KR102116223B1 - Metal/two-dimensional nanomaterial hybrid heating element and manufacturing method the same - Google Patents

Abstract

The present invention, a metal / two-dimensional nano-material hybrid heat sink and a method for manufacturing the same, the substrate; It is formed on the upper portion of the substrate, the technical core to include a hybrid particle layer made of a metal (core) and the outer wall of the metal in a shell (shell) two-dimensional nano-material. As a result, a two-dimensional nanomaterial having excellent thermal conductivity is synthesized on the outer wall of a non-precious metal-based metal having a high oxidation property, thereby preventing metal from being oxidized from air and at the same time increasing the thermal conductivity. In addition, rapid atmospheric firing is possible by a two-dimensional nanomaterial having excellent high energy light absorption such as microwave, and rapid firing can minimize metal oxidation and shorten the processing time.

Description

Metal / two-dimensional nanomaterial hybrid heating element and manufacturing method the same}

The present invention relates to a metal / two-dimensional nanomaterial hybrid radiator and a method for manufacturing the same, and more specifically, to synthesize a two-dimensional nanomaterial having excellent thermal conductivity on the outer wall of a non-precious metal-based metal having high oxidation property, and thus metal from air It relates to a metal / two-dimensional nano-material hybrid heat sink that can prevent the oxidation and increase the thermal conductivity at the same time and a method for manufacturing the same.

Nanoparticles, unlike the properties of bulk and atomic species, have unique physical properties, whereby recent research on nanomaterials is rapidly increasing worldwide. Due to these unique physical properties, application possibilities are emerging in many fields such as electrochemistry, microelectronics, optics, and biotechnology, and in particular, in the electronics field, various substrates are applied to manufacture electronic components. Nanomaterials are required to form fine interconnections in thin films through a printing method. As a method of printing a pattern on a substrate, lithography is generally used, but since it is performed through a complicated process, there is a problem in that the process cost increases. Therefore, there is an urgent need for an ink capable of printing a circuit directly on a film without going through a complicated process.

In addition, in the electronic field, not only the formation of fine wiring, but also the miniaturization of electrical and electronic components, the high power, and the integration of electronic components make the thermal integration phenomenon more severe, thereby preventing functional failure of electronic components due to thermal integration. To this end, interest in high heat dissipation materials is increasing. In particular, in semiconductor fields such as power transistors, thermistors, printed wiring boards, and IC chips, and other electrical and electronic components, heat-radiating materials containing epoxy resins and inorganic fillers are materials that constitute the radiators. It is widely adopted. Such a heat dissipation material requires excellent strength and thermal conductivity.

Conventionally, the heat problem generated by the electronic component has been solved through a heat dissipation film manufactured using a heat dissipation material composition using a composition for a heat dissipation material including alumina or silica, and a thermally conductive filler. As the depth increases, there is a need to develop a composition for a high heat dissipation material, which further improves heat dissipation properties than a composition for a conventional heat dissipation material. In addition, since the cost of the insulating ceramic (ceramic) particles, which are mainly used as heat dissipation particles in the related art, is high, it is urgently required to develop inexpensive and high heat dissipation particles and heat dissipation bodies produced therefrom.

Therefore, in recent years, precious metal-based metals such as silver (Ag), gold (Au), and platinum (Pt), which can form fine wiring, have high thermal conductivity, and have low oxidation properties, are recognized as materials that can be directly applied to the printing process. It has been. However, due to the high price and ion migration, precious metal-based metals are not easy to fabricate. To overcome this problem, non-precious metals such as copper (Cu), nickel (Ni), and aluminum (Al), which have similar thermal conductivity to precious metals, are used. It has the advantage of being possible and having good economics. Nevertheless, the problem that the process cost increases due to the high oxidation property is acting as a major obstacle to commercialization, and when using only metal, there is a limit to improving the thermal conductivity.

Korea Patent Office Registration Patent No. 10-1303229 Korea Patent Office Registration Patent No. 10-1525487 Republic of Korea Patent Office Publication No. 10-2014-074289

Accordingly, an object of the present invention is to synthesize a two-dimensional nanomaterial having excellent thermal conductivity on the outer wall of a non-precious metal-based metal having high oxidation property, to prevent metal from being oxidized from air, and at the same time to increase the thermal conductivity / It is to provide a two-dimensional nano-material hybrid heat sink and a method for manufacturing the same.

In addition, the rapid air firing is possible by the two-dimensional nano-materials that have excellent high energy light absorption such as microwaves, and the metal / two-dimensional nano-material hybrid heat radiator that minimizes the oxidation of metals and shortens the process time by the rapid firing and its manufacturing method Is to provide.

The above object is a substrate; A metal / two-dimensional nanomaterial hybrid heat sink comprising a hybrid particle layer formed on the substrate and comprising a core metal and a two-dimensional nanomaterial surrounding the outer wall of the metal in a shell form. Is achieved by.

Here, the hybrid particle layer is made through rapid atmospheric firing to irradiate high energy light to the hybrid particle layer in the atmosphere, and the two-dimensional nanomaterial absorbs the light and generates heat, and is preferably made of a material having excellent thermal conductivity. .

In addition, the two-dimensional nanomaterial is selected from the group consisting of graphene, hexagonal boron nitride (h-boron nitride), a transition metal chalcogen compound, and a mixture thereof having excellent thermal conductivity, the transition metal chalcogen The compound is represented by MX ₂ and M is titanium (Ti), vanadium (V), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), hafnium (Hf), tantalum ( Ta), tungsten (W), is composed of one of rhenium (Re), X is preferably composed of one of sulfur (S), selenium (Se), tellurium (Te).

The catalyst metal is a non-precious metal-based copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), chromium (Cr), tungsten (W), platinum (Pt), palladium (Pd), aluminum It is preferably selected from the group consisting of (Al) and mixtures thereof.

Here, the hybrid particle layer is formed by synthesizing the two-dimensional nanomaterial on the outer wall of the catalyst metal and oxidizing the catalyst metal by using a mixture of a catalyst metal dispersed in the precursor or precursor compound of the two-dimensional nanomaterial, It is preferred that the mixture is formed by synthesizing the two-dimensional nanomaterial on the outer wall of the catalytic metal by decomposing the precursor compound using energy generated when collapsing the microbubbles by irradiating ultrasonic waves to the mixed solution.

The above object is also a step of forming a mixed liquid in which a catalyst metal is dispersed in a precursor or precursor compound of a two-dimensional nanomaterial, and generating ultrasonic bubbles in the mixed liquid to generate micro bubbles and energy generated when the micro bubbles collapse. In the method of manufacturing a heat sink comprising the step of decomposing the precursor compound to synthesize the two-dimensional nanomaterial on the outer wall of the catalyst metal to form a catalyst metal / two-dimensional nanomaterial, the catalyst metal / two-dimensional nanomaterial dispersion liquid Dispersing in to prepare a thermally conductive ink; It is also achieved by a method for manufacturing a metal / two-dimensional nanomaterial hybrid heat sink for preventing metal oxidation, comprising applying the thermally conductive ink to a substrate and rapidly sintering it.

Here, the step of rapidly firing the air is made by irradiating high energy light to the substrate in the atmosphere, and it is preferable that the light is irradiated to the substrate for 0.1 to 50 milliseconds (ms).

In addition, the step of applying the thermally conductive ink to the substrate and rapid air firing may be performed through a coating, patterning, extruding, blasting, spreading, or printing method. It is made, it is preferable that the ultrasound is generated by the power of 100 to 300W.

According to the above-described configuration of the present invention, by synthesizing a two-dimensional nanomaterial having excellent thermal conductivity on the outer wall of a non-precious metal-based metal having a high oxidation property, it prevents the metal from being oxidized from air and increases the thermal conductivity. Can be obtained.

In addition, rapid atmospheric firing is possible by a two-dimensional nanomaterial having excellent high energy light absorption such as microwave, and rapid firing can minimize the oxidation of metal and shorten the processing time.

1 and 2 is a flow chart of a metal / two-dimensional nano-material hybrid heat sink manufacturing method according to an embodiment of the present invention,
Figure 3 is a scanning microscopy (SEM) picture of Examples and Comparative Examples after rapid atmospheric firing,
4 is an X-ray diffraction spectrum showing the surface oxidation state of Examples and Comparative Examples after rapid atmospheric firing,
5 and 6 are graphs showing thermal conductivity according to temperatures of Examples and Comparative Examples under air and argon atmospheres.

Hereinafter, a metal / two-dimensional nanomaterial hybrid heat sink according to an embodiment of the present invention and a method of manufacturing the same will be described with reference to the drawings.

The metal / two-dimensional nanomaterial hybrid radiator includes a hybrid particle layer formed of a substrate, a metal that is a core, and a two-dimensional nanomaterial that surrounds an outer wall of the metal in a shell form. Here, the metal / two-dimensional nanomaterial refers to a hybrid-shaped material composed of a shape in which a metal is disposed on a core and a two-dimensional nanomaterial surrounds a core metal.

 1 and 2, first, the heat dissipation body forms a mixed solution 10 in which a catalyst metal 13 is dispersed in a precursor or precursor compound 11 of a two-dimensional nanomaterial (S1).

The catalyst metal 13 dispersed in the mixed solution 10 adsorbs atoms constituting the two-dimensional nanomaterial 15 that becomes a shell structure, and serves as a template for the synthesis of the two-dimensional nanomaterial 15. Therefore, the yield, crystallinity, and number of layers of the two-dimensional nanomaterial 15 synthesized according to the purity and type of the catalytic metal 13 are changed. The higher the purity of the catalyst metal 13 is, the easier the adsorption of the two-dimensional nanomaterial 15 surrounding the catalyst metal 13 is. (13) may further include a step of purifying and reducing.

Here, the catalytic metal 13 serving as a core structure refers to a non-precious metal-based metal having excellent thermal conductivity and oxidizing well in the atmosphere, and copper (Cu), nickel (Ni), aluminum (Al), cobalt (Co), iron ( Fe), chromium (Cr), tungsten (W), palladium (Pd) and alloys containing the same, or may be at least one selected from the group consisting of organometallic compounds such as metallocene.

The precursor compound 11 of the two-dimensional nanomaterial 15 refers to a precursor synthesized from the two-dimensional nanomaterial 15, and the shell is surrounded by the two-dimensional nanomaterial 15 around the catalyst metal 13 as a core. (shell) is synthesized to form. The synthesized two-dimensional nanomaterial 15 is synthesized by any one of the group consisting of graphene, hexagonal boron nitride, transition metal chalcogen compound, and mixtures thereof having excellent thermal conductivity. Here, the transition metal chalcogenide compound is represented by MX ₂ , where M is titanium (Ti), vanadium (V), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), hafnium ( Hf), tantalum (Ta), tungsten (W), consisting of one of rhenium (Re), X has a structure composed of one of sulfur (S), selenium (Se), tellurium (Te).

The precursor compound 11 of the two-dimensional nanomaterial 15 refers to each precursor compound capable of synthesizing graphene, hexagonal boron nitride, and transition metal chalcogen compounds having high thermal conductivity.

Here, the precursor compound 11 for graphene synthesis is a compound containing carbon, acetic acid, acetone, acetyl acetone, anisole, benzene, and benzyl alcohol (benzyl alcohol), butanol, butanone, chlorobenzene, chloroform, cyclohexane, cyclohexanol, cyclohexanone, butylphthalate (butyl phthalate), dichloroethane, diethylene glycol, diglyme, dimethoxyethane, dimethyl phthalate, dioxane, ethanol, ethanol, Ethyl Acetate, Ethyl Acetoacetate, Ethyl Benzonate, Ethylene Glycol, Glycerin, Heptane, Heptanol, Hexane , Hexanol, methanol, methyl acetate, methylene chloride, octanol, pentane, pentanol, pentanone, tetra It is preferred to be selected from the group consisting of an organic solvent such as tetrahydrofuran, toluene, xylene, a solvent in which an organic monomer or polymer is dissolved, and a mixture thereof, but is not limited thereto.

The precursor compound 11 for synthesizing hexagonal boron nitride is selected from the group consisting of borazine, ammonia borane and mixtures thereof.

In addition, the precursor compound 11 for synthesizing the transition metal chalcogen compound is ammonium tetrathiomolybdate ((NH ₄ ) ₂ MoS ₄ ), molybdenum chloride (MoCl ₅ ), molybdenum oxide (MoO ₃ ), Tungsten oxytetrachloride (WOCl ₄ ), 1,2-ethanedithiol (Hs (CH ₂ ) ₂ SH), diterbutyl selenide (C ₈ H ₁₈ Se), diethyl selenide (C ₄ H ₁₀ Se ), Vanadium tetrakisdimethylamide (V (NMe ₂ ) ₄ ), tetrakisdimethylamidotitanium (Ti (NMe ₂ ) ₄ ), 2-methylpropanethiol (Bu ^t SH), tertbutyldisulfide (Bu ₂ ^t S ₂ ) and mixtures thereof.

The interior of the solution is controlled by an inert gas atmosphere by bubbling helium (He) or argon (Ar) gas into the mixed solution 10 formed through the above method and materials. When an active gas is present in the mixed solution 10, an unwanted material may be synthesized during ultrasonic irradiation in a subsequent step or a part of the catalyst metal 13 may be oxidized. Helium or argon inert gas is bubbled to remove all gas.

The mixed solution 10 is irradiated with ultrasonic waves to synthesize a catalytic metal 13 / two-dimensional nanomaterial 15 material (S2).

The catalyst metal 13 is irradiated with ultrasonic waves through the ultrasonic irradiator 30 to the mixed liquid 10 dispersed in the precursor or the precursor compound 11 to generate fine bubbles. The microbubbles gradually increase in size when continuously irradiated with ultrasonic waves, and the pressure inside the microbubbles rises and eventually collapses. The local energy generated at this time corresponds to a high temperature of 5000 ° C or higher and causes decomposition of the precursor compound 11 present around the microbubbles. The precursor compound 11, which is decomposed using energy generated when the microbubbles collapse, is adsorbed to surround the outer wall of the catalytic metal 13 serving as a catalyst to form a nucleus of the two-dimensional nanomaterial 15. In addition, through the continuous decomposition and adsorption process of the precursor compound 11, the nucleus of the two-dimensional nanomaterial 15 expands to catalyze metal 13 / two-dimensional nanomaterial 15 hybrid particles including the complete two-dimensional nanomaterial 15 Is synthesized. The catalyst metal 13 / two-dimensional nanomaterial 15 has a nano-sized catalyst metal 13 in the central region, and a core / shell structure in which the two-dimensional nanomaterial 15 is synthesized on the outer wall of the catalyst metal 13 Is made of Here, the ultrasonic irradiator 30 used to generate ultrasonic waves uses power of 100 to 200 W, and is preferably used within a range of 10 seconds to 6 hours.

The catalytic metal 13 / two-dimensional nanomaterial 15 hybrid particles obtained through the above method is surrounded by a non-noble metal-based metal, the two-dimensional nanomaterial 15 surrounds the catalytic metal 13 in the atmosphere. ) Is prevented from being oxidized. Therefore, even through a rapid atmospheric firing process using this, since the properties of the catalyst metal 13 are not changed, the thermal conductivity of the catalyst metal 13 is maintained, and the two-dimensional nanomaterial 15 having excellent thermal conductivity is also included. Therefore, it is possible to obtain much better thermal conductivity than when only the catalyst metal 13 is used.

In some cases, after synthesizing the catalyst metal 13 / two-dimensional nanomaterial 15, the method may further include separating the catalyst metal 13 / two-dimensional nanomaterial 15 from the mixed solution 10. If there is a residual catalyst metal 13 or a residual precursor compound 11 remaining unsynthesized in the mixed solution 10, these can be removed to obtain a pure catalyst metal 13 / two-dimensional nanomaterial 15. In this case, the catalyst metal 13 / two-dimensional nanomaterial 15 is filtered, and then the pure catalyst metal 13 / two-dimensional nanomaterial 15 is obtained through the washing step so that no residue remains.

The catalyst metal 13 / two-dimensional nanomaterial 15 is dispersed in the dispersion 51 to prepare a thermally conductive ink 50 (S3).

The thermally conductive ink 50 is prepared by dispersing the catalytic metal 13 / two-dimensional nanomaterial 15 obtained purely in the dispersion liquid 51. Here, the catalytic metal 13 / two-dimensional nanomaterial 15 is preferably included in 40 to 80 parts by weight of the total 100 parts by weight of the thermally conductive ink (50). When the amount is less than 40 parts by weight, the amount of the catalyst metal 13 / two-dimensional nanomaterial 15 is insufficient, and the thermal conductivity is significantly reduced. When it exceeds 80 parts by weight, the dispersibility of the catalyst metal 13 / two-dimensional nanomaterial 15 There is a disadvantage that the coating performance is reduced due to the fall and the viscosity increase.

The dispersion liquid 51 usually uses a solvent used in the coating ink composition, and it is preferable to use a polar or non-polar solvent having a boiling point of 150 to 300 ° C. The dispersion 51 is at least one of terpineol, etht cellosolve, butyl cellosolve, carbitol, butyl carbitol, and glycerol. Includes.

In the step of manufacturing the thermally conductive ink 50, an ink binder is additionally added to increase the viscosity and adhesiveness of the thermally conductive ink 50. Specifically, the binder is an organic and inorganic material, and cellulose-based resins such as methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cellulose cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, etc., polyurethane-based resins And an acrylic resin or a silane coupling agent. Here, the silane coupling agent includes vinyl alkoxy silane, epoxy alkyl alkoxy silane, methacryloxy alkyl alkoxy silane, mercapto alkyl alkoxy silane, amino alkyl alkoxy silane, and the like.

Such a binder resin may include 0.5 to 5 parts by weight out of 100 parts by weight of the thermal conductive ink 50, and when added less than 0.5 parts by weight, the amount added is small, so that viscosity and adhesiveness are not significantly improved, 5 When it exceeds the weight part, a phenomenon in which the thermal conductivity is significantly reduced occurs.

The heat conductive ink 50 is applied to the substrate 70 to form a heat sink (S4).

The thermally conductive ink 50 is formed on the substrate 70 in the form of a thin film by using the thermal conductive ink 50 including the catalytic metal 13 / the two-dimensional nanomaterial 15. Here, the substrate 70 is a plastic substrate having a low absorption rate of light energy, and the plastic substrate is polyethylene terephtalate, polyethylene naphthalate, polycarbonate, polyimide, and the like. It is preferably selected from the group consisting of mixing.

When the thermally conductive ink 50 is applied to the substrate 70, the thermally conductive ink 50 may be applied to the entirety of the substrate 70, such as an electrode pattern, and thermally conductive through patterning on a portion of the substrate 70 The ink 50 may also be applied. As a method of applying the thermal conductive ink 50 to the substrate 70 as described above, coating, patterning, extrusion, blasting, spread, printing, etc. Processing methods can be used.

The heat radiator is irradiated with light 90 in the air to rapidly fire the radiator (S5).

The electrode pattern is printed or the substrate 90 is irradiated with light 90 on the heat dissipating body to which ink is applied on the front surface to rapidly fire air at high temperatures. When the light 90 is irradiated to the radiator, the catalytic metal 13 / two-dimensional nanomaterial 15 hybrid particles, the two-dimensional nanomaterial 15 absorbs the light 90 and is instantaneously heated to high temperature. As such, when the catalyst metal 13 / the two-dimensional nanomaterial 15 is heated, heat is conducted to the surroundings, and the radiator is fired at a high temperature. At this time, the catalytic metal 13, which is a non-metallic metal, does not come into contact with air by the two-dimensional nanomaterial 15 surrounding the outer wall, thereby preventing oxidation in the firing process. Since the two-dimensional nanomaterial 15 is wrapped on the surface of the catalytic metal 13, it is also possible to use a general heat firing method in the atmosphere without using a photo-firing method in some cases.

When firing the radiator using high-energy light 90, the time for irradiating the light 90 is irradiated within a short time, such as 0.1 to 50 milliseconds. 13) / The two-dimensional nanomaterial 15 is instantaneously heated at high temperature, but the substrate 70 is fired before the temperature rises to prevent deformation of the substrate 70. When the time for irradiating the light 90 is less than 0.1 milliseconds, it is difficult to achieve perfect firing, and when it exceeds 50 milliseconds, oxidation of the catalytic metal 13 occurs and the heating temperature is excessively high, resulting in a radiator. There is a risk of damage.

Here, ultraviolet rays (ultraviolet ray), visible rays (visible ray), infrared rays (infrared ray), microwaves, and the like can be used, and the catalyst metal (13) / refers to electromagnetic waves with high absorption rate in two-dimensional nanomaterials (15) do.

Hereinafter, preferred embodiments of the present invention will be described in more detail.

<Example 1>

1-1. Copper / graphene hybrid thermal conductive ink manufacturing

5 g of copper particle powder from which the surface oxide film has been removed is added to 250 ml of xylene, and graphene is synthesized on the surface of copper particles using ultrasonic chemistry to form a hybrid core / shell structure composed of copper / graphene. To form. Then, after removing the remaining xylene through filtration and washing, a thermally conductive ink is prepared by dispersing copper / graphene particles in dimethylformamide (DMF). In addition, ethyl cellulose and terpineol are added and stirred to obtain a high-viscosity ink.

1-2. Copper / graphene hybrid radiator manufacturing

A copper / graphene hybrid heat sink was prepared by printing the thermally conductive ink prepared through steps 1-1 on top of a polyimide insulating film substrate having a width of 2 × 2 cm 2 using screen printing. Then, the substrate coated with the thermally conductive ink is dried in a heating furnace at 150 ° C.

1-3. Copper / graphene hybrid radiator firing

The substrate included in the copper / graph hybrid heat sink prepared in step 1-2 is irradiated with microwave of 1.8 kW for 10 ms to fire the heat sink.

<Example 2>

2-1. Nickel / graphene hybrid thermal conductive ink production

5 g of nickel particle powder from which the surface oxide film has been removed is added to 500 ml of xylene, and graphene is synthesized on the surface of the nickel particle using ultrasonic chemistry to form a hybrid particle of core / shell structure composed of nickel / graphene. . After removing residual xylene through filtration and washing, ink is prepared by dispersing nickel / graphene particles in dimethylformamide. In addition, ethyl cellulose and terpineol are added and stirred to obtain a high-viscosity ink.

2-2. Manufacture of nickel / graphene hybrid heat sink

After manufacturing the nickel / graphene hybrid heat sink through printing on the top of the polyimide insulating film substrate having a width of 2 × 2 cm 2 by screen printing the thermally conductive ink prepared in step 2-1, in a heating furnace at 150 ° C. The ink-coated substrate is dried.

2-3. Nickel / graphene hybrid radiator firing

The substrate included in the nickel / graphene hybrid heat sink prepared in step 2-2 is irradiated with microwave of 1.8 kW for 14 ms to fire the heat sink.

<Comparative Example 1>

3-1. Copper ink manufacturers

To remove the surface oxide film, 5 g of copper particle powder was added to 4M hydrochloric acid (HCl) and stirred for 10 minutes. After that, a filtration and washing process is performed, and ink is prepared by dispersing copper particles in dimethylformamide. In addition, ethyl cellulose and terpineol are added and stirred to obtain a high-viscosity ink.

3-2. Copper radiator manufacturing

After printing the thermally conductive ink prepared in step 3-1 on the polyimide insulating film substrate using screen printing to prepare a copper heat sink, the ink-coated substrate is dried in a heating furnace at 150 ° C.

3-3. Copper radiator firing

The substrate included in the copper radiator prepared in step 3-2 is irradiated with microwave of 1.8 kW for 5 ms to fire the radiator.

<Comparative Example 2>

4-1. Nickel ink manufacturers

To remove the surface oxide film, 5 g of nickel particle powder was added to 4M hydrochloric acid (HCl) and stirred for 10 minutes. After that, a filtration and washing process is performed, and ink is prepared by dispersing nickel particles in dimethylformamide. In addition, ethyl cellulose and terpineol are added and stirred to obtain a high-viscosity ink.

4-2. Nickel radiator manufacturing

After printing the thermally conductive ink prepared in step 4-1 on the polyimide insulating film substrate using screen printing to prepare a nickel heat sink, the ink-coated substrate is dried in a heating furnace at 150 ° C.

4-3. Nickel radiator firing

The substrate included in the nickel heat sink prepared in step 4-2 is irradiated with microwave of 1.8 kW for 5 ms to fire the heat sink.

3 is a scanning micrograph of the sample prepared through the above Examples and Comparative Examples after rapid atmospheric firing. In Example 1 (Cu / Graphene) and Example 2 (Ni / Graphene), it can be confirmed that the particles were not oxidized even after rapid air firing, but Comparative Example 1 (Cu) and Comparative Example 2 (Ni) were after rapid air firing. It can be confirmed that the surface was oxidized.

4 is an X-ray diffraction spectrum showing the surface oxidation state after rapid air firing on the samples prepared through Example 1 and Comparative Example 1. As can be seen in the spectrum, in the case of Example 1 in which the graphene, which is a two-dimensional nanomaterial, was synthesized on the outer surface, the peak of copper oxide (CuO ₂ ) was not observed, but when the copper-only particles were rapidly air-fired, it was confirmed that the peak of copper oxide appeared Can be.

5 and 6 are graphs showing the thermal diffusivity according to the temperature of samples prepared through Example 1 (Copper / Graphene) and Comparative Example 1 (Copper). 5 is a graph measuring the thermal diffusivity in an air atmosphere, and FIG. 6 is a graph measuring the thermal diffusivity in an argon (Ar) atmosphere. As described above, it can be confirmed that the heat spreader manufactured using the particles having graphene accumulated around the copper has higher thermal diffusivity than the heat radiator manufactured using only copper particles regardless of the gas atmosphere. This shows that the copper present inside the graphene is not oxidized, so that not only the original thermal conductivity of copper is maintained, but graphene with high thermal conductivity is enclosed outside, and thus exhibits a much higher thermal conductivity than the heat sink of Comparative Example 1.

Conventionally, in order to prevent the metal from being oxidized during the firing process and losing thermal conductivity, a heat radiator was manufactured by firing under an inert gas atmosphere or a vacuum atmosphere, or by forming a protective film on the top of the metal and then firing. The disadvantage of using this method is that the manufacturing process is difficult and the manufacturing cost increases. However, in the case of the present invention, a two-dimensional nanomaterial is synthesized on the outer wall of a metal, coated on a substrate, and then rapidly radiated using a high-energy light to obtain a radiator, and the two-dimensional nanomaterial is present on the outer wall of the metal. The metal oxidation is prevented even if the calcination is not performed under an inert gas atmosphere or a vacuum atmosphere and proceeds in the atmosphere. In addition, since two-dimensional nanomaterials with excellent thermal conductivity are included together, there is an advantage in that the thermal conductivity increases compared to using only metal.

10: mixed solution 11: precursor compound
13: catalytic metal 15: two-dimensional nanomaterial
30: ultrasonic irradiator 50: thermally conductive ink
51: dispersion 70: substrate
90: light

Claims (13)

Board; And
It is formed on the upper portion of the substrate, the core (core) of the metal and the outer wall of the metal in a shell (shell) hybrid particle layer made of a two-dimensional nanomaterial; includes,
The hybrid particle layer is a metal / two-dimensional nanomaterial hybrid heat dissipator, characterized in that the hybrid particle layer is made through rapid atmospheric firing of irradiating high energy light to the hybrid particle layer in the atmosphere. delete According to claim 1,
The two-dimensional nano-material absorbs the light and generates heat, and a metal / two-dimensional nano-material hybrid radiator, characterized in that it is made of a material having excellent thermal conductivity. According to claim 1,
The two-dimensional nano-material, metal / two-dimensional nano, characterized in that it is selected from the group consisting of graphene (graphene), hexagonal boron nitride (h-boron nitride), a transition metal chalcogen compound and a mixture thereof excellent in thermal conductivity Material hybrid heat sink. The method of claim 4,
The transition metal chalcogenide compound is represented by MX ₂ and M is titanium (Ti), vanadium (V), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), hafnium (Hf) ), Consisting of one of tantalum (Ta), tungsten (W), and rhenium (Re), and X having a structure composed of one of sulfur (S), selenium (Se), and tellurium (Te). Metal / two-dimensional nanomaterial hybrid radiator. According to claim 1,
The hybrid particle layer,
A metal / two-dimensional nanomaterial characterized by being formed by synthesizing the two-dimensional nanomaterial on the outer wall of the catalyst metal and oxidizing the catalyst metal using a mixed solution in which a catalyst metal is dispersed in the precursor or precursor compound of the two-dimensional nanomaterial. Hybrid heat sink. The method of claim 6,
The catalyst metal is a non-precious metal-based copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), chromium (Cr), tungsten (W), platinum (Pt), palladium (Pd), aluminum A metal / two-dimensional nano-material hybrid heat sink, characterized in that selected from the group consisting of (Al) and a mixture thereof. The method of claim 6,
The hybrid particle layer,
A metal characterized by being formed by synthesizing the two-dimensional nanomaterial on the outer wall of the catalyst metal by decomposing the precursor compound using energy generated when collapsing the microbubbles by irradiating ultrasonic waves to the mixed solution. / Two-dimensional nanomaterial hybrid radiator. Forming a mixed solution in which a catalyst metal is dispersed in a precursor or precursor compound of a two-dimensional nanomaterial, and irradiating ultrasonic waves to the mixed solution to generate micro bubbles and using the energy generated when the micro bubbles collapse. In the method of manufacturing a heat sink comprising the step of decomposing to synthesize the two-dimensional nanomaterial on the outer wall of the catalyst metal to form a catalyst metal / two-dimensional nanomaterial,
Dispersing the catalyst metal / two-dimensional nanomaterial in a dispersion to prepare a thermal conductive ink; And
Including the step of applying the thermally conductive ink to the substrate and rapid air sintering (sintering);
The rapid air firing step,
A method for manufacturing a metal / two-dimensional nanomaterial hybrid heat sink for preventing metal oxidation, characterized in that the substrate is irradiated with high energy light in the air. delete The method of claim 9,
The rapid air firing step,
Method of manufacturing a metal / two-dimensional nano-material hybrid heat sink, characterized in that the light is irradiated to the substrate for 0.1 to 50 milliseconds (ms). The method of claim 9,
The step of applying the thermally conductive ink to the substrate and rapidly firing it,
A method of manufacturing a metal / two-dimensional nanomaterial hybrid heat sink, characterized in that it is made through a coating, patterning, extruding, blasting, spreading, or printing method. The method of claim 9,
The ultrasonic wave is a method of manufacturing a metal / two-dimensional nanomaterial hybrid heat sink, characterized in that generated by the power of 100 to 300W.

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