KR20170083713A - Manufacturing method of thermal conduction EMI shield paint for semiconductor with copper and nickel and graphene - Google Patents
Manufacturing method of thermal conduction EMI shield paint for semiconductor with copper and nickel and graphene Download PDFInfo
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- KR20170083713A KR20170083713A KR1020160002913A KR20160002913A KR20170083713A KR 20170083713 A KR20170083713 A KR 20170083713A KR 1020160002913 A KR1020160002913 A KR 1020160002913A KR 20160002913 A KR20160002913 A KR 20160002913A KR 20170083713 A KR20170083713 A KR 20170083713A
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Abstract
The present invention relates to a method of manufacturing a thermally conductive electromagnetic wave shielding paint for semiconductor comprising copper, nickel and graphene, and more particularly, to a method of manufacturing a thermally conductive electromagnetic wave shielding paint for semiconductor, comprising: removing an oxide film on a surface of a copper powder; A nickel coating step of coating the surface of the copper powder that has undergone the oxide film removing step with nickel to form an oxidation preventing film; And a graphene synthesis step of synthesizing graphene on the copper powder (1) having undergone the nickel coating step,
When the coating paint prepared by the present invention is coated on a heat radiating member of a semiconductor, not only the heat generated from the semiconductor device is effectively released, but also electromagnetic interference (EMI) is reduced and the lifetime of the electronic device is increased by shielding the electromagnetic wave. And the like.
Description
The present invention relates to a method of manufacturing a thermally conductive electromagnetic wave shielding coating for a semiconductor made of copper, nickel, and graphene, and more particularly, And a method of manufacturing a thermally conductive electromagnetic wave shielding paint for semiconductors.
In recent years, miniaturization of electronic products such as mobile phones and notebooks has led to a reduction in the size of semiconductor devices, and a rapid increase in the operating voltage, resulting in a large increase in semiconductor heat generation. So that a heat sink capable of replacing the heat sink is being studied.
According to a conventional semiconductor component having a heat-radiating coating layer of Patent Registration No. 10-1072293, a heat-radiating coating layer is formed by coating a surface of a semiconductor component with a heat radiating coating agent composed of an infrared radiator powder and a binder, , Silicon oxide, ceriaite, cordierite, germanium, iron oxide, mica, manganese dioxide, silicon carbide, cobalt oxide, carbon, copper oxide, cobalt oxide, nickel oxide, antimony pentoxide, chromium oxide, boron nitride, aluminum nitride and silicon nitride Wherein the organic binder is selected from the group consisting of a vinyl group, an acrylic group, an ester group, a urethane group, a urethane group, and a urethane group capable of thermopolymerizing both ends of the carbon chain or side chains of the carbon chain, An epoxy group, an amino group, an imide group and an organic functional group capable of thermosetting at least one functional group Wherein the organic polymer is one selected from the group consisting of organic polymers containing at least one functional group capable of photopolymerizable and vinyl groups, allyl groups, acryl groups, methacrylate groups and photopolymerizable groups, And a semiconductor component in which a coating layer is formed.
As another prior art, there is disclosed a semiconductor package having an electromagnetic wave shielding function, a manufacturing method thereof, and a jig according to Patent Registration No. 10-0877551, a semiconductor manufacturing step of manufacturing a semiconductor chip; Bonding the chip to the substrate; A molding step of covering the surface of the chip with a mold to produce a semiconductor package; And a sputtering step of coating a surface of the semiconductor package with a metal containing nickel by using a plasma sputtering apparatus to form an electromagnetic wave shielding film for electromagnetic waves emitted from the semiconductor package, The target is an alloy of nickel and silver or an alloy of nickel and copper, and the sputtering step is performed by sputtering for 20 to 30 minutes by injecting a reaction gas of 100 to 150 sccm into a sputtering chamber having a degree of vacuum of 2.0 to 3.0 * 10 -3 Torr And the thickness of the coated electromagnetic wave shielding film is set to 4000 to 8000 ANGSTROM.
However, the conventional heat dissipater has a disadvantage in that, when the heat generation of the electronic device exceeds a certain level, the temperature is lowered by forcibly reducing the performance of the device.
In addition, the conventional heating element has no electromagnetic wave shielding function, and noise is generated due to radio wave mutual disturbance between the heat generating, transmitting and receiving devices of the electronic device, and the lifetime of the electronic device is reduced.
SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a semiconductor device capable of effectively dissipating heat generated from semiconductor devices, reducing electromagnetic interference (EMI), shielding electromagnetic waves, And a thermally conductive electromagnetic wave shielding coating for a semiconductor made of nickel and graphene.
The present invention relates to a method of manufacturing a thermally conductive electromagnetic wave shielding coating for a semiconductor made of copper, nickel and graphene, the method comprising: an oxide film removing step of removing an oxide film on the surface of a copper powder; A nickel coating step of coating the surface of the copper powder that has undergone the oxide film removing step with nickel to form an oxidation preventing film; And a graphene synthesis step of synthesizing graphene on the copper powder that has undergone the nickel coating step.
Therefore, coating the coating paint prepared according to the present invention on a heat radiator of a semiconductor effectively dissipates heat generated from the semiconductor device, reduces electromagnetic interference (EMI), shields electromagnetic waves, And the like.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing removal of an oxide film on the surface of a copper powder according to the present invention. Fig.
FIG. 2 is a schematic view showing the formation of an oxidation preventing film on the surface of the copper powder of the present invention. FIG.
3 is a schematic diagram showing the synthesis of graphene of the present invention by graphene oxide.
4 is a schematic diagram showing the functional groups of the graphene oxide of the present invention.
5 is a schematic diagram illustrating the growth of graphene in nickel-coated copper powder of the present invention.
6 is a schematic view of a chemical vapor deposition apparatus for growing graphene on a nickel substrate.
7 is a graph showing growth conditions of the graphene of the present invention.
The present invention relates to a method for manufacturing a thermally conductive electromagnetic wave shielding paint for semiconductor comprising copper, nickel and graphene, wherein the method for producing a thermally conductive electromagnetic wave shielding paint for semiconductor comprises the steps of removing an oxide film (2) step; A nickel coating step of coating the nickel (4) on the surface of the copper powder (1) after the oxide film removing step to form the oxidation preventing film (3); And a graphene synthesis step of synthesizing graphene in the copper powder (1) through the nickel coating step.
The oxide film removing step is characterized in that the
The graphene synthesis step is characterized in that graphene is synthesized on the surface of nickel through chemical vapor deposition (CVD).
Hereinafter, a method for manufacturing a thermally conductive electromagnetic wave shielding coating for a semiconductor made of copper, nickel, and graphene will be described in detail.
FIG. 1 is a schematic diagram showing the removal of an oxide film on the surface of the copper powder according to the present invention. FIG. 2 is a schematic view showing the formation of an oxidation- Fig. 4 is a schematic view showing the functional group of the graphene oxide of the present invention. Fig.
The present invention provides a method for manufacturing a thermally conductive electromagnetic wave shielding coating for a semiconductor made of copper, nickel, and graphene.
The method for manufacturing a thermally conductive electromagnetic wave shielding paint for copper, nickel, and graphene for semiconductor includes an oxide film removing step for removing the oxide film (2) on the surface of the copper powder (1); Nickel (4) is coated on the surface of the copper powder (1) which has undergone the oxide film removing step A nickel coating step of forming an
First, the oxide film on the surface of the copper powder is removed.
The oxide film has a property of lowering the electrical and thermal characteristics of the copper powder.
The oxide film removing step removes the oxide film on the surface of the copper powder using a hydrogen chloride (HCl) aqueous solution. In the oxide film removing step, the surface of the copper powder reacts with oxygen (O 2 ) to generate water (H 2 O) Cl - ions are bound to C 2 + on the copper powder surface.
That is, when oxidation occurs on the surface of the copper powder, the conductivity is lowered and induction of chemical bonding becomes difficult. First, the oxide film on the surface of the copper powder is removed. In the present invention, the oxide film on the surface of the copper powder is removed by using hydrogen chloride Remove.
The oxide film of the copper powder is removed by a process of CuO + 2HCl-> CuCl 2 (aq) + H 2 O (I), Cu 2 O + 2HCl-> 2 CuCl (aq) + H 2 O ) Is ion-bonded to copper (Cu), so it is removed in the course of ethanol rinsing.
The reason for using HCl is that strong acids such as nitric acid and sulfuric acid etch the metal, while hydrogen ions of hydrochloric acid tend to ionize more than copper ions.
It is a general theory that Cu and hydrochloric acid do not react.
As an experimental method, the oxide film on the surface of Cu is removed by using a solution of 1 to 5 mol of HCl.
The reaction time is adjusted to 5 to 10 minutes depending on the molar concentration of HCl.
HCl does not react with Cu, but it reacts with oxygen in the air to oxidize and etch the Cu surface, so that the molarity and the reaction time must be appropriately controlled.
After that, Graphene is synthesized on the copper via the functional group, so that the energization between the copper elements is performed well.
In addition, the oxidation preventive film formed at the step of nickel coating induces a chemical reaction by binding with a graphene oxide functional group, wherein the surface of the copper powder is coated with nickel and the oxide film is removed, and the copper- And then reacted for 5 days at 50 ° C. in an aqueous solution of 2'-bithiophene to form an antioxidant film as a self-assembled monolayer on the nickel-coated copper powder.
As an experimental method, 0.1 to 0.5 mol of 2,2'-bithiophene was added to the ethanol solution, and the copper with the oxide film removed was added thereto, followed by stirring at 40 to 50 ° C. for 5 to 7 days.
When the concentration of 2,2'-bithiophene is increased, it is necessary to adjust the temperature, time, and molar concentration appropriately since the polymerization can proceed beyond the self-assembly step.
After the reaction was completed, it was thoroughly rinsed with ethanol and then dried in a vacuum oven at 40 ° C
The graphene oxide is synthesized through graphene powder, sodium nitrate (NaNO 3 ), sulfuric acid (H 2 SO 4 ), potassium permanganate (KMnO 4 ) and hydrogen peroxide (H 2 O 2 ).
More specifically, the flask was charged with 150 ml of sulfuric acid (H 2 SO 4 ) at 0 ° C., 4.45 g of graphene powder and 3.37 g of sodium nitrate (NaNO 3 ) were added to the flask containing the sulfuric acid, Add potassium permanganate (KMnO 4 ) separately and stir to maintain the temperature of the mixture at 0 캜 to below 20 캜.
Since potassium permanganate is very reactive, it reacts slowly at low temperature because the temperature rises sharply due to the abrupt reaction when the temperature is more than 20 ° C, and the reaction does not occur well at less than 0 ° C.
When the chemical reaction of the mixture is stable, the mixture is stirred at a temperature of 30 ° C or more and 40 ° C or less for 2 hours, and then maintained for 4 to 5 days.
The abrupt reaction is reacted at low temperature and then the temperature is raised to allow the reaction of the remaining solution to proceed.
Thereafter, when the chemical reaction is completed, 500 ml of an aqueous solution having a 5 wt% weight ratio of sulfuric acid (H 2 SO 4 ) is added, followed by stirring for 3 hours.
This is because after the reaction type, the unreacted ions are finally reacted and sulfuric acid (H 2 SO 4 ) is added to neutralize the overall pH.
Thereafter, 10 ml of hydrogen peroxide (H 2 O 2 ) was added, followed by stirring for 24 hours.
Hydrogen peroxide serves to neutralize the acidic solution as a reducing agent and terminate the overall reaction.
The mixture is then centrifuged at 3000 rpm for 30 minutes in a centrifuge and rinsed with DI water to remove the acid, resulting in a graphene oxide.
The mixture inside the flask can be maintained at a low temperature through a low-temperature container used for lowering the temperature.
The graphene oxide has poor thermal and electrical properties and must be reduced to graphene. During the synthesis of the copper and graphene oxide functional groups, thiophene (C 4 H 4 S) is used to reduce graphene oxide.
Thiophene alpha hydrogen reacts with epoxy functional groups of graphene oxide to induce reduction.
The graphene is formed by using at least one of an oxygen bond of graphene oxide, a covalent bond of a single electron, and an incomplete bond by a hydrocarbon of thiophene.
In the present invention, as the functional group, 2,2'-Bithiophene in the form of a 6-membered sulfur (S) or selenium (Se) substituted at the carbon position of cyclopentadien, Thiophene, and Selenophene. In the present invention, an organic solvent such as ethanol is used to remove the surface oxide film from the copper powder, and 2,2'-bithiophene (2, 2'-Bithiophene) self-assembly.
Thereafter, chemical vapor deposition (CVD), hummers, and the like were performed to separate the graphene powder by synthesizing graphene in copper powder to which 2,2'-bithiophene was bonded. Method. In the present invention, graphene powder is peeled off by acid treatment of graphite by the hummers method.
6 is a schematic diagram of a chemical vapor deposition apparatus for growing graphene on a nickel substrate, and FIG. 7 is a schematic view of a chemical vapor deposition apparatus according to an embodiment of the present invention. FIG. 5 is a schematic view showing growth of graphene on copper- And FIG.
In the present invention, graphene is synthesized through a chemical vapor deposition (CVD) process. The chemical vapor deposition refers to making graphene using a transition metal that sucks carbon well at high temperature as a catalyst.
Copper is low in carbon melting to form uniform graphene, but since nickel has high carbon melting ability, it forms multi-layer graphene, so nickel is coated on the surface of copper powder and then graphene is synthesized .
First, methane hydrogen gas is injected into the coated nickel layer at a high temperature of 1000 占 폚 to allow carbon to penetrate between the grains of nickel.
Thereafter, when the nickel layer is cooled, carbon is precipitated on the surface of the nickel layer while being cooled, and becomes graphene.
Accordingly, the present invention provides a semiconductor device that is coated on a heat sink of a semiconductor to effectively dissipate heat generated from the semiconductor device, reduce electromagnetic interference (EMI), shield the electromagnetic wave, The present invention relates to a method of manufacturing a thermally conductive electromagnetic wave shielding paint for semiconductor comprising copper, nickel and graphene.
The thermally conductive electromagnetic shielding coating for copper, nickel and graphene for semiconductors is composed of nickel coated on the surface of the copper powder and graphene synthesized on the surface of the nickel.
Recently, electronic products such as mobile phones and notebooks have become miniaturized, and heat generated by batteries, CPUs, displays,
Since the atomic radius of nickel is 0.25, the atomic radius of copper is 0.28, and the atomic radius is similar, and since it has the same Fface centered cubic structure, the affinity between copper and carbon nanotube It acts as an intermediary and improves surface bonding force.
The nickel prevents corrosion of the copper powder surface.
In addition, the graphene is a carbon nanomaterial that is a single layer of a surface layer of graphite, which is composed of sp2 hybrid bonds of carbon by continuous chemical bonding of carbon atoms, has high electrical and thermal conductivity, and has high mechanical properties. It is in the form of a 2D plane and has a thickness of 0.2 nm (1 nm is one billionth of a meter), which is extremely thin, about 2 billionths of a billionths, and has high physical and chemical stability.
Therefore, coating the coating paint prepared according to the present invention on a heat radiator of a semiconductor effectively dissipates heat generated from the semiconductor device, reduces electromagnetic interference (EMI), shields electromagnetic waves, And the like.
1. Copper powder
2. Oxide film
3. Oxidation prevention film
4. Nickel
Claims (3)
The method for manufacturing a thermally conductive electromagnetic wave shielding paint for semiconductor includes an oxide film removing step of removing an oxide film (2) on a surface of a copper powder (1);
A nickel coating step of coating the nickel (4) on the surface of the copper powder (1) after the oxide film removing step to form the oxidation preventing film (3);
A graphene synthesis step of synthesizing graphene on the copper powder (1) through the nickel coating step;
Wherein the copper and nickel and graphene is characterized in that it comprises copper and nickel and graphene.
And removing the oxide film (2) on the surface of the copper powder (1) by using hydrogen chloride (HCl), nickel and graphene.
Wherein the graphene is synthesized by chemical vapor deposition (CVD) on the surface of nickel, wherein the graphene is synthesized on the surface of nickel.
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| KR1020160002913A KR101890023B1 (en) | 2016-01-08 | 2016-01-08 | Manufacturing method of thermal conduction EMI shield paint for semiconductor with copper and nickel and graphene |
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| KR1020160002913A KR101890023B1 (en) | 2016-01-08 | 2016-01-08 | Manufacturing method of thermal conduction EMI shield paint for semiconductor with copper and nickel and graphene |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100332109B1 (en) * | 1999-06-29 | 2002-04-10 | 박종섭 | Method of forming a via-hole in a semiconductor device |
| KR20110059946A (en) * | 2009-11-30 | 2011-06-08 | 한국지질자원연구원 | Preparation of copper powder coated with silver by electroless coating method and copper powder coated with silver thereof |
| KR101386104B1 (en) * | 2012-08-20 | 2014-04-16 | (주)우주일렉트로닉스 | Graphene coated metal conductor and flexible flat cable containing the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100332109B1 (en) * | 1999-06-29 | 2002-04-10 | 박종섭 | Method of forming a via-hole in a semiconductor device |
| KR20110059946A (en) * | 2009-11-30 | 2011-06-08 | 한국지질자원연구원 | Preparation of copper powder coated with silver by electroless coating method and copper powder coated with silver thereof |
| KR101386104B1 (en) * | 2012-08-20 | 2014-04-16 | (주)우주일렉트로닉스 | Graphene coated metal conductor and flexible flat cable containing the same |
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