KR20160027452A - Multi-functional nano/micro solders and their methods for preparing the same - Google Patents

Abstract

The present invention relates to various types of nano/micro solders and a manufacturing method thereof and, more specifically, provides various types of nano/micro solders comprising: magnetic particles coated with an antioxidant; supports; and solder particles, wherein the supports are made of one or more selected from a group of tin, copper, aluminum, gold, silver, zinc, tungsten, lead, bismuth, indium, nickel, iron, antimony, manganese, titanium, silicon, magnesium, chrome, and oxides, nitrides, sulfides, phosphides, and halides thereof. The various types of the nano/micro solders include 0.1-30 mass% of the supports. According to the present invention, the various types of the nano/micro solders enhances solder mounting efficiency when the solders are sintered in an induction heating manner; and reduces process consumption time, costs, and an energy input amount because the solders have a magnetic property, and also minimize thermal influence on other electronic components because only a magnetic body of the solder is able to locally be heated. In addition, the present invention has magnetic property and is also manufactured by mixing particles with antioxidant activities and electric conductivity to enhance the properties and compatibility thereof.

Description

Multi-functional nano / micro solders and their manufacturing methods

The present invention relates to a multi-type nano / micro solder and a manufacturing method thereof, and more particularly, to a multi-type nano / micro solder having a magnetic body, an antioxidant, a support and solder particles, .

The solder is easily defective during the sintering process. Particularly when the heat is unevenly distributed, thermal stress may concentrate on a specific area of the solder surface, resulting in defects. This problem can be solved by mixing the magnetic particles well with the solder and sintering the heat uniformly by induction sintering method.

Solder is a material used to physically bond two or more electronic components. Therefore, the solder must have high spreadability and wettability during the melting process so that it can be fully attached to the bonded body. It must be able to accommodate expansion and contraction of integrated circuits and circuit boards made of various materials, easily wet the integrated circuits while spreading around in the melting process, and be able to completely solidify between the circuit boards during the cooling process.

The solder has the disadvantage of reacting with oxygen in the air during sintering to produce oxides. The resulting oxide may cause cracks and dross on the solder surface. Therefore, most of the currently commercialized solders contain antioxidants such as lead, gold, silver and indium. However, lead is harmful to the human body and is replaced by other metals, and gold, silver, and indium are used in a limited amount because of high price. A new antioxidant-based solder that solves these drawbacks is being developed.

The solder must have a high electrical conductivity to be able to rapidly transfer various electrical signals generated between the integrated circuit and the circuit board. In particular, solders containing gold, silver and the like are high in electric conductivity, but have high disadvantages. Also, it may be difficult to completely bond the circuit boards together in a conventional process having a high melting point and a low sintering temperature. To compensate for this, increasing the sintering temperature can damage integrated circuits with low melting points.

Solder necessarily has an indispensable problem, and this problem is fundamentally difficult to solve.

For example, Korean Patent No. 10-1007326 discloses a tin-copper-silver alloy nanoparticle, a method for producing the same, and an ink or paste using the alloy nanoparticle. Specifically, the method comprises: dissolving a tin salt and a surfactant in a solvent; Adding a reducing agent to the solution in which the tin salt and the surfactant are dissolved in a solvent to form tin nanoparticles; Forming a tin-copper alloy nanoparticle by adding a copper salt within 3 minutes to 60 minutes after the step of forming the tin nanoparticle in the solution to which the reducing agent is added; And forming a tin-copper-silver alloy nanoparticle by adding a silver salt after the step of forming the tin-copper alloy nanoparticle.

The tin-silver-lead-free solder (melting point of 217.0 ° C) as described above has a melting point of 34.0 ° C higher than that of tin-lead solder (melting point of 183.0 ° C). When the tin content is increased to lower the melting point of the lead-free solder, the melting point is lowered but the antioxidant property is decreased. On the contrary, when the silver content is increased, the antioxidant property is increased but the melting point is increased again. Copper improves the bonding strength by refining the surface texture of the solder, but if the copper content is too high, the compound (Cu ₆ Sn ₅ ) is produced and the melting point is increased and the bonding strength is lowered again.

Accordingly, the inventors of the present invention developed a compatible solder which can be used by attaching magnetic particles, antioxidant particles, solder particles and the like to various support micro powders in order to solve the problems of conventional solder alloys, And has an excellent antioxidative, electric conductivity and compatibility with each other, and completed the present invention.

SUMMARY OF THE INVENTION [0006]

It is to provide multi-nano / micro solder.

Another object of the present invention is to provide

And a method of manufacturing a nano / micro solder.

A further object of the present invention is to provide

And a method of sintering the multi-nano / micro solder.

According to an aspect of the present invention,

It is a multi-species nano / micro solder containing magnetic particles coated with antioxidants, supports and solder particles,

The support may be selected from the group consisting of tin, copper, aluminum, gold, silver, zinc, tungsten, lead, bismuth, indium, nickel, iron, antimony, manganese, titanium, silicon, magnesium, chromium, oxides, nitrides, sulfides, And at least one selected from the group consisting of cargoes,

The multi-type nano / micro solder includes 0.1 to 30 mass% of a support.

Further, according to the present invention,

Preparing antioxidant-coated magnetic particles, support particles and solder particles (step 1); And

And a step (step 2) of preparing a solder by mixing the antioxidant-coated magnetic particles, support particles and solder particles prepared in the step 1 (step 2).

Further,

Micro solder is sintered at a temperature of 50 to 1000 ° C for 1 second to 6 hours by an induction heating method.

Since the multi-type nano / micro solder according to the present invention has magnetic properties, it is possible to improve the solder packaging efficiency when the solder is sintered by the induction heating method, and to reduce the time required for the process, cost and energy input, It is possible to minimize the thermal influence on other electronic components.

In addition, since the particles exhibiting antioxidative and electric conductivity are mixed with the magnetic properties, the above characteristics and their compatibility are improved.

1 is a schematic view showing an example of a multi-type nano / micro solder according to the present invention;
2 is a photograph of the multi-type nano / micro solder fabricated in Example 2 by scanning electron microscope;
3 is a graph showing the magnetic properties of the multi-type nano / micro solder manufactured in Examples 2 and 4 and Comparative Examples 1, 2 and 4;
4 is a graph showing the degree of oxidation of the multi-type nano / micro solder prepared in Examples 1 to 5 and Comparative Examples 1 to 4;
5 is a graph showing electrical characteristics of the multi-type nano / micro solder manufactured in Examples 1 to 5 and Comparative Examples 1 to 4;
6 is a photograph of the multi-type nano / micro solder manufactured in Comparative Example 1 by scanning electron microscope;
7 is a photograph of the multi-type nano / micro solder manufactured in Comparative Example 4 with a scanning electron microscope;
8 is a graph showing magnetic properties of the multi-type nano / micro solder manufactured in Examples 7 and 9 and Comparative Examples 1, 5, and 7;
9 is a graph showing the degree of oxidation of the multi-type nano / micro solder manufactured in Examples 6 to 10 and Comparative Examples 1 and 5 to 7;
10 is a graph showing electrical characteristics of the multi-type nano / micro solder manufactured in Examples 6 to 10 and Comparative Examples 1 and 5 to 7;
11 is a photograph of the multi-type nano / micro solder manufactured in Comparative Example 7 by scanning electron microscopy;
12 is a graph showing the magnetic properties of the multi-type nano / micro solder manufactured in Examples 12 and 14 and Comparative Examples 1, 8, and 10;
13 is a graph showing the degree of oxidation of the multi-type nano / micro solder produced in Examples 11 to 15 and Comparative Examples 1 and 8 to 10;
14 is a graph showing electrical characteristics of the multi-type nano / micro solder manufactured in Examples 11 to 15 and Comparative Examples 1 and 8 to 10;
15 is a photograph of the multi-type nano / micro solder manufactured in Comparative Example 10 with a scanning electron microscope.

According to the present invention,

It is a multi-species nano / micro solder containing magnetic particles coated with antioxidants, supports and solder particles,

The support may be selected from the group consisting of tin, copper, aluminum, gold, silver, zinc, tungsten, lead, bismuth, indium, nickel, iron, antimony, manganese, titanium, silicon, magnesium, chromium, oxides, nitrides, sulfides, And at least one selected from the group consisting of cargoes,

The multi-type nano / micro solder includes 0.1 to 30 mass% of a support.

Hereinafter, FIG. 1 shows an example of a multi-type nano / micro solder according to the present invention, and a multi-type nano / micro solder according to the present invention will be described in detail.

The multi-species nano / micro solder according to the present invention is a multi-species nano / micro solder including magnetic particles coated with an antioxidant, a support, and solder particles.

As described above, the multi-type nano / micro solder can exhibit magnetic properties by including magnetic particles, can exhibit antioxidative properties by coating the antioxidant on the magnetic body, exhibit the property of supporting the constituent by including the support, By including solder particles it is possible to show electrical conductivity.

On the other hand, when the support particles and the solder particles have the same composition, the wettability of the solder particles to the support particles is high, so that the solder particles can be more adhered to the support particles. However, if desired, support particles and solder particles of different compositions may be used. For example, iron support particles may be used if high magneticity is required, and copper support particles may be used if high electrical conductivity is required.

If appropriate magnetic and electrical conductivity is required, the multi-nano / micro solder may comprise from 0.1 to 30 mass% of iron support particles.

At this time, the antioxidant-coated magnetic particles, the support and the solder particles may each have a diameter of 10 nm to 100 탆.

If the diameter of each particle is less than 10 nm, there may arise a problem that the characteristics (antioxidative property, magnetic property, electric conductivity, etc.) due to each particle are lowered, and the diameter of each particle exceeds 100 탆 The compatibility of the characteristics of the particles may deteriorate.

Preferably, the antioxidant-coated magnetic particles have a diameter of 10 to 100 nm, the support has a diameter of 0.1 to 50 μm, and the solder particles have a diameter of 100 to 500 nm.

If the diameter of the magnetic particles coated with the antioxidant is less than 10 nm, there may arise a problem that the antioxidative effect and the magnetic property due to the antioxidant and the magnetic particles do not play a role. The diameter of the magnetic particles coated with the antioxidant If the thickness exceeds 100 nm, the electrical conductivity and compatibility may decrease.

If the diameter of the support is less than 0.1 탆, the characteristics of supporting the construct may be insignificant. When the diameter of the support is more than 50 탆, the magnetic properties, antioxidation, electrical conductivity and compatibility are reduced Can occur.

If the diameter of the solder particles is less than 100 nm, the electrical conductivity may be insignificant. If the diameter of the solder particles exceeds 500 nm, there may be a problem that the antioxidant property, magnetic property and compatibility are reduced .

In the multi-kind nano / micro solder containing the antioxidant-coated magnetic particles, the support and the solder particles according to the present invention, the support may be selected from the group consisting of tin, copper, aluminum, gold, silver, zinc, tungsten, lead, bismuth, At least one element selected from the group consisting of iron, antimony, manganese, titanium, silicon, magnesium, chromium, oxides, nitrides, sulfides, phosphides and halides thereof.

Solder nanoparticles have the advantages of low melting point and high electrical conductivity, but they have high disadvantages. Such disadvantages can be solved by using solder particles attached to the low-cost support micropowder as described above. In addition, solder nanoparticles alone are difficult to apply to conventional microbump printing processes, but support micropowders with solder nanoparticles can be easily applied to the same microbump printing process.

Also, the multi-nano / micro solder includes 0.1 to 30 mass% of a support.

If the multi-kind nano / micro solder contains the support powder at a content of less than 0.1% by mass, there is a problem that the supporting property of the constituent is weakened, and the content of the multi-kind nano / micro solder exceeds 30% by mass When a support powder is included, there is a problem that magnetism, antioxidative property, electrical conductivity and compatibility are reduced.

In the multi-species nano / micro solder containing the antioxidant-coated magnetic particles, the support and the solder particles according to the present invention, the magnetic particles may be selected from the group consisting of vanadium, tungsten, nickel, iron, cobalt, titanium, silicon, chromium, rare earths, But it is not limited to the above-mentioned magnetic particles, and it is possible to use a material capable of imparting magnetic properties to the multi-nano / micro solder It can be selected and used properly. The multi-type nano / micro solder having magnetic properties can have various magnetic properties depending on the kind of the magnetic material.

By including the magnetic particles as described above, the solder ball can be more precisely transferred to the circuit board in the flip-chip bump process using the magnetic properties. When the conventional micro solder with no magnetic properties is sintered, the heat is distributed unevenly, and thermal stress concentrates on a specific portion of the solder surface, resulting in defects. However, when the multi-type nano / micro solder having magnetic properties is sintered by the induction heating method, heat may be uniformly distributed and defects may be reduced.

The antioxidant may be at least one selected from the group consisting of aluminum, gold, silver, zinc, indium, nickel, antimony, manganese, titanium, chromium, rare earths, oxides, nitrides, sulfides, However, the antioxidant is not limited thereto, and an antioxidant material to compensate for the disadvantages of the solder particles oxidized at a high temperature can be appropriately selected and used. In particular, the oxide magnetic material has the advantage that the surface is oxidized to reduce the possibility of generating a support, an antioxidant, a solder and an intermetallic compound.

The multi-nano / micro solder may contain 0.1 to 5 mass% of an antioxidant.

If the content of the nano / micro solder is less than 0.1% by mass, the antioxidant property is insufficient. If the nano / micro solder contains more than 5% by mass of the antioxidant, There is a problem that electrical conductivity and compatibility are reduced.

The multi-type nano / micro solder may include 0.1 to 5 mass% of magnetic particles.

If the multi-type nano / micro solder contains magnetic particles at a content of less than 0.1% by mass, there is a problem in that the magnetic properties are insignificant. When the multi-type nano / micro solder contains magnetic particles at a content exceeding 5% There is a problem that electrical conductivity and compatibility are reduced.

The solder may further include neodymium. By further including neodymium in the multi-nano / micro solder, the antioxidative and magnetic properties can be further improved.

In addition, the solder may further include iron particles having a diameter of 1 to 50 mu m. By further including the solder with the iron powder as an additional magnetic material, a stronger magnetic property can be exhibited.

If the multi-kind nano / micro solder contains iron powder at a content of less than 0.1% by mass, there is a problem in that the magnetic property is insignificant. When the multi-kind nano / micro solder contains iron powder at a content exceeding 30% There is a problem that the antioxidant property, the electric conductivity and the compatibility are reduced.

The solder particles may be selected from the group consisting of tin, copper, gold, silver, zinc, tungsten, lead, bismuth, indium, antimony, Manganese. However, the solder particles are not limited thereto, and a material having a low melting point and a high electric conductivity may be appropriately selected and used.

The multi-type nano / micro solder may include 0.1 to 97 mass% of solder particles.

If the nano / micro solder contains less than 0.1% by mass of the solder, the electrical conductivity is insufficient. If the nano / micro solder contains more than 97% by mass of the solder There is a problem that antioxidant activity, magnetism and compatibility are reduced.

At this time, it is preferable to use cerium oxide (CeO ₂ ) as the antioxidant, iron oxide (Fe ₂ O ₃ ) as the magnetic substance, copper or iron as the support, and tin-zinc particles as the solder particles. It is not.

The multi-type nano / micro solder according to the present invention may have a form in which magnetic particles coated with solder particles and an antioxidant are adhered on a support.

At this time, the multi-nano / micro solder has the characteristics of the magnetic particles, the support and the solder particles coated with each antioxidant to some extent, Other characteristics can be sacrificed).

The multi-type nano / micro solder may have magnetic properties and antioxidative properties at the same time.

Since the multi-type nano / micro solder according to the present invention includes the magnetic particles coated with the antioxidant, the support particles and the solder particles, the multi-type nano / micro solder according to the present invention can have the magnetic property due to the magnetic material and the antioxidant due to the antioxidant. In addition, by using the support in addition, it is possible to support the constituent while solving the problem that it is expensive to use only solder particles, and it can exhibit low melting point and high electric conductivity due to the solder particles, .

The multi-kind nano / micro solder may have a residual magnetization value of 0.1 to 30.0 KG, a coercive force of 0.0001 to 10,000 Oe, an elastic modulus of 1 to 100,000,000 kg / cm < ² < / RTI > cm.

According to the present invention,

Preparing antioxidant-coated magnetic particles, support particles and solder particles (step 1); And

And a step (step 2) of preparing a solder by mixing the antioxidant-coated magnetic particles, support particles and solder particles prepared in the step 1 (step 2).

Hereinafter, a method for manufacturing a multi-type nano / micro solder according to the present invention will be described in detail for each step.

In the method for manufacturing multi-species nano / micro solder according to the present invention, step 1 is a step of producing magnetic particles coated with an antioxidant, support particles and solder particles.

By preparing each particle in the above step and mixing them in a subsequent process, it is possible to produce a solder that exhibits both magnetic properties, antioxidative properties and electrical conductivity.

At this time, the preparation of the particles of the step 1 may be carried out using at least one process selected from the group consisting of an atomization process, a centrifugal classification process, a plasma nano-process, an electric explosion process, and a chemical synthesis process, The manufacturing method is not limited thereto, and the manufacturing method can be appropriately selected in consideration of the size of the particles to be manufactured.

For example, a powder having a diameter of 1 μm or more and less than 100 μm can be produced by an atomizing process and can be classified into a centrifugal classifier. Particles smaller than 10 nm and smaller than 1 μm can be produced by a combined process of an atomization process and a plasma nano-fabrication process. Particles smaller in diameter than 10 nm and smaller than 100 nm can be produced by an electric explosion process. Particles with diameters of at least 1 nm and less than 25 nm can be prepared by a chemical synthesis process.

The preparation of the magnetic particles coated with the antioxidant of the step 1 may be carried out using an electric explosion process and a chemical synthesis process, and the production of the support particles of the step 1 is carried out by using an atomization process and a centrifugal classification process And the production of the solder particles in the step 1 may be performed using an atomization process and a plasma nano-fabrication process.

In the method for manufacturing multi-type nano / micro solder according to the present invention, step 2 is a step of preparing solder by mixing the antioxidant-coated magnetic particles, support particles and solder particles prepared in step 1 above.

In step 2, the particles and powders produced and classified in step 1 may be mixed in an appropriate ratio as required to produce a multi-type nano / micro solder having magnetic properties.

At this time, the manufacturing of the solder in the step 2 may be performed using a mixing process and a ball milling process, but the method of manufacturing the solder is not limited thereto, and the particles produced in the step 1 may be mixed to form a multi- Any method that can be used can be used without limitation.

According to the present invention,

Micro solder is sintered at a temperature of 50 to 1000 ° C for 1 second to 6 hours by an induction heating method.

The multi-type nano / micro solder having magnetic properties, such as the multi-nano / micro solder including the magnetic body, can be sintered by the induction heating method. For example, if alternating current is supplied to the induction coil within a range that does not damage the integrated circuit and the circuit board, an alternating magnetic flux may be generated and an induced current may be generated. The multi-type nano / micro solder having magnetic properties can be melted while dissipating heat sensitively according to the electromagnetic force. The solder can be melted by dissipating the heat due to the resistance against the eddy current loss, and the magnetic body can be easily melted by dissipating heat due to addition of resistance against electrical loss due to magnetization of hysteresis loss in addition to eddy current loss.

Unlike the conventional heating method, the induction heating method is capable of indirect sintering and local sintering, has a high energy supply density, and is easy to control. In addition, the induction heating furnace is advantageous in that it is more compact and lightweight than the conventional heating furnace, has a stable operation control device, and is convenient in maintenance and repair.

At this time, the multi-nano / micro solder is sintered at a temperature of 50 to 1000 ° C. for 1 second to 6 hours by an induction heating method.

If the multi-type nano / micro solder is sintered by induction heating for less than 50 ° C or less than 1 second, there is a problem in that the strength of the solder joint portion is lowered. In addition, The other electronic parts are damaged or the sintering cost is increased.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the following examples are intended to illustrate the present invention, but the present invention is not limited to the following examples.

≪ Example 1 >

Step 1: An iron wire 0.5 μm in diameter was detonated at 10 kV in a vessel containing cerium nitrate (Ce (NO ₃ ) ₃ 6H ₂ O), ammonium hydroxide (NH ₄ OH) was added in an appropriate ratio, Ferric oxide (Fe ₂ O ₃ ) particles coated with 50 nm diameter cerium oxide (CeO ₂ ) were fabricated by a combination of electrical explosion and chemical synthesis processes (magnetic particles coated with antioxidants).

Copper powder with a diameter of 10 μm was prepared and classified by atomization and centrifugal classification (scaffold).

Tin-zinc particles with a diameter of 200 nm were prepared by a combined process of an atomization process and a plasma nano-process (solder particles).

Step 2: 2.97 mass% of magnetic nanoparticles coated with antioxidant of ferric oxide (Fe ₂ O ₃ ) coated with cerium oxide (CeO ₂ ) having a diameter of 50 nm prepared in the above step 1, 0.97 Mass% and tin-zinc solder nanoparticles having a diameter of 200 nm of 96.06 mass% were mixed and ball-milled to prepare various nano / micro solders.

≪ Examples 2 to 15 and Comparative Examples 2 to 10 >

Instead of preparing a copper powder having a diameter of 10 占 퐉 in the step 1 of Example 1, iron or copper powder may be prepared as shown in the following table, or the mass% of the magnetic particles, the support and the solder nano- The nano / micro solder was prepared in the same manner as in Example 1, except that the composition was prepared as shown in the following Tables.

(unit:
mass%) Solder nanoparticles Support Antioxidant-coated magnetic material 200 nm tin-zinc solder nanoparticles 10 탆 copper
Iron oxide coated on 50 nm cerium oxide Example 1 96.06 0.97 2.97 Example 2 92.29 4.86 2.85 Example 3 87.56 9.73 2.71 Example 4 78.07 19.52 2.41 Example 5 68.51 29.37 2.12 Comparative Example 2 58.91 39.27 1.82 Comparative Example 3 49.24 49.24 1.52 Comparative Example 4 39.51 59.27 1.22 200 nm tin-zinc solder nanoparticles 10 탆 iron Iron oxide coated on 50 nm cerium oxide Example 6 96.06 0.97 2.97 Example 7 92.29 4.86 2.85 Example 8 87.56 9.73 2.71 Example 9 78.07 19.52 2.41 Example 10 68.51 29.37 2.12 Comparative Example 5 58.91 39.27 1.82 Comparative Example 6 49.24 49.24 1.52 Comparative Example 7 39.51 59.27 1.22 200 nm tin-zinc solder nanoparticles 1 탆 copper Iron oxide coated on 50 nm cerium oxide Example 11 96.06 0.97 2.97 Example 12 92.29 4.86 2.85 Example 13 87.56 9.73 2.71 Example 14 78.07 19.52 2.41 Example 15 68.51 29.37 2.12 Comparative Example 8 58.91 39.27 1.82 Comparative Example 9 49.24 49.24 1.52 Comparative Example 10 39.51 59.27 1.22 200 nm tin-zinc solder nanoparticles Support Iron oxide coated on 50 nm cerium oxide Comparative Example 1 97.00 - 3.00

≪ Comparative Example 1 &

In the same manner as in Example 1, except that the support was not prepared, and 3.00% by mass of the magnetic substance coated with the antioxidant in Step 2 and 97.00% by mass of the solder nano particles were mixed in Example 1, Solder.

EXPERIMENTAL EXAMPLE 1 Comparison of Examples 1 to 5 and Comparative Examples 1 to 4

The mixing ratios of the multi-type nano / micro solders prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were measured with an electronic balance, and the results are shown in Table 1. In Table 1, Micro solders were observed with a scanning electron microscope and the results are shown in FIG. 2. The magnetic susceptibility to the external magnetic field of the multi-type nano / micro solder manufactured in Examples 2 and 4 and Comparative Examples 1, 2, The results are shown in Fig. 3 after measurement with a magnetic susceptibility meter. The oxygen saturation of the multi-type nano / micro solder manufactured in Examples 1 to 5 and Comparative Examples 1 to 4 was measured with an oxygen analyzer. The results are shown in FIG. 4, and the electrical resistivity was measured with a sheet resistance meter The results are shown in Fig.

The multi-type nano / micro solder prepared in Comparative Examples 1 and 4 was observed with a scanning electron microscope, and the results are shown in Figs. 6 and 7. Fig.

200 nm Sn-Zn alloy 10? Cu 50 nm CeO ₂ coated Fe ₂ O ₃ Sn, mass% Zn, mass% Cu, mass% CeO ₂ , mass% Fe ₂ O ₃ , mass% Example 1 87.41 8.65 0.97 1.98 0.99 Example 2 83.98 8.31 4.86 1.90 0.95 Example 3 79.68 7.88 9.73 1.81 0.90 Example 4 71.04 7.03 19.52 1.61 0.80 Example 5 62.34 6.17 29.37 1.41 0.71 Comparative Example 2 53.61 5.30 39.27 1.21 0.61 Comparative Example 3 44.81 4.43 49.24 1.01 0.51 Comparative Example 4 35.95 3.56 59.27 0.81 0.41 200 nm Sn-Zn alloy 10? Fe 50 nm CeO ₂ coated Fe ₂ O ₃ Sn, mass% Zn, mass% Fe, mass% CeO ₂ , mass% Fe ₂ O ₃ , mass% Example 6 87.41 8.65 0.97 1.98 0.99 Example 7 83.98 8.31 4.86 1.90 0.95 Example 8 79.68 7.88 9.73 1.81 0.90 Example 9 71.04 7.03 19.52 1.61 0.80 Example 10 62.34 6.17 29.37 1.41 0.71 Comparative Example 5 53.61 5.30 39.27 1.21 0.61 Comparative Example 6 44.81 4.43 49.24 1.01 0.51 Comparative Example 7 35.95 3.56 59.27 0.81 0.41 200 nm Sn-Zn alloy One ? Cu 50 nm CeO ₂ coated Fe ₂ O ₃ Sn, mass% Zn, mass% Cu, mass% CeO ₂ , mass% Fe ₂ O ₃ , mass% Example 11 87.41 8.65 0.97 1.98 0.99 Example 12 83.98 8.31 4.86 1.90 0.95 Example 13 79.68 7.88 9.73 1.81 0.90 Example 14 71.04 7.03 19.52 1.61 0.80 Example 15 62.34 6.17 29.37 1.41 0.71 Comparative Example 8 53.61 5.30 39.27 1.21 0.61 Comparative Example 9 44.81 4.43 49.24 1.01 0.51 Comparative Example 10 35.95 3.56 59.27 0.81 0.41 Comparative Example 1 88.27 8.73 0.00 2.00 1.00

As shown in Table 2, the content of other constituents (magnetic particles coated with 200 nm of solder particles and 50 nm of antioxidants) decreases as the content of copper powder of 10 μm in diameter increases in multi-nano / micro solders.

Fig. 2 shows a scanning electron microscope image of a multi-nano / micro solder prepared in Example 2 containing 4.86 mass% of a copper powder having a diameter of 10 占 퐉. The tin-zinc solder particles with a diameter of 200 nm and the iron oxide (Fe ₂ O ₃ ) coated with 50 nm diameter cerium oxide (CeO ₂ ) (magnetic particles coated with antioxidants) are attached to 10 μm copper powder Able to know.

As shown in Fig. 3, in Comparative Example 1 containing 3.00 mass% of iron oxide (Fe ₂ O ₃ ) particles (antioxidant coated magnetic particles) coated with cerium oxide (CeO ₂ ) having a diameter of 50 nm, RTI ID = 0.0 > emu / g. ≪ / RTI > In Examples 2 and 4, the magnetic susceptibility of the solder is higher than that of Comparative Examples 2 and 4. The magnetic susceptibility of the multi-nano / micro solder prepared in Comparative Example 4 containing 1.22 mass% of iron oxide (Fe ₂ O ₃ ) coated with cerium oxide (CeO ₂ ) having a diameter of 50 nm (antioxidant coated magnetic particles) emu / g. As a result, the magnetic susceptibility increases with the content of the magnetic nanoparticles coated with antioxidants in the multi-nano / micro solder.

As shown in Fig. 4, the oxygen saturation of the multi-type nano / micro solder prepared in Comparative Example 1, which does not contain the copper powder having a diameter of 10 mu m, is 0.4012 mass%. The oxygen saturation of the multi-type nano / micro solder prepared in Comparative Example 4 containing 59.27% by mass of copper powder having a diameter of 10 μm is 0.4325% by mass. As a result, the oxygen saturation increases as the content of copper powder with a diameter of 10 μm increases in multi-nano / micro solder.

As shown in Fig. 5, the electrical resistivity of the multi-type nano / micro solder prepared in Comparative Example 1 containing no copper powder of 10 mu m in diameter was found to be 12.92 mu OMEGA cm. The electric resistivity of the multi-type nano / micro solder prepared in Comparative Example 4 containing 59.27 mass% of copper powder having a diameter of 10 占 퐉 is 22.67 占 ㎝ m. As a result, the electrical resistivity increases as the content of copper powder with a diameter of 10 μm increases in a multi-nano / micro solder.

6 shows a scanning electron microscope image of the multi-type nano / micro solder prepared in Comparative Example 1 containing no copper powder. It can be seen that the mixture of iron oxide (Fe ₂ O ₃ ) coated with cerium oxide (CeO ₂ ) having a diameter of 50 nm (magnetic particle coated with antioxidant) and tin-zinc solder particles having a diameter of 200 nm are mixed.

Fig. 7 shows a scanning electron microscope image of a multi-type nano / micro solder prepared in Comparative Example 4 containing 59.27 mass% of a copper powder having a diameter of 10 占 퐉. The tin-zinc solder particles with a diameter of 200 nm and the iron oxide (Fe ₂ O ₃ ) coated with 50 nm diameter cerium oxide (CeO ₂ ) (magnetic particles coated with antioxidants) are attached to 10 μm copper powder Able to know.

≪ Experimental Example 2 > A comparison of Examples 6 to 10 and Comparative Examples 1 and 5 to 7

The magnetic susceptibility of the multi-type nano / micro solder manufactured in Examples 7 and 9 and Comparative Examples 1, 5, and 7 to the external magnetic field was measured with a vibration sample susceptibility meter, and the results are shown in FIG. The oxygen saturation of the multi-type nano / micro solder prepared in Examples 6 to 10 and Comparative Examples 1 and 5 to 7 was measured with an oxygen analyzer. The results are shown in FIG. 9, and the electrical resistivity was measured by a sheet resistance meter After measurement, the results are shown in Fig.

The multi-type nano / micro solder prepared in Comparative Example 7 was observed with a scanning electron microscope, and the results are shown in Fig.

As shown in Table 2, the content of other constituents (magnetic particles coated with 200 nm of solder particles and 50 nm of antioxidants) decreases as the content of iron powder of 10 μm in diameter increases in many nano / micro solders.

As shown in Fig. 8, in Comparative Example 1 containing 3.00 mass% of iron oxide particles coated with cerium oxide having a diameter of 50 nm (antioxidant coated magnetic particles), the magnetic susceptibility is about 0.9 emu / g. In Examples 7 and 9, the susceptibility of the solder is lower than that of Comparative Examples 5 and 7. [ The magnetic susceptibility of the multi-nano / micro solder prepared in Comparative Example 7 containing 1.22 mass% of iron oxide coated with cerium oxide of 50 nm in diameter (antioxidant coated magnetic particles) and containing 10.2 μm of iron in an amount of 59.27 mass% Gt; 100 < / RTI > emu / g. From this, it can be seen that the content of iron has the greatest influence on the susceptibility of the nano / micro solder, and the magnetization rate increases with the content of iron.

As shown in Fig. 9, the oxygen saturation of the multi-type nano / micro solder prepared in Comparative Example 1 which does not contain the iron powder of 10 mu m in diameter is 0.4012 mass%. The oxygen saturation of the multi-type nano / micro solder prepared in Comparative Example 7 containing 59.27 mass% of iron powder having a diameter of 10 占 퐉 was 0.45 mass%. It can be seen that the oxygen saturation increases as the iron content of 10 μm diameter increases in multi-nano / micro solder.

As shown in Fig. 10, the electrical resistivity of the multi-type nano / micro solder prepared in Comparative Example 1 containing no iron powder of 10 mu m in diameter was found to be 12.92 mu OMEGA cm. The electric resistivity of the multi-type nano / micro solder prepared in Comparative Example 7 containing 59.27% by mass of iron powder having a diameter of 10 μm is 35 μΩcm. As a result, the electrical resistivity increases as the content of iron powder with a diameter of 10 μm increases in a multi-nano / micro solder.

11 shows a scanning electron microscope image of a multi-type nano / micro solder prepared in Comparative Example 7 containing 59.27 mass% of iron powder having a diameter of 10 占 퐉. A tin-zinc solder particle with a diameter of 200 nm and iron oxide (Fe ₂ O ₃ ) coated with 50 nm diameter cerium oxide (CeO ₂ ) (magnetic particle coated with antioxidant) Able to know.

≪ Experimental Example 3 > A comparison of Examples 11 to 15 and Comparative Examples 1 and 8 to 10

The magnetic susceptibility of the multi-type nano / micro solder manufactured in Examples 12 and 14 and Comparative Examples 1, 8, and 10 to the external magnetic field was measured with a vibration sample susceptibility meter, and the results are shown in FIG. The oxygen saturation of the multi-type nano / micro solder manufactured in Examples 11 to 15 and Comparative Examples 1 and 8 to 10 was measured with an oxygen analyzer. The results are shown in FIG. 13, and the electric resistivity was measured by a sheet resistance meter After measurement, the results are shown in Fig.

The multi-type nano / micro solder prepared in Comparative Example 10 was observed with a scanning electron microscope, and the results are shown in Fig.

As shown in Table 2, the content of other constituents (200 nm solder particles and 50 nm antioxidant-coated magnetic particles) decreases as the copper powder content of 1 μm in diameter increases in many nano / micro solders.

As shown in Fig. 12, in Comparative Example 1 containing 3.00 mass% of iron oxide particles coated with cerium oxide having a diameter of 50 nm (antioxidant coated magnetic particles), the magnetic susceptibility is about 0.9 emu / g. In Examples 12 and 14, the magnetic susceptibility of the solder is higher than that of Comparative Examples 8 and 10. The magnetic susceptibility of the multi-nano / micro solder prepared in Comparative Example 10 containing 1.22 mass% of iron oxide (antioxidant-coated magnetic particles) coated with 50 nm diameter cerium oxide was found to be as low as about 0.4 emu / g.

As a result, the magnetic susceptibility increases with the content of the magnetic nanoparticles coated with antioxidants in the multi-nano / micro solder.

As shown in Fig. 13, the degree of oxygen saturation of the multi-type nano / micro solder prepared in Comparative Example 1 which does not contain the copper powder having a diameter of 1 占 퐉 is 0.4012 mass%. The oxygen saturation of the multi-type nano / micro solder prepared in Comparative Example 10 containing 59.27 mass% copper powder having a diameter of 10 占 퐉 was found to be 0.45 mass%. It can be seen that the oxygen saturation increases as the content of copper powder of 1 μm diameter increases in multi-nano / micro solder.

As shown in Fig. 14, the electrical resistivity of the multi-type nano / micro solder prepared in Comparative Example 1 containing no copper powder of 1 mu m in diameter was found to be 12.92 mu OMEGA cm. The electric resistivity of the multi-type nano / micro solder prepared in Comparative Example 10 containing 59.27 mass% of copper powder having a diameter of 1 占 퐉 is represented by 21 占 cm. As a result, the electrical resistivity increases as the content of copper powder with a diameter of 1 μm increases in a multi-nano / micro solder.

Fig. 15 shows a scanning electron microscope image of a multi-type nano / micro solder prepared in Comparative Example 10 containing 59.27 mass% of a copper powder having a diameter of 1 占 퐉. A tin-zinc solder particle with a diameter of 200 nm and ferric oxide (Fe ₂ O ₃ ) coated with 50 nm diameter cerium oxide (CeO ₂ ) (magnetic particle coated with antioxidant) are attached to 1 μm copper powder Able to know.

Claims (17)

It is a multi-species nano / micro solder containing magnetic particles coated with antioxidants, supports and solder particles,
The support may be selected from the group consisting of tin, copper, aluminum, gold, silver, zinc, tungsten, lead, bismuth, indium, nickel, iron, antimony, manganese, titanium, silicon, magnesium, chromium, oxides, nitrides, sulfides, And at least one selected from the group consisting of cargoes,
Wherein the multi-type nano / micro solder comprises 0.1 to 30 mass% of a support.
The method according to claim 1,
The magnetic particles coated with the antioxidant have a particle size of 10 to 100 nm,
The support has a thickness of 0.1 to 50 탆,
Wherein the solder particles have a diameter of 100 to 500 nm.
The method according to claim 1,
Wherein the magnetic particles are at least one selected from the group consisting of vanadium, tungsten, nickel, iron, cobalt, titanium, silicon, chromium, rare earths, oxides, nitrides, sulfides, phosphides and halides thereof. Micro solder.
The method according to claim 1,
The antioxidant is at least one selected from the group consisting of aluminum, gold, silver, zinc, indium, nickel, antimony, manganese, titanium, chromium, rare earths, oxides thereof, nitrides, sulfides, phosphides and halides Many nano / micro solders.
The method according to claim 1,
Wherein the solder particles are at least one selected from the group consisting of tin, copper, gold, silver, zinc, tungsten, lead, bismuth, indium, antimony and manganese.
The method according to claim 1,
Wherein the multi-type nano / micro solder comprises 0.1 to 5 mass% of an antioxidant.
The method according to claim 1,
Wherein the multi-type nano / micro solder comprises 0.1 to 5 mass% of magnetic particles.
The method according to claim 1,
Wherein the multi-type nano / micro solder comprises 0.1 to 97 mass% of solder particles.
The method according to claim 1,
Wherein the support has a form in which magnetic particles coated with solder particles and an antioxidant are adhered.
The multi-nano / micro solder according to claim 1,
Wherein the nano / micro solder has both magnetic properties and antioxidative properties.
Preparing antioxidant-coated magnetic particles, support particles and solder particles (step 1); And
And a step (step 2) of preparing the solder by mixing the antioxidant-coated magnetic particles, the support particles and the solder particles prepared in the step 1) (step 2).
12. The method of claim 11,
The production of the particles of the step 1 is carried out using at least one process selected from the group consisting of an atomization process, a centrifugal classification process, a plasma nano-fabrication process, an electric explosion process, and a chemical synthesis process. A method of manufacturing a solder.
12. The method of claim 11,
Wherein the manufacturing of the solder in the step 2 is performed using at least one process selected from the group consisting of a mixing process and a ball milling process.
12. The method of claim 11,
Wherein the production of the magnetic particles coated with the antioxidant of step 1 is performed by using an electric explosion process and a chemical synthesis process.
12. The method of claim 11,
Wherein the production of the support particles in the step 1 is carried out using an atomization process and a centrifugal classification process.
12. The method of claim 11,
Wherein the production of the solder particles in step 1 is performed using an atomization process and a plasma nano-process.
A method for sintering multiple nano / micro solders according to claim 1, wherein the multi-nano / micro solder is sintered at a temperature of 50 to 1000 占 폚 for 1 second to 6 hours by induction heating.

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