonded material having Ni-Cu thermal and amorphous characteristics produced by the present invention measured by differential thermal analysis (DTA). FIG. 17 shows the Ni- There is disclosed a low temperature bonding of 304 stainless steel at 600 ° C, 700 ° C, 800 ° C, and 1000 ° C for 10 minutes using a bonding material having Cu heating and amorphous properties, A tensile test was carried out after low-temperature bonding of 304 stainless steel at 900 ° C for 10 minutes using a bonding material having Ni-Cu exothermic and amorphous characteristics as a bonding medium.

FIG. 19 is a graph showing thermal characteristics of a bonded material having Sn-Cu thermal and amorphous characteristics manufactured by the present invention measured by differential scanning calorimetry (DSC), and FIG. 20 is a graph showing thermal and amorphous A method of manufacturing a bonded material having a Sn-Cu thermal and amorphous characteristics is disclosed in which a bonding material having a heat and amorphous characteristic is formed on a copper substrate. Temperature bonding of copper plates for 10 minutes at 160 ° C, 170 ° C, and 210 ° C in the atmosphere or in a vacuum of 10 -3 torr using a bonding material having Sn-Cu thermal and amorphous properties as a bonding medium .

FIG. 22 is a graph showing the thermal characteristics of a bonded material having Cu-Ag heating and amorphous characteristics produced by a method of manufacturing a bonded material having an exothermic and amorphous characteristics according to the present invention, measured by DTA, The first and second plating layers (left) in the plated state of the bonding material having the Sn-Cu thermal and amorphous characteristics prepared by the method for producing the bonding material having the exothermic and amorphous characteristics according to the present invention, (Right) in which the second plating layer has disappeared.

FIG. 24 is a graph showing the relationship between the first and second plating layers (left) before plating and the first and second plating layers of the bonding material having heat and amorphous characteristics of Ni-Cu produced according to the present invention, (Right) photograph is disclosed. 25 is a graph showing the amorphous characteristics (left) of the bonded material having the exothermic and amorphous characteristics Sn-Cu produced by the present invention as a result of XRD analysis of the bonded material having the exothermic and amorphous characteristics, And a graph showing a crystalline characteristic (right) as a result of phase analysis by XRD of a state in which the first and second plating layers disappear due to diffusion after heating.

FIG. 26 shows an electron microscope (SEM) photograph showing a cross-section of a multi-layered metal material produced by thickening the sum of the thicknesses of the two plated layers to 5 .mu.m. FIG. 27 shows the sum of the thicknesses of the two plated layers 28 shows a heating graph in which the thickness of the coating layer is 5 占 퐉 and the thermal property is measured using a differential scanning calorimeter (DSC). Fig. 28 shows a heating graph in which a multi- FIG. 29 shows an optical microscope photograph showing a cross-section of a copper electrode made by laminating six layers of a multi-layered metal material to form a low-temperature bonded structure.

30 shows an optical microscope photograph showing an end face portion of a Sn-Cu-based metal plating thin film produced by lengthening the plating time of a multilayer metal material to have a total plating thickness of 300 mu m.

Hereinafter, with reference to these drawings, specific examples of the method for producing a bonded material having the exothermic and amorphous characteristics of the present invention will be described.

For example, a process of forming a multilayered plating film by a method of manufacturing a bonded material having exothermic and amorphous characteristics using the plating method of the present invention will be described.

[Example 1]

In this embodiment, the plating was performed by dissolving the first metal salt and the second metal salt in a molar ratio of 1: 1 to 200: 1 in the alloy plating solution. 8 and 9A to 9H, when the ratio of the first metal salt to the second metal salt is less than 2: 1, for example, when the ratio of 6: 4 and 5: 5 is satisfied, the first and second plating layers The difference in the concentration of the second metal is reduced, so that a bonding material having heat and amorphous characteristics is not formed. If the ratio of the first metal salt to the second metal salt exceeds 100: 1, for example, when the ratio of the first metal salt to the second metal salt is in the range of 200: 1, the second metal salt is easily consumed during plating and the concentration of the second metal salt becomes thin, Instead, the hydrogen ions in the plating liquid are reduced to generate hydrogen bubbles. Therefore, it is difficult to form a bonding material having heat and amorphous properties.

In order to determine the first and second metal salts forming the bonding material having the exothermic and amorphous characteristics, a metal salt of an element having a standard reduction potential of 0.004 V or more and 1.5614 V or less was selected and multilayer plating was performed And Figs. 9A to 9H). When the reduction potential difference of the first and second metal salts is reduced to less than 0.029 V, the first and second metal salts are reduced when the first and second plating layers are formed, and the boundary between the plating layers disappears and the multilayered thin film is not formed. In addition, when the reduction potential difference of the first and second metal salts exceeds 1.0496 V, the second metal interferes with the plating of the first metal, so that the boundary between the plating layers also disappears and the multilayered thin film is not formed.

9A to 9H show cross-sectional views of the bonded materials having the exothermic and amorphous characteristics corresponding to the respective conditions of FIG. 8, and it is possible to confirm by photographs whether or not the bonding material having heat and amorphous characteristics according to the plating conditions is formed. The numbers in Figs. 9A to 9H correspond to the numbers in Fig. For example, the photograph of the condition 2-3 'in FIG. 8 shows the photograph' 2-3 'in FIGS. 9A to 9H.

FIG. 10 is a graph showing the range of conditions under which the multilayer plating is formed as a result of FIG.

As a result, in order to produce a bonding material having an exothermic and amorphous characteristics in the manufacturing method according to the present invention, a metal salt having a reduction potential difference of 0.029 V or more and 1.0496 V or less in the first metal salt and the second metal salt in the plating solution is used, The concentration ratio of the first metal salt and the second metal salt is preferably in the range of 2: 1 to 100: 1.

[Example 2]

200 ml of a sulfuric acid-based Sn-Cu alloy plating solution was prepared in order to form a multi-layer plated film of Sn and Cu.

SnSO4: 17.175 g

CuSO4.6H2O: 1.998 g

H2SO4: 10.72 ml

HCl: 0.03 ml

POELE: 0.8g

In this case, the plating voltage was -0.6 V, the current density was -30 mA / cm 2 and the plating time was 30 seconds in the first section, the plating voltage was -0.45 V, the current density was -2 mA / The plating time was 2 minutes. The first and second sections were tested repeatedly 400 times each.

As a result of the plating, it can be confirmed that a tin plating layer having a thickness of 600 nm and a copper plating layer having a thickness of 100 nm are alternately plated by 400 layers as shown in FIG.

Using the same plating solution, when the plating current or plating time was increased, the Sn and Cu layers were alternately plated thicker. The plating conditions were as follows: a plating voltage of -0.6 V, a current density of -30 mA / cm 2, and a plating time of 10 minutes in the first section, a plating voltage of -0.45 V and a current density of -2 mA / cm 2 , And the plating time was 10 minutes. The first and second sections were repeated five times each.

As a result of the plating, it can be confirmed that the tin plating layer having a thickness of 7 탆 and the copper plating layer having a thickness of 10 탆 are alternately plated by five layers each in a thicker thickness in Fig.

[Example 3]

A process for forming a Zn-Ni multi-layered plating film by a method of manufacturing a bonded material having exothermic and amorphous characteristics using the plating method of the present invention will be described below.

First, 200 ml of a sulfuric acid-based Zn-Ni alloy plating solution was prepared to form a Zn and Ni multi-layered plating film, followed by plating.

ZnSO4-7H2O: 46.0 g

NiSO4-6H2O: 4.20 g

H2SO4: 4ml

HCl: 0.03 ml

POELE: 0.8g

As shown in Fig. 13, a zinc layer having a thickness of 6 탆 and a nickel layer having a thickness of 3 탆 were alternately plated in 20 layers each. The plating conditions were as follows: a plating voltage of -1.8 V, a current density of -250 mA / cm 2, and a plating time of 10 minutes in the first section, a plating voltage of -1.2 V, and a current density of -100 mA / cm 2 , And the plating time was 10 minutes. The first and second sections were repeated 20 times each.

Further, although not shown in the drawing, if the same plating solution is used and the plating current or the plating time is increased, the Zn and Ni layers are alternately plated thicker.

When a third metal salt is additionally added to the plating solution of the above [Examples 1, 2 and 3] and the reducing potential of the metal salt is applied, a third metal precipitates and the first plating layer, the second plating layer, Layered plating film can be formed. A sectional view of the formed plating layer is shown in FIG. 14, and a structure in which a multilayer thin film layer composed of the first plating layer 42, the second plating layer 43, and the third plating layer 44 are alternately laminated is shown on the base material 41 .

FIG. 15 is a graph showing conditions under which an oxide film of a material to be bonded is removed, that is, reduction is performed in order to explain a method of bonding at a low temperature using a bonding material having heat and amorphous characteristics using the plating method of the present invention. In the soldering and brazing joints of metals, the oxide layer on the surface of the bonding material greatly reduces the bonding property. Since ordinary metals except precious metals, such as gold, form a surface oxide layer in an atmospheric ambient atmosphere, in order to achieve good bonding, the oxide layer on the surface must be removed by adjusting the temperature and the bonding atmosphere. The bonding medium of the bonding material having the exothermic and amorphous characteristics prepared in the present invention is unstable due to an increase in the surface area between the laminated layers and easily diffuses and melts at a low temperature, thereby enabling bonding at a low temperature. At this time, the bonding is performed at a temperature equal to or higher than the temperature at which the oxide film on the surface of the bonding material of Fig. 15 is removed.

In the graph of FIG. 15, the X axis represents the temperature and the left Y axis represents the dew point temperature in the atmosphere containing hydrogen at the time of bonding, and the right Y axis represents the degree of vacuum or the partial pressure of water vapor in the vacuum atmosphere at the time of bonding. In the figure, the upper part of each curve is stable in the state of the metal oxide and the lower part of the curve is stable in the state of the metal being reduced. In order for the material to be bonded to be brazed or soldered, the temperature and atmosphere of the reduction zone belonging to the lower part of the oxide curve of Fig. 15 are necessarily required. The atmosphere can also be created using chemicals (brazing, soldering flux) that remove oxides when in the atmosphere.

For example, all stainless steels contain chromium. In order to bond stainless steel, chromium oxide must be reduced to chromium because the chromium oxide is strong in stainless steel. That is, maintaining the temperature and atmosphere below the chromium oxide (Cr2O3) curve indicated by number 1 in FIG. 15 is indispensable for brazing and soldering of stainless steel. For example, when the bonding atmosphere is maintained at 10 -2 torr, the chromium oxide (Cr 2 O 3) on the surface is reduced to chromium at a temperature of 800 ° C or higher and at a temperature of 10 -3 torr, Bonding becomes possible. When 10 -5 torr is maintained, chromium oxide (Cr 2 O 3) on the surface is not present at a temperature of 500 ° C. or higher, so that stainless steel bonding is also possible. When joining in a reducing gas atmosphere containing hydrogen, the dew point of the left Y-axis may be used instead of the degree of vacuum.

However, when a Ni-Cu-based alloy (bulk material) is used as a bonding medium for bonding stainless steel in general, the melting point increases as Ni increases. Therefore, the lowest melting temperature is 100% Cu-0% Ni Lt; RTI ID = 0.0 &gt; 1083 C, &lt; / RTI &gt; Therefore, a normal bonding temperature (for example, a brazing temperature of a Ni-Cu bulk alloy or stainless steel using Cu or Ni as a bonding medium) using a Ni-Cu bulk alloy as a bonding medium is approximately 1200 ° C or higher.

On the other hand, when a bonding material having Ni-Cu thermal and amorphous characteristics prepared by the manufacturing method of the present invention is used as a bonding medium, it is unstable due to its wide surface area and the exothermic reaction in the interdiffusion process of atoms in the multi- It happens. At this time, the bonded material having the Ni-Cu exothermic and amorphous characteristics is melted at a low temperature, and the stainless steel can be bonded at a temperature of 900 ° C or lower at a low temperature as shown in Example 4. In addition, bonding can be performed at 800 ° C or 700 ° C or less depending on the plating conditions of the bonding material having heat and amorphous characteristics. Thus, it can be seen that the content of the graph of Fig. 15 conforms to the fact that bonding is possible in the reduction region where the surface oxide of the material to be bonded is removed.

When the bonding material having the Ni-Cu thermal and amorphous characteristics of the present invention is used as a bonding medium in comparison with the bonding temperature (1200 ° C) of the stainless steel of the conventional general bulk Ni-Cu based bonding medium alloy, 600 ℃ lower, and the percentage is only 50 ~ 83 compared to the existing junction temperature. Therefore, the energy saving rate of the bonding method using the bonding material having the Ni-Cu heating and amorphous characteristics is 17 to 50. Of course, a similar effect can be obtained in ordinary carbon steels not containing chromium (in Fig. 14, FeO is located at the upper left side of Cr2O3).

[Example 4]

The bonding material having the Ni-Cu thermal and amorphous properties developed in the present invention diffuses at low temperature between the laminated plating layers. When heat is generated and measured by DTA, Cu (melting point 1083 ° C), Ni (melting point 1445 ° C), peaks appear at 567 ° C, which is lower than the melting point, and the bonded materials having Ni-Cu exothermic and amorphous characteristics are melted. The thermal characteristics of the bonded material having the Ni-Cu thermal and amorphous characteristics at this time are measured by DTA and are shown in FIG. The peak in Fig. 15 corresponds to about 52.3% of the lowest melting point of the Ni-Cu-based alloy at 1083 캜. The results show that the melting point of Ni-Cu-based bulk alloys is lower than that of Cu (melting point: 1083 ℃) and Ni (melting point: 1445 ℃), which are elements of the plating layer, 700 ° C, 800 ° C, 900 ° C and 1000 ° C which is lower than the lowest melting point of 1083 ° C. Layer metal plating thin film is melted at a temperature lower than the melting point of Cu (melting point: 1083 DEG C), Ni (melting point: 1445 DEG C) and the lowest melting point of these bulk alloys due to the exothermic effect of the multilayered metal-plated thin film.

In detail, a bonded material having Ni-Cu thermal and amorphous characteristics was formed on a 304 stainless steel sheet of 30 X 10 X 0.3 (mm) size. Fever, and by bonding material is rolled up to face the stainless steel stainless steel specimen the specimen that is not coated is formed using a vacuum of 10 -4 torr having amorphous characteristics 600 ℃, 700 ℃, 800 ℃ , 900 ℃, in 1000 ℃ 10 The results are shown in Fig. Stainless steel specimens bonded at 900 ℃ were subjected to tensile test. The tensile strength reached 117kgf.

FIG. 18 shows the wavefront of the joint at this time, and it can be confirmed that the multilayered plated thin film is well bonded.

On the other hand, the iron oxide (FeO) indicated by 2 in FIG. 15 exists in the upper left of the figure and is much easier to be reduced than the chromium oxide. That is, as shown in the graph, at a temperature of 100 ° C or more, FeO is reduced to Fe metal and a good low-temperature bonding can be achieved. In addition, at a high degree of vacuum of 10 -3 torr or less, Fe is present even at a temperature of 100 ° C or lower, so that good low-temperature bonding can be achieved.

The metal group Au, Pt, Ag, Pd, Ir, Cu, Pb, Co, Ni, Sn, Os and Bi shown in FIG. 15 are present in the upper left part of the graph, It can be seen that it is easier to remove and that bonding can be performed at a lower temperature (for example, 100 ° C or less) than that under which FeO is reduced, or even if the vacuum and reducing atmosphere is worse.

On the other hand, the lowest melting point of the Sn-Cu alloy (bulk material) is 227 ° C (eutectic temperature) when the composition is 99.3% Sn-0.7% Cu. The bonding (soldering) temperature when the alloy is used as a bonding medium is about 260 to 270 ° C, which is about 40 ° C higher than the melting point. For example, when an electronic component is soldered to a brazing material having a composition of 99.3% Sn-0.7% Cu, the soldering temperature is about 260 to 270 ° C.

On the other hand, when the bonding material having the Sn-Cu thermal and amorphous characteristics developed in the present invention is used as the bonding medium, the bonding material having the exothermic and amorphous characteristics is unstable due to its wide surface area, An exothermic reaction occurs due to diffusion (see Example 5). At this time, the bonding material having Sn-Cu exothermic and amorphous characteristics melts at a low temperature, and as shown in Example 5, the melting point is lower than Sn (melting point 232 ° C) and Cu (melting point 1083 ° C) Copper can be bonded at a low temperature of 160, 170, 210 ° C, which is lower than 227 ° C, which is the lowest melting point of Cu-based bulk alloys. Therefore, compared with the bonding temperature (260 to 270 ° C) in which a conventional general-purpose Sn-Cu alloy is used as a bonding medium (solder), a bonding material having Sn- When used as a bonding medium, the bonding temperature is 50 to 110 ° C lower, and the percentage is only 59 to 81% of the existing junction temperature. As a result, the energy saving rate of the bonding method using the bonding material having the Sn-Cu heating and amorphous characteristics is 19 to 41% of that of the conventional Sn-Cu type solder.

[Example 5]

The bonding material having the Sn-Cu thermal and amorphous characteristics developed in the present invention diffuses at a low temperature and generates heat. When measured by DSC, a peak appears at 144 ° C., and a bonding material having Sn-Cu thermal and amorphous characteristics Is melted. The thermal properties at this time are measured by DSC and are shown in Fig. The peak in Fig. 19 corresponds to about 63.4% of the lowest melting point (eutectic temperature) of 227 캜 of the Sn-Cu based alloy. As shown in FIG. 19, the copper plates were bonded at 160 ° C., 170 ° C., and 210 ° C. at a low temperature using a bonding material having Sn-Cu thermal and amorphous characteristics as a bonding medium. In detail, a bonding material having Sn-Cu heating and amorphous characteristics was formed on a Cu plate having a size of 30 X 10 X 0.3 (mm). FIG. 20 is a photograph showing a bonding material having Sn-Cu exothermic and amorphous characteristics at this time. Cu specimens with Sn-Cu heating and amorphous properties were laminated facing the plated layer and bonded to each other at 160 ° C, 170 ° C and 210 ° C for 10 minutes in air or a vacuum of 10 -3 torr. FIG. 21 shows a joint photograph at this time. The tensile strength of the specimens bonded at 170 ℃ reached 38kgf.

In Example 5 of the present invention, copper was bonded at a temperature of 160 ° C or higher in the atmosphere or in a vacuum of 10 -3 torr, and in Example 4, stainless steel was bonded at a temperature of 600 ° C or higher in a vacuum of 10 -4 torr . These bonding examples are shown in Fig. As a result, when the bonding material having the exothermic and amorphous characteristics manufactured by the method of the present invention is used as the bonding medium, it can be seen that the bonding at a low temperature is possible at a temperature higher than the corresponding temperature in the region where the bonding material is reduced. The highest bonding temperature, of course, is below the melting point of the bonding material.

In another embodiment, a multilayered nanotube film exhibiting Cu-Ag heating and amorphous characteristics was prepared by the present invention, and the thermal characteristics at this time were measured by DTA and shown in FIG. At this time, a peak appears at 678.54 ° C, which is lower than the melting points of Ag (melting point 961 ° C) and Cu (melting point 1083 ° C), which are elements of the plating layer due to exothermic characteristics. This is because the lowest melting point (eutectic temperature , Cu-40% Ag), which corresponds to about 87.1% of 779 ° C.

From the experimental results of the above-mentioned thermal characteristics, it was confirmed that the bonding material having the exothermic and amorphous characteristics prepared by the present invention had a Cu-Ag content of at least 87.3% (52.3% of the Ni-Cu type multilayer thin film) (Multi-layered thin film)), peaks were observed in the temperature range below, and even if the conventional bonding medium was not melted and thus the bonding (brazing and soldering) was impossible, (Brazing, soldering) is possible. Naturally, even at the above-mentioned temperature of 87.1% or higher, bonding can be carried out by using the medium of the present invention, and the upper limit of the bonding temperature ranges from the melting point of the existing bonding medium or below the melting point of the bonding material.

The bonding material having the exothermic and amorphous characteristics of the present invention exists as a layered structure in a plated state, but when used as a bonding medium for low-temperature bonding, the bonding material having heat and amorphous characteristics, when heated, The plating layers are annihilated by mutual diffusion and are easily melted and crystallized as a joining portion. A Sn-Cu-based multi-layered nano-thin film layer having a heat generation characteristic was formed and heated at 160 ° C to confirm that the multi-layered nano-film layer was extinguished. FIG. 23 shows the disappearance of the first and second plating layers before and after the heating of the bonding material having the Sn-Cu thermal and amorphous characteristics at this time, and the diffusion of the first and second plating layers due to diffusion after heating.

In addition, a bonding material having Ni-Cu heating and amorphous characteristics was formed, and it was confirmed that the multi-layered nano thin film layer was extinguished by heating at 650 ° C. FIG. 24 shows the first and second plating layers before the heating of the Ni-Cu based multi-layered nano thin film layer and the disappearance of the first and second plating layers due to diffusion after heating.

In addition, the phase was analyzed using XRD to confirm the amorphous phase characteristics of the bonded materials with exothermic and amorphous properties. The bonding material having the exothermic and amorphous characteristics as a plated state before heating of the bonding material having Sn-Cu thermal and amorphous properties produced by the method of producing a bonding material having the exothermic and amorphous characteristics according to the present invention is analyzed by XRD FIG. 25 is a graph showing an amorphous characteristic (left) as a result and a crystalline characteristic (right) as a result of XRD analysis of the state in which the first and second plating layers disappear due to diffusion after heating.

[Comparative Example 1] A multilayered metal material having no exothermic reaction

If the thickness of each layer of the multilayer metal plating layer becomes thicker or the number of plating layers decreases, the area of the interface in the multilayer metal plating layer becomes smaller. In this embodiment, a Sn-Cu-based bonding material having a thickness of 5 μm and a thickness of two layers is prepared so as not to generate an exothermic reaction. The cross section of the Sn-Cu multi-layer material manufactured to have a total thickness of 5 占 퐉 of the two layers at this time was confirmed by an electron microscope and is shown in Fig. The thermal characteristics of the multi-layer material were measured by DTA and are shown in Fig. As a result, the DSC measurement did not show a low-temperature exothermic peak, and an endothermic peak appeared at 228 ° C at which the tin, which is an element constituting the plating, melts at a high temperature. That is, an exothermic peak at 144 ° C, which was exhibited in a Sn-Cu-based bonding material prepared by thinning the thickness of the two layers to 40 nm, was not found in the thick-made 5 μm thick material.

In order to avoid the exothermic reaction at this time, the semiconductor was heated to a copper electrode at a temperature of 170 ° C using a material in which each plating layer was made thick. The junction between the semiconductor and the electrode at this time was observed by an optical microscope and was not bonded. The result is shown in Fig. The bonding material in which each of the plated layers is made thick can be judged not to be bonded because only the endothermic peak is shown by the thermal analysis and the endothermic quantity is larger than the calorific value.

In addition, a Sn-Cu multilayered metal plating thin film having six layers of plating layers was prepared, and the copper electrode was bonded at 160 占 폚 at low temperature. FIG. 29 shows a cross section at this time. The joints at this time were partially bonded. This is because the amount of the plated layer was insufficient and the amount of molten metal was not sufficient.

In addition, the plating time was elongated to produce a Sn-Cu-based multilayered metal plating thin film having a total plating thickness of 300 m, and a cross section at this time is shown in Fig. The multilayered metal thin film produced by the present invention may have defects on the surface of the plating layer as the plating progresses. When the defects grow continuously on the vertical surface and the plating layer is formed to a thickness of 300 탆 or more, the proportion of defects in the multilayered plating layer increases, The plating layer is not well formed, the amorphous and exothermic characteristics are not exhibited, and the low temperature bonding is not achieved.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible.

Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the equivalents of the appended claims, as well as the appended claims.

10: Device for manufacturing bonded materials having exothermic and amorphous properties
11: container
12: Reference electrode
13: anode
14: cathode 14,
16: Magnetic for stirring
20: PC
30: Bonding material with exothermic and amorphous properties
31: conductive substrate
32: Insulation tape
33: First metal layer 33
34: second metal layer
41: Plated substrate
42: First metal layer
43: second metal layer
44: third metal layer

Claims (19)

Preparing an aqueous alloy plating solution containing two or more metal salts including a first metal salt and a second metal salt;
Immersing the electrode in the aqueous alloy plating solution to form an electrolytic plating circuit;
A voltage between +2 V and -4.5 V or a corresponding current value based on a 25 DEG C standard hydrogen electrode is input to a control unit for controlling the electrolytic plating circuit according to the reduction potential value of the metal salt to be plated, Applying a potential or current; And
Forming at least two or more multilayer amorphous metal plating films on the mother substrate by a standard reduction potential difference of the metal salts;
Wherein the multilayer amorphous metal plating film has exothermic and amorphous characteristics in which heat is generated when the multilayer amorphous metal plating film is changed to crystalline.
The method according to claim 1,
Wherein the range of the reduction potential value of the metal salt is a voltage between + 1.83V and -1.67V based on a standard hydrogen electrode at 25 캜 or a current value corresponding thereto, and having exothermic and amorphous characteristics.
The method according to claim 1,
Wherein said aqueous alloy plating solution has exothermic and amorphous characteristics including a first metal salt, a second metal salt, an acid and a base, and an additive in a plating solution based on water.
The method of claim 3,
The first and second metal salts include Sn, Cu, Zn, Ni, Al, Ti, V, Cr, Mn, Fe, Co, Ga, Ge, As, Zr, Nb, Mo, Ru, Rh, Pd, , At least one metal salt selected from the group consisting of In, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb and Bi metal salt. .
5. The method of claim 4,
Wherein the first and second metal salts have an exothermic and amorphous characteristics by using at least two metal salts of elements showing differences in standard reduction potentials.
The method of claim 3,
The acid is selected from the group consisting of sulfuric acid, hydrochloric acid, methanesulfonic acid (MSA), nitric acid, boric acid, acetic acid, organic sulfuric acid, citric acid, formic acid, ascorbic acid, hydrofluoric acid, phosphoric acid, A method of manufacturing a bonded material having a characteristic.
The method of claim 3,
Wherein the additive is selected from the group consisting of polyoxyethylene lauryl ether (POELE), a plating flatting agent (smoothing agent), an accelerator, an inhibitor, a defoamer, a polishing agent and an oxidation inhibitor.
The method according to claim 1,
The step of applying a reducing potential or current to the electrode may include a first voltage period in which the first metal and the second metal are simultaneously plated, and a second voltage period in which the second metal only is plated alternately. A method of manufacturing a bonded material having a characteristic.
The method according to claim 1,
Wherein the metal plating film has exothermic and amorphous characteristics in which the sum of the two film thicknesses is in the range of 0.1 nm to 5 占 퐉 when the two metal films are laminated.
The method according to claim 1,
Wherein the metal plating film has an exothermic and amorphous characteristics in which the thickness of the metal plating film is in a range of 0.6 to 300 mu m.
The method according to claim 1,
Wherein the bonding material is a bonding material for low temperature bonding which bonds the base material and the bonding material by an exothermic reaction caused by a change in crystal phase from amorphous to crystalline.
A bonding material having exothermic and amorphous characteristics including at least two metal elements exhibiting an exothermic reaction upon alloying and including at least two amorphous metal plating films.
13. The method of claim 12,
Wherein the metal element is selected from the group consisting of Sn, Cu, Zn, Ni, Al, Ti, V, Cr, Mn, Fe, Co, Ga, Ge, As, Zr, Nb, Mo, Ru, Rh, Pd, Ag, And at least one metal element selected from the group consisting of Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb and Bi.
13. The method of claim 12,
Wherein the metal element is a metal salt, and the metal element is selected from two or more metal elements showing a difference in the standard reduction potential.
13. The method of claim 12,
Wherein the metal plating film has exothermic and amorphous characteristics in which the sum of the two film thicknesses is in the range of 0.1 nm to 5 m when the two metal films are laminated.
13. The method of claim 12,
Wherein the multilayered metal plating film has exothermic and amorphous characteristics formed in a thickness ranging from 0.6 to 300 mu m as a whole.
13. The method of claim 12,
Wherein the metal plating film has a structure in which six or more layers are laminated and has heat and amorphous characteristics.
13. The method of claim 12,
Wherein the metal plating film has exothermic and amorphous characteristics used as a bonding material at a temperature lower than the melting point of the entire bulk composition constituting the plating layer.
13. The method of claim 12,
The bonding material having the exothermic and amorphous properties is a bonding material having a heat and amorphous characteristic, which is a material for low temperature bonding, which bonds the base material and the bonding material by an exothermic reaction caused by a change in crystal phase from amorphous to crystalline.
KR1020150104651A 2015-04-22 2015-07-23 Bonding material with exothermic and amorphous characteristics and manufacturing method thereof KR101818963B1 (en)

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PCT/KR2016/008063 WO2017014605A1 (en) 2015-07-23 2016-07-22 Metal plating film having heat-generating and amorphous properties and method for manufacturing same, use of same and low-temperature bonding method using same

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KR100415984B1 (en) 2001-04-18 2004-01-24 한국과학기술연구원 Preparing Method of Iron Thermit Welding Material with Mill Scale

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113234973A (en) * 2021-05-14 2021-08-10 中南大学 High-quality mirror aluminum alloy material and preparation method thereof

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