KR20190004214A - Metal multi-coating thin film layer with dispersed nano-wires and its fabrication method - Google Patents

Abstract

The present invention relates to a method of manufacturing a nanowire-dispersed metal multilayer thin film bonding material. Provided is a method of manufacturing a bonding material in which mechanical properties such as a tensile strength, a yield strength, and toughness of a bonding part are improved by dispersion of a nanowire reinforcement inside the bonding material to suppress crack propagation in the bonding material, and is able to provide excellent mechanical reliability and a long life-cycle even when bonded at low temperatures.

Description

TECHNICAL FIELD [0001] The present invention relates to a metal multi-layer thin film bonding material in which nanowires are dispersed, and a method of manufacturing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a metal multilayer thin film bonding material in which nanowires are dispersed and a method for manufacturing the same. More specifically, the present invention relates to a metal multilayer thin film having nanowires dispersed therein by electrolytic plating, and using the metal multilayer thin film as a bonding material, To a method of bonding. More particularly, the present invention relates to a metal multilayer thin film bonding material in which nanowires in a bonding material can suppress crack propagation by producing the present metal multilayer thin film bonding material including nanowires and using the same as a bonding material, and a manufacturing method thereof .

The conventional bonding method is to insert a bonding material (brazing has a melting point of 450 or higher and soldering has a melting point of 450 or lower) between the members to be bonded such as brazing (brazing) or soldering (softening) Heat it to bond.

At this time, the bonding material is in the form of a bulk and has substantially the same composition throughout the bonding material, and has a melting point according to the composition. In the diffusion bonding, the bonding material as the bonding medium is not used, the bonding materials are brought into contact with each other, and then the bonding is performed by heating the bonding materials or using the mechanical friction heat such as ultrasonic waves or friction.

Nano paste may be used for low temperature bonding. This is due to the phenomenon that the melting point of the nano powder is lowered. Nanometer sized powders are unstable and easily aggregated with neighboring powders. It is known that the melting point of the nano powder is lower than the melting point of the original bulk material in the course of the addition of the powders. The metal powder has a melting point (TM (d)) lower than the melting point (TMB) of the mass metal such as the melting point (TM) according to the particle diameter (d) (see Gibbs Thomson equation). Therefore, the lower the diameter d of the particles, the lower the melting point thereof.

Accordingly, various attempts have been made for a low melting point bonding material. However, conventional materials having low-temperature bonding properties have a disadvantage in that they are brittle and inferior in ductility. Therefore, there is a disadvantage that long-term reliability is lacking when joining this material to a power semiconductor power module junction or a highly reliable electronic, automobile, or industrial bonded material.

In order to solve the problems of the metal multilayer thin film bonding material as described above, there is a demand for a material capable of suppressing crack propagation in the bonding material by improving the ductility and toughness of the bonding material.

(Patent Document 1) KR 2012-0123829 A

(Patent Document 2) KR 2013-0013722 A

SUMMARY OF THE INVENTION An object of the present invention is to provide a method of manufacturing a nanowire-dispersed metal multilayer thin film low temperature bonding material in order to solve the problems of the prior art. More specifically, the bonding material may be composed of an amorphous metal multilayer thin film.

The bonding material of the present invention has the characteristics of a metal multilayer thin film bonding material which is melted at a low temperature as compared with the prior art and disperses the nanowire into the metal multilayer thin film so that the nanowire suppresses the propagation of the crack when the crack propagates in the bonding material .

As a result, the breakage of the metal multilayer thin film bonded portion to be bonded at a low temperature is delayed to increase the ductility of the bonded portion and to bond the bonded material at a low temperature, thereby reducing thermal stress and thermal damage.

Another object of the present invention is to provide a method of manufacturing a metal multilayer thin film, wherein when the material to be bonded using the bonding material is bonded, each individual layer of the metal multilayer thin film is melted and crystallized with amorphous characteristics, And increases by the melting point of the entire bulk composition alloy constituting it. Accordingly, it is an object of the present invention to provide a bonding material useful for joining a metal or a ceramic material having a heat resistance at a higher temperature than a bonding temperature, the joining being performed at a low temperature and the melting point elevated after solidification of the bonding material.

Another object of the present invention is to provide a nanowire as a reinforcing material in a bonding material, which improves the mechanical properties such as tensile strength, yield strength and toughness of a joint, thereby providing excellent mechanical reliability and long life even when bonded at a low temperature And to provide a bonding material in which the ductility of the conventional metal multilayer thin film bonding material is improved and the brittleness thereof is relaxed, and a method of manufacturing the same.

In order to accomplish the above object, the present invention provides a metal material having a metal multilayer thin film bonding material in which nanowires are dispersed in a joining region between two bonding materials.

More specifically, in one embodiment of the present invention, there is provided a bonding material in which nanowires in the metal thin film are dispersed, wherein the metal thin films are alternately stacked in at least two layers.

The nanowire may be a metal nanowire.

The nanowires may be SiC nanowires.

The nanowires may be non-metallic nanowires.

The nanowire may be a metal oxide nanowire.

The nanowire may have a surface plated with metal.

The nanowires dispersed in the metal multilayer thin film are formed on the surface of the nanowire by using a metal such as In (indium), Sn (tin), Sb (antimony), Bi (bismuth), Zn (zinc), Cu (copper) Coated with at least one of Ni (nickel), Pt (platinum), Pd (palladium), Fe (iron), Co (cobalt), Ti (titanium), Cr (chromium) May be nanowires.

The number of nanowires located at the interface between the different kinds of metal thin films may be 1 to 100 per 27.68 탆 ² .

The specific surface area of the nanowire may be 1 to 3,000 m ² / g.

Each of the metal thin films constituting the metal multilayer thin film is composed of Sn (tin), Cu (copper), Ag (silver), Ni (nickel), Zn (zinc), Cr (chromium) (Iron), Co (cobalt), Se (selenium), Tc (technetium), Ru (ruthenium), Rh (rhodium), Pd (palladium), Cd (cadmium) A group consisting of Te (tellurium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Tl (thallium), Pb (lead), Bi (bismuth) , And the like.

Each of the metal thin films constituting the metal multilayer thin film is made of a metal such as Ti, V, Ga, Ge, Al, Zr, Nb ), At least one metal element selected from the group consisting of Mo (molybdenum), Hf (hafnium), Ta (tantalum), W (tungsten), and Re (rhenium).

The nanowires dispersed in the metal multilayer thin film may be at least one selected from the group consisting of B (boron), Ti (titanium), Al (aluminum), V (vanadium), Cr (chromium), Mn (manganese) (Bismuth), Bi (bismuth), Ni (nickel), Zr (zirconium), Nb (niobium), Mo (molybdenum), Y (yttrium) , An oxide, a nitride, a carbide, a boride and an intermetallic compound containing Cu (copper), Au (gold), Mg (magnesium), Pd (palladium), Pt (platinum), and Zn And at least one nanowire selected from the group consisting of

The nanowires dispersed in the metal multilayer thin film may be CNTs.

One layer of the metal thin film of the metal multilayer thin film bonding material in which the nanowires are dispersed may have a thickness ranging from 1 nm to 1 占 퐉.

The metal thin film of the metal multi-layer thin film bonding material in which the nanowires are dispersed may have a thickness ranging from 1 nm to 500 nm.

In another embodiment of the present invention, there is provided a method of manufacturing a plating solution, comprising: preparing a plating solution containing different kinds of metal raw materials; Introducing a nanowire dispersion into the plating solution; And alternately applying electrical energy corresponding to the different kinds of metal raw materials by using the plating solution to alternately laminate at least two or more layers of different kinds of metal thin films. .

The nanowire dispersion may include: plating a metal on a surface of the nanowire; And dispersing the metal-coated nanowires in a solvent.

The step of plating metal on the surface of the nanowire can be performed by using a vacuum sputtering method, electroless plating method or CVD (Chemical Vapor Deposition) on the nanowire.

And alternately laminating at least two or more different kinds of metal thin films by applying electrical energy corresponding to the different kinds of metal raw materials by using the plating solution in the alternating manner, May be entirely or partially embedded in a structure in which at least two or more metal thin films are alternately stacked.

In the step of alternately laminating at least two or more different types of metal thin films by applying electrical energy corresponding to the different kinds of metal raw materials by using the plating solution, the individual layers are formed to have a thickness of 1 nm to 1 탆 .

One layer of the metal thin film of the metal multilayer thin film bonding material in which the nanowires are dispersed may be a metal material joining method capable of forming a thickness in the range of 1 nm to 500 nm.

According to the present invention, the metal multi-layer thin film bonding material in which the nanowires are dispersed is obtained by melting the bonding material at a temperature lower than the melting point of the bulk alloy of the same composition to bond the materials to be bonded and preventing the dispersed nanowires from interfering with crack propagation paths in the bonding material It suppresses crack progression. This improves the ductility, toughness and fracture life of the bonding material and has the effect of reducing thermal stress and thermal damage of the bonding material.

The present invention also provides a method of manufacturing a metal multi-layer thin film bonding material, comprising the steps of: melting a metal multilayer thin film having amorphous characteristics during crystallization using a metal multi-layer thin film bonding material having nanowires dispersed therein; It is increased by an alloy of the entire bulk composition and has heat resistance at a higher temperature than the bonding temperature.

1 is a schematic view showing a process of manufacturing a metal multilayer thin film bonding material in which nanowires are dispersed according to an embodiment of the present invention.
2 is a schematic view showing a cross section of a metal multilayer thin film bonding material and a base material manufactured according to an embodiment of the present invention.
3 is a schematic view of a bonding material manufactured according to one embodiment of the present invention.
FIG. 4 is a schematic view showing a bonding process of a metal multi-layer thin film bonding material in which nanowires are dispersed according to an embodiment of the present invention.
FIG. 5 is an image showing the crack relaxation pattern due to the nanowire of the bonding material manufactured according to an embodiment of the present invention. FIG.
FIG. 6 is a result of analysis using FE-SEM (Field Emission Scanning Electron Microscope) to confirm the number of nanowires per unit area of the interface between the metal thin films according to Example 1. FIG.
Fig. 7 is a graph showing the results of measurement of a Cu / Sn metal multi-layer thin film bonding material in which Ni-plated CNT nanowires are dispersed on a surface thereof measured using a differential scanning calorimeter according to Example 1, Fig.
FIG. 8 is a result of analysis using FE-SEM (Field Emission Scanning Electron Microscope) to confirm the number of nanowires per unit area of the interface between the metal thin films according to Example 2. FIG.
FIG. 9 is a heating curve graph of the Cu / Sn metal multilayer thin film bonding material in which Ag nanowires are dispersed, measured using a differential scanning calorimeter according to Example 2, before and after bonding (before heating).
FIG. 10 is a result of analysis using FE-SEM (Field Emission Scanning Electron Microscope) to confirm the number of nanowires per unit area of the interface between the metal thin films according to Example 3. FIG.
Fig. 11 is a graph showing the relationship between (before heating) bonding (before heating) and after bonding (after heating) of a Cu / Sn metal multilayer thin film bonding material in which Ni- plated SiC nanowires are dispersed on the surface, which is measured using a differential scanning calorimeter according to Example 3. Fig. Fig.
12 is a result of analysis using FE-SEM (Field Emission Scanning Electron Microscope) in order to confirm the number of nanowires per unit area in the interface between the metal thin films according to the fourth embodiment.
Fig. 13 is a graph showing the relationship between (before heating) and after bonding (after heating) the Cu / Sn metal multilayer thin film bonding material in which Ni-plated ZnO nanowires are dispersed on the surface measured using a differential scanning calorimeter according to Example 4. Fig. Fig.
14 is a scanning electron microscope (SEM) image obtained by analyzing the junction according to the fifth embodiment.
Fig. 15 is a graph showing the results of analyzing the components of the joint elements using the energy dispersion spectrum (EDS) according to Example 5. Fig.
16 is a cross-sectional SEM photograph of the bonding material produced according to Example 6. Fig.
17 is a photograph of a shear strength specimen in which nanowires are dispersed according to Example 6. Fig.
18 shows the shear strength measurement results of various specimens.
19 is a photograph of a specimen prepared according to various conditions.
20 shows the tensile test results of various specimens.
21 shows the results of specific surface area measurement according to Example 14. Fig.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

In addition, since the sizes and thicknesses of the respective components shown in the drawings are arbitrarily shown for convenience of explanation, the present invention is not necessarily limited to those shown in the drawings.

Also, throughout the specification, when an element is referred to as "including" an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

The metal multi-layer thin film bonding material in which the nanoparticles of the present invention are dispersed is prepared by electrodepositing different kinds of metal layers by electroplating so as to alternately laminate the nanometer-scale layers to form a metal multilayer thin film, So as to form a coating layer.

The metal multilayer thin film of the present invention is not a powder but a safe multi-layer thin film having amorphous characteristics, but has a melting point lower than that of a bulk material similarly to a nano-sized powder state .

For example, the metal powder has a melting point (T _M (d)) lower than the melting point (T _MB ) of the lump material, such as Gibbs Thomson equation below, depending on the particle diameter d. Therefore, the smaller the diameter d of the particles, the lower the melting point thereof.

At this time, the metal multilayer thin film is formed by applying a current density in the range of -10 A / dm ² to -0.1 mA / dm ² and a voltage corresponding to at least two kinds of metal salts, acids and additives to the reduction potential difference The plating time is adjusted so that each of the alternately plated layers in the multilayer is formed to have a thickness ranging from 1 nm to 10 탆 or less.

The metal multilayer thin film refers to a structure in which two or more types of metal layers of a nanometer-scale thickness are stacked in a regular order in the form of a wide surface to form a layer. When these layers are formed between different kinds of materials, their characteristics are completely different from those of bulk alloys. That is, the metallic multilayer thin film having such a layered structure of nanometer-scale thickness is in a very unstable state due to its large surface area in contact with dissimilar materials and high surface energy. Therefore, even if heated slightly, diffusion easily occurs between the metal layers and the movement of atoms becomes active. In addition, the interlayer thickness is thin and the amorphous phase characteristics are exhibited, and crystallization occurs upon heating at a low temperature.

Here, the metal multilayered thin film may be at least one selected from Sn (tin), Cu (copper), Ag (silver), Ni (nickel), Zn (zinc), Ti (titanium), V (vanadium) ), Fe (iron), Co (cobalt), Ga (gallium), Ge (germanium), Al (aluminum), Se (selenium), Zr (zirconium) (Technetium), Ru (ruthenium), Rh (rhodium), Pd (palladium), Cd (cadmium), In (indium), Sb (antimony), Te (tellurium) (Tin), Pb (lead), Bi (bismuth), Po (polonium), W (tungsten), Re (rhenium), Os (osmium), Ir ≪ RTI ID = 0.0 > and / or < / RTI >

1 is a schematic view showing a process of manufacturing a metal multilayer thin film bonding material in which nanowires are dispersed according to an embodiment of the present invention.

As described above, the nanowires can be dispersed in the plating liquid when the metal multilayer thin film using different kinds of metals is produced. The thus dispersed nanowires can then be uniformly dispersed in the bonding material produced in the form of a multilayer thin film.

3 is a schematic view of a bonding material manufactured according to one embodiment of the present invention. As shown in FIG. 3, the bonding material can be produced in the form of uniformly dispersed nanowires (white) in the multilayer thin film.

FIG. 5 is an image showing the crack relaxation pattern due to the nanowire of the bonding material manufactured according to an embodiment of the present invention. FIG. A portion where cracks are suppressed due to the nanowire is schematically shown.

2 is a schematic view showing a cross section of a metal multilayer thin film bonding material and a base material manufactured according to an embodiment of the present invention. FIG. 4 is a schematic view showing a bonding process of a metal multi-layer thin film bonding material in which nanowires are dispersed according to an embodiment of the present invention.

Since the bonding material according to an embodiment of the present invention is a heterogeneous multi-layer metal bonding material, the first and second base materials can be bonded at a low temperature as described above. In addition, the presence of nanowires can improve the strength and cracking properties of the problem of low temperature bonding.

< Example  1> CNT  Nano Wire  The dispersed plating solution Metal multilayer thin film binder  Produce

For the low - temperature bonding, metal multilayer thin - film bonding materials in which Cu and Sn dispersed CNT nanowires were alternately stacked were fabricated.

Ni is plated on the surface of the CNT nanowire having an average diameter of 20 nm and an average length of 10 μm using a vacuum sputtering method and then 1 g of CNT nanowire is dispersed by ultrasonic in 100 ml of ethanol.

And then CuSO ₄ 5H ₂ O 1.879g, SnCl ₂ and 2H ₂ O 16.924g, and a molecular weight of 4000 PEG 0.5g, Triammonium Citrate 25g and distilled water to prepare a plating solution of 250ml. To the prepared plating solution, add 3 ml of ethanol in which Ni-coated CNT nanowires are dispersed. At this time, the plating solution should be continuously stirred.

The purpose of plating the metal such as Ni, Au, Cu on the surface of CNT in the preparation of the plating solution is to improve the bonding property with the bonding material due to the hooking effect due to the roughness of the surface and to allow easy movement to the cathode when plating, And to improve the bonding property of the bonding material component metal.

CNTs coated with metal components on the surface inhibit floating or segregation of CNT components on the bonding material through good wetting with the metal components in the bonded bonding material, thereby suppressing the separation of CNTs and metallic components in the bonding material The bonding property is improved.

In this embodiment, a nickel (Ni) bumper layer is formed on a copper (Cu) plate of 25 mm x 25 mm area by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a voltage corresponding thereto for 10 minutes after forming an area, a nickel layer on the bumper -3A / dm ² to -7A / dm ² of current density range and the corresponding voltage and -0.1A / dm ² to about -0.5A / dm ² of current density and hence the range of A corresponding voltage is applied in pulse form for 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm and plating the entire bonding material to laminate alternately 40 占 퐉 to 50 占 퐉 thickness, The Ni in the plating solution was embedded in the metal thin films to be plated and deposited on the copper plate.

The number of nanowires per unit area of the interface between the metal thin films was analyzed by FE-SEM (Field Emission Scanning Electron Microscope). The measured image is shown in Fig. The number of nanowires located at the interface between the metal thin films is 1 to 20 per 27.68 占 퐉 ² .

The nickel (Ni) layer was prepared by electrolytic plating to prevent the diffusion of the metal atoms constituting the bonding material to the inside of the base material and the good bonding between the metal multilayer thin films.

The metal multi-layer thin film bonding material in which the nanowires are dispersed according to the present invention can be bonded at a low temperature in a nano-sized thin film. To confirm this, the bonding material before and after heating was analyzed by differential scanning calorimetry (DSC). The heating curve before (before heating) and after (after heating) the Cu / Sn metal multilayer thin film bonding material in which Ni-plated CNT nanowires are dispersed on the surface measured by differential scanning calorimetry is shown in FIG. .

The bonding material with amorphous properties before bonding shows an endothermic peak at 198.34 ° C, a solidus point of 167.19 ° C and a liquidus point of 198.34 ° C. It can be confirmed that no peak occurs at 300 ° C in the case of the crystallized bonding material after bonding. It can be seen that the bonding material produced by the method of this embodiment has a melting point of about 200 ° C before bonding and a heat-resistant temperature of 300 ° C or higher after bonding.

< Example  2> Ag  Nano Wire  The dispersed plating solution Metal multilayer thin film binder  Produce

For the low - temperature bonding, a metal multilayer thin film bonding material in which Cu and Sn dispersed Ag nanowires were alternately laminated was prepared. 1 g of Ag nanowire having an average diameter of 20 to 40 nm and an average length of 10 to 20 μm is dispersed in 100 ml of ethanol by ultrasonic wave. And then CuSO ₄ 5H ₂ O 1.879g, SnCl ₂ and 2H ₂ O 16.924g, and a molecular weight of 4000 PEG 0.5g, Triammonium Citrate 25g and distilled water to prepare a plating solution of 250ml.

5 ml of Ethanol in which Ag nanowires are dispersed is added. At this time, the plating solution should be continuously stirred.

In this embodiment, a nickel (Ni) bumper layer is formed on a copper (Cu) plate of 25 mm x 25 mm area by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a voltage corresponding thereto for 10 minutes after forming an area, a nickel layer on the bumper -3A / dm ² to -7A / dm ² of current density range and the corresponding voltage and -0.1A / dm ² to about -0.5A / dm ² of current density and hence the range of A corresponding voltage is applied in pulse form for 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm and plating the entire bonding material to laminate alternately 40 占 퐉 to 50 占 퐉 thickness, The Ag nanowires in the plating solution were embedded in the metal thin films to be plated and deposited on the copper plate. The nickel (Ni) layer was prepared by electrolytic plating to prevent the diffusion of the metal atoms constituting the bonding material to the inside of the base material and the good bonding between the metal multilayer thin films.

The number of nanowires per unit area of the interface between the metal thin films was analyzed by FE-SEM (Field Emission Scanning Electron Microscope). The measured image is shown in Fig. The number of nanowires located at the interface between the metal thin films is 1 to 20 per 27.68 占 퐉 ² .

The metal multi-layer thin film bonding material in which the nanowires are dispersed according to the present invention can be bonded at a low temperature in a nano-sized thin film. To confirm this, the bonding material before and after heating was analyzed by differential scanning calorimetry (DSC). FIG. 9 shows a heating curve before (before heating) and after (after heating) the Cu / Sn metal multi-layer thin film bonding material in which Ag nanowires are dispersed, measured using a differential scanning calorimeter. The bonding material with amorphous properties before bonding shows an endothermic peak at 197.49 ° C, a solidus point of 168.97 ° C and a liquidus point of 197.49 ° C. It can be confirmed that no peak occurs at 300 ° C in the case of the crystallized bonding material after bonding. It can be seen that the bonding material produced by the method of this embodiment has a melting point of about 200 ° C before bonding and a heat-resistant temperature of 300 ° C or higher after bonding.

< Example  3> SiC nano Wire  The dispersed plating solution Metal multilayer thin film binder  Produce

For the low temperature bonding, a metal multilayer thin film bonding material in which Cu and Sn dispersed SiC nanowires were alternately laminated was prepared. Ni is plated on the surface of the SiC nanowire of diameter <2.5 μm and L / D ≥ 20 using a vacuum sputtering method and electroless plating, and then 0.5 g of SiC nanowire is dispersed by ultrasonic wave in 100 ml of ethanol.

And then CuSO ₄ 5H ₂ O 1.879g, SnCl ₂ and 2H ₂ O 16.924g, and a molecular weight of 4000 PEG 0.5g, Triammonium Citrate 25g and distilled water to prepare a plating solution of 250ml. 3 ml of Ethanol in which Ni-plated SiC nanowire is dispersed is added to the prepared plating solution. At this time, the plating solution should be continuously stirred.

The purpose of plating Ni, Au, Cu and other metal components on the surface of SiC during plating liquid production is to improve the bonding property with the bonding material due to the hooking effect due to the roughness of the surface and to easily move to the cathode when plating, And the bonding material component metal, the metal component is applied to the surface of the SiC. SiC coated with a metal on the surface suppresses floating or segregation of the SiC component on the bonding material due to good wetting with the metal component in the molten bonding material, thereby suppressing the separation of the SiC and the metallic component in the bonding material The bonding property is improved.

In this embodiment, a nickel (Ni) bumper layer is formed on a copper (Cu) plate of 25 mm x 25 mm area by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a voltage corresponding thereto for 10 minutes after forming an area, a nickel layer on the bumper -3A / dm ² to -7A / dm ² of current density range and the corresponding voltage and -0.1A / dm ² to about -0.5A / dm ² of current density and hence the range of A corresponding voltage is applied in pulse form for 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm and plating the entire bonding material to laminate alternately 40 占 퐉 to 50 占 퐉 thickness, The Ni in the plating solution was filled in the metal thin films on which the plated SiC nanowires were plated to deposit the copper on the copper plate. The nickel (Ni) layer was prepared by electrolytic plating to prevent the diffusion of the metal atoms constituting the bonding material to the inside of the base material and the good bonding between the metal multilayer thin films.

The number of nanowires per unit area of the interface between the metal thin films was analyzed by FE-SEM (Field Emission Scanning Electron Microscope). The measured images are shown in Fig. The number of nanowires located at the interface between the metal thin films is 1 to 15 per 27.68 탆 ² .

The metal multi-layer thin film bonding material in which the nanowires are dispersed according to the present invention can be bonded at a low temperature in a nano-sized thin film. To confirm this, the bonding material before and after heating was analyzed by differential scanning calorimetry (DSC). The heating curve before (before heating) and after (after heating) the Cu / Sn metal multi-layer thin film bonding material in which Ni-plated SiC nanowires are dispersed on the surface measured by differential scanning calorimetry is shown in FIG. . The bonding material with amorphous properties before bonding shows an endothermic peak at 197.56 ° C, a solidus point of 167.10 ° C and a liquidus point of 197.56 ° C. It can be confirmed that no peak occurs at 300 ° C in the case of the crystallized bonding material after bonding. It can be seen that the bonding material produced by the method of this embodiment has a melting point of about 200 ° C before bonding and a heat-resistant temperature of 300 ° C or higher after bonding.

< Example  4> ZnO  Nano Wire  The dispersed plating solution Metal multilayer thin film binder  Produce

For the low temperature bonding, a metal multilayer thin film bonding material in which Cu and Sn dispersed ZnO nanowires were alternately laminated was prepared. Ni is plated on the surface of ZnO nanowires of diameter 50nm, length ≥ 300nm by electroless plating and vacuum sputtering method. Then, 0.1g of ZnO nanowire is dispersed by ultrasonic in 100ml of ethanol.

And then CuSO ₄ 5H ₂ O 1.879g, SnCl ₂ and 2H ₂ O 16.924g, and a molecular weight of 4000 PEG 0.5g, Triammonium Citrate 25g and distilled water to prepare a plating solution of 250ml. 3 ml of Ethanol dispersed with Ni-plated ZnO nanowire is added to the prepared plating solution. At this time, the plating solution should be continuously stirred.

The purpose of plating the metal such as Ni, Au, Cu on the surface of ZnO during the plating solution production is to improve the bonding property with the bonding material due to the hooking effect due to the roughness of the surface and to allow easy movement to the cathode when plating, And the bonding material component metal, the metal component is applied to the surface of the ZnO. ZnO coated with metal on the surface suppresses the floating or segregation of the ZnO component on the bonding material through good wetting with the metal component in the molten bonding material, thereby suppressing the separation of ZnO from the metallic component in the bonding material The bonding property is improved.

In this embodiment, a nickel (Ni) bumper layer is formed on a copper (Cu) plate of 25 mm x 25 mm area by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a voltage corresponding thereto for 10 minutes after forming an area, a nickel layer on the bumper -3A / dm ² to -7A / dm ² of current density range and the corresponding voltage and -0.1A / dm ² to about -0.5A / dm ² of current density and hence the range of A corresponding voltage is applied in pulse form for 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm and plating the entire bonding material to laminate alternately 40 占 퐉 to 50 占 퐉 thickness, The Ni in the plating solution was prepared by plating ZnO nanowires on the plated metal thin films and plating the copper plates together. The nickel (Ni) layer was prepared by electrolytic plating to prevent the diffusion of the metal atoms constituting the bonding material to the inside of the base material and the good bonding between the metal multilayer thin films.

The number of nanowires per unit area of the interface between the metal thin films was analyzed by FE-SEM (Field Emission Scanning Electron Microscope). The measured image is shown in Fig. The number of nanowires located at the interface between the metal thin films is 1 to 8 per 27.68 탆 ² .

The metal multi-layer thin film bonding material in which the nanowires are dispersed according to the present invention can be bonded at a low temperature in a nano-sized thin film. To confirm this, the bonding material before and after heating was analyzed by differential scanning calorimetry (DSC). A graph of the heating curves before (before heating) and after (after heating) the Cu / Sn metal multilayer thin film bonding material in which Ni-plated ZnO nanowires are dispersed on the surface measured using a differential scanning calorimeter is shown in FIG. . The bonding material with amorphous properties before bonding shows an endothermic peak at 183.63 ° C, a solidus point of 174.69 ° C and a liquidus point of 183.63 ° C. It can be confirmed that no peak occurs at 300 ° C in the case of the crystallized bonding material after bonding. It can be seen that the bonding material produced by the method of this embodiment has a melting point of about 180 ° C before bonding and a heat-resistant temperature of 300 ° C or higher after bonding.

< Example  5> CNT  Nano Wire  Distributed Metal multilayer thin film Bonding material  Low temperature bonding

The metal multilayer thin film bonding material according to the present invention contains amorphous characteristics and can be used for low temperature bonding by melting at a low temperature as compared with the bulk alloy of the same composition due to heat generated during crystallization of amorphous. After the bonding, the melting point of the bonding material is increased as much as the alloy of the entire bulk composition by crystallization, and the bonding material can be used at a temperature higher than the bonding temperature. The microstructure of the bonding material was observed using a scanning electron microscope (SEM) to confirm the bonding state and crystallization. A metal multilayer thin film bonding material in which a 10 mm x 10 mm nickel bumper and CNT nanowires were dispersed on a 25 mm x 25 mm copper top plate was prepared, and the composition and manufacturing method of the plating solution were the same as in Example 1.

10 mm x 10 mm nickel (Ni) was bonded on a plated copper (Cu) top plate at a temperature of 200 ° C under a vacuum of 10 ^{- 5} torr, and a scanning electron microscope (SEM) image of the junction was shown in Fig. It can be seen that the joints are completely bonded without interface defects.

In addition, the components of the junction elements were analyzed using the energy dispersion spectrum (EDS), and the results are shown in FIG. As a result of EDS analysis, it was found that good bonding was achieved between the nickel (Ni) element, the bonding material layer and the copper (Cu) plate, and the CNT dispersion was achieved.

In order to confirm the crystallization, the microstructure of the specimen prepared by the above method was immersed in the ethanol solution of 92 vol% - HCl of 8 vol% for several minutes in water for several minutes and analyzed by scanning electron microscope (SEM) Is shown in Fig. It can be seen that after the bonding, the metal is bonded and crystallized.

< Example  6> CNT  Nano Wire  Distributed Metal multilayer thin film As a bonding material  Shear strength of bonded copper

Shear test specimens were fabricated to confirm the change of shear strength due to nanowire dispersion in metal multilayer thin film bonding material. For this purpose, Cu / Sn multilayer thin film bonding materials with CNT nanowires dispersed and Cu / Sn multilayer thin film bonding materials without CNT nanowires were fabricated. The concrete production method is as follows. Using a diamond cutter, a copper (Cu) sheet having a thickness of 1T is processed into a size of 1 mm x 1 mm. In order to manufacture a bonding material including CNT nanowires, plating was performed on a copper (Cu) upper plate having a size of 25 mm x 25 mm with the same plating solution composition as the plating solution prepared in Example 1.

A nickel (Ni) bumper layer was formed on a copper (Cu) plate of 25 mm × 25 mm in area of 10 mm × 10 mm by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a corresponding voltage for 10 minutes, a bumper layer -3A / dm ² to -7A / dm ² of current density range and the corresponding voltage and -0.1A / dm ² to a current density of -0.5A / dm ^2, and the corresponding voltage range over which to a pulse-type For 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm so as to alternately laminate 40 to 50 占 퐉 thickness of the entire bonding material, CNT nanowires were embedded in a metal thin film to be plated and deposited on a copper plate.

16 is a cross-sectional SEM photograph of the bonding material produced according to Example 6. Fig.

Control group in order to prepare a multi-layer metal thin film bonding material containing no CNT nanowires and CuSO ₄ 5H ₂ O 1.879g, SnCl ₂ and 2H ₂ O 16.924g, the molecular weight of the PEG 4000 0.5g, Triammonium Citrate to 25g and distilled water 250ml (Ni) bumper was fabricated under the above conditions and a Cu / Sn multilayer thin film bonding material without CNT nanowire was fabricated on the bumper.

Then 1mm x 1mm x copper (Cu) made of 1mm in size after removal of the sample oxide layer of each CNT nanowires are dispersed bonding material and the CNT nanowires placed on a non-distributed bonding material 10 ^{- 5} torr melting point of the bonding material in a vacuum Lt; RTI ID = 0.0 &gt; 200 C. &lt; / RTI &gt; Of course, bonding can be performed at a temperature of 200 占 폚 or more, that is, at a normal soldering temperature of 300 占 폚 or less, and the highest bonding temperature of the Sn-Cu alternating laminated bonding material can be below the solidus of the base material from which the base material begins to melt. The shear strength test specimen in which the prepared nanowires are dispersed is shown in Fig.

The average shear strength of specimens bonded with dispersed nanowires was 52.095MPa and the average shear strength of specimens bonded without using nanowires was 25μm / s. Is 39.977 MPa. As a result of measuring the shear strength, it can be seen that the shear strength of the specimen bonded by dispersing the nanowires on average is increased by 30% (12.118 MPa) or more. The shear strength measurement results are shown in Fig.

< Example  7> Ag  Nano Wire  Distributed Metal multilayer thin film As a bonding material  Shear strength of bonded copper

Shear test specimens were fabricated to confirm the change of shear strength due to nanowire dispersion in metal multilayer thin film bonding material. For this purpose, Cu / Sn multilayer thin film bonding materials with Ag nanowires dispersed and Cu / Sn multilayer thin film bonding materials without Ag nanowires were fabricated. The concrete production method is as follows. Using a diamond cutter, a copper (Cu) sheet having a thickness of 1T is processed into a size of 1 mm x 1 mm. For the preparation of the bonding material including the Ag nanowire, plating was performed on the copper (Cu) upper plate having a size of 25 mm x 25 mm with the same plating solution composition as the plating solution prepared in Example 2.

A nickel (Ni) bumper layer was formed on a copper (Cu) plate of 25 mm × 25 mm in area of 10 mm × 10 mm by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a corresponding voltage for 10 minutes, a bumper layer -3A / dm ² to -7A / dm ² of current density range and the corresponding voltage and -0.1A / dm ² to a current density of -0.5A / dm ^2, and the corresponding voltage range over which to a pulse-type The tin thin film and the copper thin film of two or more layers are plated at a thickness of 40 nm to 50 nm for each individual layer so that the thickness of the entire bonding material is alternately laminated in the range of 40 탆 to 50 탆 and the Ag nano wire in the plating liquid is plated And then plating and depositing copper on the copper plate.

Control group with CuSO ₄ and to produce a multilayer thin film metal bonding material containing no Ag nanowire 5H ₂ O 1.879g, SnCl ₂ and 2H ₂ O 16.924g, the molecular weight of the PEG 4000 0.5g, Triammonium Citrate to 25g and distilled water 250ml (Ni) bumper under the same conditions as above, and a Cu / Sn multilayer thin film bonding material without Ag nanowire was fabricated on the bumper.

Then 1mm x 1mm x copper (Cu) made of 1mm in size after removal of the sample oxide layer of each Ag nanowires are dispersed bonding material and the Ag nanowire was placed on the bonding material are not dispersed 10 ^{- 5} torr melting point of the bonding material in a vacuum Lt; RTI ID = 0.0 &gt; 200 C. &lt; / RTI &gt; Of course, bonding can be performed at a temperature of 200 占 폚 or more, that is, at a normal soldering temperature of 300 占 폚 or less, and the highest bonding temperature of the Sn-Cu alternating laminated bonding material can be below the solidus of the base material from which the base material begins to melt.

The average shear strength of specimens bonded with dispersed nanowires was 49.189MPa, and the average shear strength of specimens joined without using nanowires was 25μm / s with a shear height of 25mm / s. Is 39.977 MPa. As a result of measuring the shear strength, it can be seen that the shear strength of specimens bonded by dispersing nanowires on average increased by 23% (9.212 MPa) or more. The shear strength measurement results are shown in Fig.

< Example  8> SiC nano Wire  Distributed Metal multilayer thin film As a bonding material  Shear strength of bonded copper

Shear test specimens were fabricated to confirm the change of shear strength due to nanowire dispersion in metal multilayer thin film bonding material. For this purpose, Cu / Sn multilayer thin film bonding materials with SiC nanowires dispersed and Cu / Sn multilayer thin film bonding materials without SiC nanowires were fabricated. The concrete production method is as follows. Using a diamond cutter, a copper (Cu) sheet having a thickness of 1T is processed into a size of 1 mm x 1 mm. In order to manufacture a bonding material including SiC nanowires, plating was performed on a copper (Cu) upper plate having a size of 25 mm x 25 mm with a plating solution composition similar to that of the plating solution prepared in Example 3. A nickel (Ni) bumper layer was formed on a copper (Cu) plate of 25 mm × 25 mm in area of 10 mm × 10 mm by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a corresponding voltage for 10 minutes, a bumper layer -3A / dm ² to -7A / dm ² of current density range and the corresponding voltage and -0.1A / dm ² to a current density of -0.5A / dm ^2, and the corresponding voltage range over which to a pulse-type For 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm so as to alternately laminate 40 to 50 占 퐉 thickness of the entire bonding material, SiC nanowires were embedded in a metal thin film to be plated and deposited on a copper plate.

Control group in order to prepare a multi-layer metal thin film bonding material that does not contain SiC nanowires and CuSO ₄ 5H ₂ O 1.879g, SnCl ₂ and 2H ₂ O 16.924g, the molecular weight of the PEG 4000 0.5g, Triammonium Citrate to 25g and distilled water 250ml (Ni) bumper was fabricated under the same conditions as above, and a Cu / Sn multilayer thin film bonding material without SiC nanowire was fabricated thereon.

Then 1mm x 1mm x copper (Cu) made of 1mm in size after removal of the sample oxide layer of each SiC nanowires are dispersed bonding material and SiC nanowire is placed on a non-distributed bonding material 10 ^{- 5} torr melting point of the bonding material in a vacuum Lt; RTI ID = 0.0 &gt; 200 C. &lt; / RTI &gt; Of course, bonding can be performed at a temperature of 200 占 폚 or more, that is, at a normal soldering temperature of 300 占 폚 or less, and the highest bonding temperature of the Sn-Cu alternating laminated bonding material can be below the solidus of the base material from which the base material begins to melt.

The average shear strength of specimens bonded with dispersed nanowires was 48.775MPa, and the average shear strength of specimens bonded without using nanowires was 25μm / s with a shear height of 25mm / s. Is 39.977 MPa. As a result of measuring the shear strength, it was found that the shear strength increased by 22% (8.798 MPa) or more in the specimen bonded with dispersed nanowires on average. The shear strength measurement results are shown in Fig.

< Example  9> ZnO  Nano Wire  Distributed Metal multilayer thin film As a bonding material  Shear strength of bonded copper

Shear test specimens were fabricated to confirm the change of shear strength due to nanowire dispersion in metal multilayer thin film bonding material. For this purpose, Cu / Sn multilayer thin film bonding materials with ZnO nanowires dispersed and Cu / Sn multilayer thin film bonding materials without ZnO nanowires were fabricated. The concrete production method is as follows. Using a diamond cutter, a copper (Cu) sheet having a thickness of 1T is processed into a size of 1 mm x 1 mm. In order to manufacture a bonding material containing ZnO nanowires, plating was performed on a copper (Cu) upper plate having a size of 25 mm x 25 mm with the same plating solution composition as the plating solution prepared in Example 4. A nickel (Ni) bumper layer was formed on a copper (Cu) plate of 25 mm × 25 mm in area of 10 mm × 10 mm by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a corresponding voltage for 10 minutes, a bumper layer -3A / dm ² to -7A / dm ² of current density range and the corresponding voltage and -0.1A / dm ² to a current density of -0.5A / dm ^2, and the corresponding voltage range over which to a pulse-type For 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm so as to alternately laminate 40 to 50 占 퐉 thickness of the entire bonding material, ZnO nanowires were embedded in a metal thin film to be plated and deposited on a copper plate.

Comparing the group of ZnO for the production of multi-layer thin film to metal bonding material that comprises a nanowire and CuSO ₄ 5H ₂ O 1.879g, SnCl ₂ and 2H ₂ O 16.924g, the molecular weight of the PEG 4000 0.5g, Triammonium Citrate to 25g and distilled water 250ml (Ni) bumper was fabricated under the above conditions and a Cu / Sn multilayer thin film bonding material without ZnO nanowire was fabricated on the bumper.

Then 1mm x 1mm x copper (Cu) made of 1mm in size after removal of the sample oxide layer of each of ZnO nanowires are dispersed bonding material and SiC nanowire is placed on a non-distributed bonding material 10 ^{- 5} torr melting point of the bonding material in a vacuum Or more. Of course, it is possible to bond even at a temperature of 200 or more, that is, at a normal soldering temperature of 300 占 폚 or less. The highest bonding temperature of the Sn-Cu alternately laminated bonding material can be below the solidus of the base material from which the base material begins to melt.

The average shear strength of specimens bonded with dispersed nanowires was 48.471MPa, and the average shear strength of specimens joined without using nanowires was 25μm / s at shear height of 25mm / s. Is 39.977 MPa. As a result of measuring the shear strength, it can be seen that the shear strength of the specimen bonded by dispersing the nanowires on average is increased by 21% (8.494 MPa) or more. The shear strength measurement results are shown in Fig.

< Example  10> CNT  Nano Wire  Distributed Metal multilayer thin film Bonding material  Tensile strength and elongation

Tensile test specimens were fabricated to confirm the change of tensile strength and ductility due to nanowire dispersion in metal multilayer thin film bonding material. A nickel (Ni) bumper layer was formed on a copper (Cu) plate of 25 mm × 25 mm area by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a corresponding voltage for 10 minutes to the top end of a copper a rear bumper on the nickel layer formed as x 10mm area -3A / dm ² to -7A / dm ² of current density range and the corresponding current density and voltage of -0.1A / dm ² to about -0.5A / dm ² and for a range The corresponding voltage is applied in pulse form for 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm to plate the entire bonding material so that the thickness of the entire bonding material is alternately laminated to 40 to 50 탆 , CNT nanowires in the plating solution were embedded in the metal thin films to be plated and deposited on the copper plate. Thereafter, a current density in the range of -9 A / dm ² to -11 / dm ² and a voltage corresponding thereto were applied for 10 minutes to another copper (Cu) upper plate having a surface area of 30 mm x 10 mm, The bumper layer was formed to have a size of 10 mm x 10 mm, and the CNT nanowires were placed on the portion where the CNT nanowires were dispersed. Then, the CNT nanowires were bonded in a vacuum of 10 ^{- 5} torr to a temperature of 160, which is higher than the melting point of the present bonding material. Of course, it is possible to bond even at a temperature of 160 or more, that is, at a normal soldering temperature of 300C or less. The highest bonding temperature of the Sn-Cu alternating laminated bonding material can be below the solidus of the base material from which the base material begins to melt. The composition of the plating solution is the same as in Example 1. The fabricated tensile strength specimen is shown in Fig.

In order to confirm the change of tensile strength, a metal multilayer thin film without CNT nanowires was prepared and subjected to tensile test. And CuSO ₄ 5H ₂ O 1.879g, SnCl ₂ and 2H ₂ O 16.924g, molecular weight of the PEG 4000 0.5g, 250ml of a plating solution in Triammonium Citrate and 25g of distilled water was prepared. Thereafter, a current density in the range of -9 A / dm ² to -11 / dm ² was applied to the end of a copper (Cu) upper plate having a surface area of 30 mm x 10 mm, and a voltage corresponding thereto was applied for 10 minutes to form a nickel (Ni) bumper layer a 10mm x 10mm area of the rear bumper nickel layer on -3A / dm ² to a current density of -7A / dm ^2, and the corresponding voltage range and -0.1A / dm ² to about -0.5A / dm ² of current range to form a Density and a voltage corresponding thereto in pulse form for 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm to deposit the entire bonding material in a thickness of 40 탆 to 50 탆 alternately Respectively.

A current density in the range of -9 A / dm ² to -11 / dm ² and a voltage corresponding thereto were applied to the other end of a copper (Cu) upper plate having a surface area of 30 mm x 10 mm for 10 minutes to form a nickel (Ni) bumper layer Was formed on a 10 mm x 10 mm area and then put on the part where the metal multilayer thin film bonding material was formed and bonded at a temperature of 200 ° C or higher, which is higher than the melting point of the present bonding material, in a vacuum of 10 ^{- 5} torr. Of course, bonding can be performed at a temperature of 200 占 폚 or more, that is, at a normal soldering temperature of 300 占 폚 or less, and the highest bonding temperature of the Sn-Cu alternating laminated bonding material can be below the solidus of the base material from which the base material begins to melt.

As a result of the tensile test of specimens bonded with CNT nanowires dispersed and bonded at a tensile speed of 5 mm / min using CNT nanowires without using CNT nanowires, In the case of the specimen bonded with the multilayer thin-film bonding material, the ductility of the bonding portion increased about twice as compared with the specimen bonded with the metal multilayer thin-film bonding material without the nanowire. The tensile test results are shown in Fig.

In addition, the tensile strength of the CNT nanowire-dispersed metal multilayer thin-film bonded specimen was 267.2974 N, and the tensile strength of the specimen bonded with the metal multilayer thin-film bonding agent without dispersing the nanowire was 239.7039 N. Due to the CNT nanowire dispersion, The strength is also increased.

< Example  11> Ag  Nano Wire  Distributed Metal multilayer thin film Bonding material  Tensile strength and Elongation

Tensile test specimens were fabricated to confirm the change of tensile strength and ductility due to nanowire dispersion in metal multilayer thin film bonding material. A nickel (Ni) bumper layer was formed on a copper (Cu) plate of 25 mm × 25 mm area by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a corresponding voltage for 10 minutes to the top end of a copper a rear bumper on the nickel layer formed as x 10mm area -3A / dm ² to -7A / dm ² of current density range and the corresponding current density and voltage of -0.1A / dm ² to about -0.5A / dm ² and for a range The corresponding voltage is applied in pulse form for 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm to plate the entire bonding material so that the thickness of the entire bonding material is alternately laminated to 40 to 50 탆 And Ag nanowires in the plating solution were embedded in the metal thin films to be plated and deposited on the copper plate. Thereafter, a current density in the range of -9 A / dm ² to -11 / dm ² and a voltage corresponding thereto were applied for 10 minutes to another copper (Cu) upper plate having a surface area of 30 mm x 10 mm, The bumper layer was formed to have a size of 10 mm x 10 mm. The bumper layer was placed on the portion where the Ag nanowires were dispersed and then bonded at a temperature of 200 ° C or higher, which is higher than the melting point of the present bonding material, in a vacuum of 10 ^{- 5} torr. Of course, bonding can be performed at a temperature of 200 占 폚 or more, that is, at a normal soldering temperature of 300 占 폚 or less, and the highest bonding temperature of the Sn-Cu alternating laminated bonding material can be below the solidus of the base material from which the base material begins to melt. The composition of the plating solution is the same as in Example 2. The fabricated tensile strength specimen is shown in Fig.

To confirm the change of tensile strength, a metal multilayer thin film without Ag nanowire was prepared and subjected to a tensile test. The method is the same as in Example 10.

As a result of the tensile test of specimens bonded with CNT nanowires dispersed and bonded at a tensile speed of 5 mm / min using CNT nanowires without using CNT nanowires, In the case of the specimen bonded with the multilayer thin-film bonding material, the ductility of the bonding portion increased about twice as compared with the specimen bonded with the metal multilayer thin-film bonding material without the nanowire. The tensile test results are shown in Fig.

In addition, the tensile strength of the bonded metal multilayer thin film bonded Ag nanowire was 466.12N, and the tensile strength of the specimen bonded with the metal multilayer thin film bonding material without dispersing the nanowire was 239.7039N. The strength is also increased.

< Example  12> SiC nano Wire  Distributed Metal multilayer thin film Bonding material  Tensile strength and elongation

Tensile test specimens were fabricated to confirm the change of tensile strength and ductility due to nanowire dispersion in metal multilayer thin film bonding material. A nickel (Ni) bumper layer was formed on a copper (Cu) plate of 25 mm × 25 mm area by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a corresponding voltage for 10 minutes to the top end of a copper a rear bumper on the nickel layer formed as x 10mm area -3A / dm ² to -7A / dm ² of current density range and the corresponding current density and voltage of -0.1A / dm ² to about -0.5A / dm ² and for a range The corresponding voltage is applied in pulse form for 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm to plate the entire bonding material so that the thickness of the entire bonding material is alternately laminated to 40 to 50 탆 , And SiC nanowires in the plating solution were embedded in the metal thin films to be plated and deposited on the copper plate. Thereafter, a current density in the range of -9 A / dm ² to -11 / dm ² and a voltage corresponding thereto were applied for 10 minutes to another copper (Cu) upper plate having a surface area of 30 mm x 10 mm, The bumper layer was formed to have a size of 10 mm x 10 mm. The bumper layer was placed on the portion where the SiC nanowires were dispersed and then bonded at a temperature of 200 ° C or higher, which is higher than the melting point of the present bonding material, in a vacuum of 10 ^{- 5} torr. Of course, bonding can be performed at a temperature of 200 占 폚 or more, that is, at a normal soldering temperature of 300 占 폚 or less, and the highest bonding temperature of the Sn-Cu alternating laminated bonding material can be below the solidus of the base material from which the base material begins to melt. The composition of the plating solution is the same as in Example 3. The fabricated tensile strength specimen is shown in Fig.

To confirm the change of tensile strength, a metal multilayer thin film without SiC nanowire was fabricated and subjected to a tensile test. The method is the same as in Example 10.

As a result of tensile test of specimens bonded with SiC nanowires dispersed and bonded at a tensile speed of 5 mm / min using SiC nanowires without using SiC nanowires, In the case of specimens bonded with multilayer thin film bonding material, the ductility of the bonded part increased about 1.5 times as compared with the specimen bonded with metal multilayer thin film bonding material without nanowire. The tensile test results are shown in Fig.

The tensile strength of the specimen bonded with the metal multilayer thin film bonded with the SiC nanowire dispersed was 367.85 N. The tensile strength of the specimen bonded with the metallic multilayer thin film bonding agent without dispersing the nanowire was 239.7039 N. Due to the dispersion of the SiC nanowire, The strength is also increased.

< Example  13> ZnO  Nano Wire  Distributed Metal multilayer thin film Bonding material  Tensile strength and elongation

Tensile test specimens were fabricated to confirm the change of tensile strength and ductility due to nanowire dispersion in metal multilayer thin film bonding material. A nickel (Ni) bumper layer was formed on a copper (Cu) plate of 25 mm × 25 mm area by applying a current density in the range of -9 A / dm ² to -11 / dm ² and a corresponding voltage for 10 minutes to the top end of a copper a rear bumper on the nickel layer formed as x 10mm area -3A / dm ² to -7A / dm ² of current density range and the corresponding current density and voltage of -0.1A / dm ² to about -0.5A / dm ² and for a range The corresponding voltage is applied in pulse form for 40 minutes to deposit two or more layers of tin and copper thin films each having a thickness of 40 nm to 50 nm to plate the entire bonding material so that the thickness of the entire bonding material is alternately laminated to 40 to 50 탆 , ZnO nanowires in the plating solution were embedded in the metal thin films to be plated and deposited on the copper plate. Thereafter, a current density in the range of -9 A / dm ² to -11 / dm ² and a voltage corresponding thereto were applied for 10 minutes to another copper (Cu) upper plate having a surface area of 30 mm x 10 mm, The bumper layer was formed to have a size of 10 mm x 10 mm. The bumper layer was placed on the portion where the SiC nanowires were dispersed and then bonded at a temperature of 200 ° C or higher, which is higher than the melting point of the present bonding material, in a vacuum of 10 ^{- 5} torr. Of course, bonding can be performed at a temperature of 200 占 폚 or more, that is, at a normal soldering temperature of 300 占 폚 or less, and the highest bonding temperature of the Sn-Cu alternating laminated bonding material can be below the solidus of the base material from which the base material begins to melt. The composition of the plating solution is the same as in Example 4. The fabricated tensile strength specimen is shown in Fig.

To confirm the change of tensile strength, a metal multilayer thin film without ZnO nanowire was fabricated and subjected to tensile test. The method is the same as in Example 10.

As a result of tensile testing of specimens bonded with ZnO nanowires dispersed with a tensile speed of 5 mm / min using ZnO nanowires using the specimen prepared as in FIG. 19, In the case of specimens bonded with multilayer thin film bonding material, the ductility of the bonded part increased about 1.5 times as compared with the specimen bonded with metal multilayer thin film bonding material without nanowire. The tensile test results are shown in Fig.

In addition, the tensile strength of the bonded ZnO nanowires was 387.02 N, and the tensile strength of the bonded specimens was 239.7039N. The tensile strength of the ZnO nanowire dispersed ZnO nanowires was 387.02 N, The strength is also increased.

< Example  14> ZnO  Nano Of wire Specific surface area

The specific surface area of the nanowires dispersed in the metal multilayer thin film was measured. The specific surface area of the ZnO nanowire was measured. The size of the nanowire was a diameter of 50 nm and a length of 300 nm. The specific surface area of the ZnO nanowire was 11.718 m ² / g at a temperature of 77.350 K using a nitrogen gas. The results of ZnO specific surface area measurement are shown in FIG.

While the preferred embodiments of the present invention have been described with reference to the drawings, it is to be understood that the present invention is not limited to the above-described embodiments, and various changes and modifications can be made by those skilled in the art And shall include all modifications of the scope which are deemed to be equivalent.

Claims (20)

At least two or more metal thin films of different types are alternately stacked,
And the nanowires in the metal thin film are dispersed.
The method according to claim 1,
Wherein the nanowire is a metal nanowire.
The method according to claim 1,
Wherein the nanowire is a SiC nanowire.
The method according to claim 1,
Wherein the nanowire is a non-metallic nanowire.
The method according to claim 1,
Wherein the nanowire is a metal oxide nanowire.
The method according to claim 1,
Wherein the nanowire has a surface plated with metal.
The method according to claim 6,
The nanowires dispersed in the metal multilayer thin film are formed on the surface of the nanowire by using a metal such as In (indium), Sn (tin), Sb (antimony), Bi (bismuth), Zn (zinc), Cu (copper) Coated with at least one of Ni (nickel), Pt (platinum), Pd (palladium), Fe (iron), Co (cobalt), Ti (titanium), Cr (chromium) The bonding material is a nanowire.
The method according to claim 1,
Wherein the number of nanowires located at the interface between the different kinds of metal thin films is 1 to 100 per 27.68 占 퐉 ² .
The method according to claim 1,
Wherein the nanowire has a specific surface area of 1 to 3,000 m ² / g.
The method according to claim 1,
Each of the metal thin films constituting the metal multilayer thin film is composed of Sn (tin), Cu (copper), Ag (silver), Ni (nickel), Zn (zinc), Cr (chromium) (Iron), Co (cobalt), Se (selenium), Tc (technetium), Ru (ruthenium), Rh (rhodium), Pd (palladium), Cd (cadmium) A group consisting of Te (tellurium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Tl (thallium), Pb (lead), Bi (bismuth) &Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
The method according to claim 1,
Each of the metal thin films constituting the metal multilayer thin film is made of a metal such as Ti, V, Ga, Ge, Al, Zr, Nb ), At least one metal element selected from the group consisting of Mo (molybdenum), Hf (hafnium), Ta (tantalum), W (tungsten), and Re (rhenium).
The method according to claim 1,
The nanowires dispersed in the metal multilayer thin film may be at least one selected from the group consisting of B (boron), Ti (titanium), Al (aluminum), V (vanadium), Cr (chromium), Mn (manganese) (Bismuth), Bi (bismuth), Ni (nickel), Zr (zirconium), Nb (niobium), Mo (molybdenum), Y (yttrium) , An oxide, a nitride, a carbide, a boride and an intermetallic compound containing Cu (copper), Au (gold), Mg (magnesium), Pd (palladium), Pt (platinum), and Zn Wherein the nanowire is at least one selected from the group consisting of nanowires.
The method according to claim 1,
Wherein the nanowires dispersed in the metal multilayer thin film are CNTs.
The method according to claim 1,
Wherein the metal thin film of the metal multilayer thin film bonding material in which the nanowires are dispersed has a thickness ranging from 1 nm to 1 占 퐉.
The method according to claim 1,
Wherein the metal thin film of the metal multilayer thin film bonding material in which the nanowires are dispersed has a thickness ranging from 1 nm to 500 nm.
Preparing a plating solution containing different kinds of metal raw materials;
Introducing a nanowire dispersion into the plating solution; And
Applying alternating electrical energy corresponding to the different kinds of metal raw materials by using the plating solution and alternately laminating at least two or more different kinds of metal thin films;
Wherein the joining material has a thickness of 10 mm or less.
17. The method of claim 16,
The nanowire dispersion is prepared by dispersing,
Plating a metal on the nanowire surface; And
And dispersing the metal-coated nanowires in a solvent.
18. The method of claim 17,
Plating the surface of the nanowire with a metal;
Wherein the nanowire is carried out using a vacuum sputtering method, an electroless plating method, or a CVD (Chemical Vapor Deposition) method.
17. The method of claim 16,
Applying alternating electrical energy corresponding to the different kinds of metal raw materials by using the plating solution to alternately stack different types of metal thin films on at least two or more layers,
Wherein the nanowires are partially or entirely embedded in a structure in which the different types of metal thin films are alternately stacked in at least two layers.
17. The method of claim 16,
Applying alternating electrical energy corresponding to the different kinds of metal raw materials by using the plating solution to alternately stack different types of metal thin films on at least two or more layers,
And the individual layers are formed to a thickness of 1 nm to 1 占 퐉.

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