[go: up one dir, main page]

WO2015016404A1 - CuO NANOPARTICLES, INK THEREOF, AND METHOD FOR PREPARING CU THIN FILM BY REDUCING CuO THIN FILM THROUGH MICROWAVE IRRADIATION - Google Patents

CuO NANOPARTICLES, INK THEREOF, AND METHOD FOR PREPARING CU THIN FILM BY REDUCING CuO THIN FILM THROUGH MICROWAVE IRRADIATION Download PDF

Info

Publication number
WO2015016404A1
WO2015016404A1 PCT/KR2013/006945 KR2013006945W WO2015016404A1 WO 2015016404 A1 WO2015016404 A1 WO 2015016404A1 KR 2013006945 W KR2013006945 W KR 2013006945W WO 2015016404 A1 WO2015016404 A1 WO 2015016404A1
Authority
WO
WIPO (PCT)
Prior art keywords
cuo
thin film
ink
nanoparticles
microwave irradiation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2013/006945
Other languages
French (fr)
Korean (ko)
Inventor
한윤봉
모하매드바즘
홍아라
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Industry Academic Cooperation Foundation of Chonbuk National University
Original Assignee
Industry Academic Cooperation Foundation of Chonbuk National University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Industry Academic Cooperation Foundation of Chonbuk National University filed Critical Industry Academic Cooperation Foundation of Chonbuk National University
Publication of WO2015016404A1 publication Critical patent/WO2015016404A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention relates to a method of preparing copper oxide (CuO) nanoparticles and using them to produce CuO nanoparticle ink.
  • the present invention also relates to a method of reducing a CuO thin film printed on a substrate using the CuO nanoparticle ink to a metallic copper (Cu) thin film through microwave irradiation.
  • the present invention also relates to a gel pen manufacturing method using the CuO nanoparticle ink.
  • Ink-printing of functional materials overcomes the shortcomings of conventional photolithography processes by direct printing of various patterns and studies and uses them as a low cost alternative. Ink printing will be widely used in the manufacture of conductive circuits for the electronics industry.
  • conductive ink-jet inks consist of a liquid carrier (water or organic solvent) that determines the dispersion or dissolution of components that provide the basic properties of the ink and the desired function.
  • Most conductive inks use silver (Ag), gold (Au) and platinum (Pt), which are expensive and have limited application in terms of mass production and economics.
  • copper metal is a good substitute for silver, gold and platinum. The only drawback with copper is that it oxidizes easily.
  • copper nanoparticles require toxic compounds, surfactants or post-synthetic surface treatment to prevent oxidation. Therefore, after printing and drying the liquid, the copper nanoparticles are covered with an organic stabilizer and an oxide that act as an insulator. The filtration process is limited due to the presence of organics and oxides between the particles. Additional post-printing composites, such as vacuum sintering, photosintering and pulsed electromagnetic sintering, are required to obtain conductive patterns. As a result, the production of conductor copper-based inks is expensive.
  • the present invention for solving the above problems is an object of the present invention to provide a method for producing copper oxide (CuO) nanoparticles without additional oxidation problems in an inexpensive solution method.
  • An object of the present invention is to provide a method for producing an electronic ink using CuO nanoparticles.
  • the purpose is to convert the printed CuO nanoparticles to copper nanoparticles through vacuum microwave irradiation.
  • the present invention for achieving the above object provides a copper oxide (CuO) nanoparticles produced by a simple solution method.
  • the present invention provides the CuO nanoparticles, wherein the CuO nanoparticles are characterized by a size of 5 to 8 nm in a black colloidal state.
  • step 1 of mixing acetic acid with an aqueous solution of copper acetate; 2 steps of heating the resultant of the first step to 9 (rC, reflux; and 3 steps of adding a metal hydroxide while maintaining the resultant of the second step at 90 ° C .; It provides a method for producing CuO nanoparticles comprising the fourth step after centrifugation and washing.
  • the metal hydroxide in the method for preparing copper oxide (CuO) nanoparticles, is provided with CuO nanoparticles manufacturing method, characterized in that any one selected from LiOH, NaOH, KOH, RbOH or CsOH. do.
  • the copper oxide (CuO) nanoparticles manufacturing method the copper acetate solution has a concentration of 0.2M
  • the first step is to mix the copper acetate solution and acetic acid in a ratio of 100: 0.5 It provides a method for producing CuO nanoparticles, characterized in that.
  • the present invention provides a method for producing CuO nanoparticles, characterized in that the black colloidal solution obtained after reflux for 10 to 15 minutes in the method of producing CuO nanoparticles is sonicated for 15 minutes.
  • the present invention provides an electronic ink prepared by mixing the CuO nanoparticles and an ink solvent.
  • the present invention is the electronic ink, the ink solvent is 30-40 wt% water, ethanol
  • the present invention provides the electron ink, wherein the CuO nanoparticle concentration is 25-35 wt% in the electron ink.
  • the present invention provides the electronic ink, wherein the CuO nanoparticles and the ink solvent are homogenized by using a homogenizer (Thinky ARE-100 Conditioning Mixer).
  • a homogenizer Thinky ARE-100 Conditioning Mixer
  • the present invention provides an electron ink, wherein in the electron ink, ethylene glycol serves as a reducing agent for reducing CuO to copper.
  • the present invention provides an electronic ink, wherein in the electronic ink, ethylene glycol can also use a solvent based on other glycols (diethylene glycol, propylene glycol).
  • the thin film deposition using the electronic ink is performed by spin coating, spray printing, ink pen, inkjet printing, screen printing, -to- (R2R), offset, etc. It provides an electronic ink, characterized in that can be used.
  • the electron ink in the thin film manufacturing process by spin coating of the electron ink, is microwave in a vacuum state on a CuO thin film deposited by spin coating on a glass substrate. It provides a thin film manufacturing process characterized in that to investigate.
  • the present invention provides a device characterized in that the vacuum microwave equipment is manufactured using a device including a microwave generator in the thin film manufacturing process of the electronic ink.
  • the pressure is atmospheric pressure or a vacuum pressure range provides an apparatus that is characterized by 1 X 10- 1 to 1 X 10- 5 Pa.
  • the present invention provides a device characterized in that a thin film including CuO nanoparticles is rapidly heated by microwave irradiation, and ethylene glycol present in the thin film is heated to a boiling point.
  • the present invention provides an apparatus, wherein in the vacuum microwave apparatus, ethylene glycol heated to the boiling point dehydrates acetaldehyde. ⁇ 25> In the present invention, the acetaldehyde in the reduction process of the CuO nanoparticle ink
  • the present invention provides a preparation of a CuO nanoparticle gel pen for producing a CuO nanoparticle ink pen, wherein the electronic ink is prepared using a gel pen having a 300 tip.
  • the present invention provides a gel pen characterized in that the CuO nanoparticle gel pen is used for paper, glass, polymer, and silicon substrates.
  • the present invention provides an electrode fabricated on paper with the CuO nanoparticle gel pen.
  • an electrode made of a CuO nanoparticle gel pen is provided.
  • the electrode made of the nanoparticle gel pen is irradiated with microwaves at 54.31 y Q. to provide a resistance of cm.
  • an electrode made of a CuO nanoparticle gel pen has an electric resistance improved as the microwave irradiation time increases, and provides an electrode having a constant resistance when the microwave irradiation time is 60 seconds or more.
  • the electrode produced by continuous printing with the CuO nanoparticle gel pen provides a characteristic that the electrical resistance is improved as the number of continuous printing.
  • the continuous printing is filled with pores formed in the thin film as the number of times increases Dense copper thin film on paper substrate Provide the properties that are created in the.
  • the present invention provides a method for producing CuO nanoparticles by a solution method having a simple process and low cost.
  • the present invention provides a method for producing an ink which is economical, environmentally friendly, long-term oxidation-free, and stable at room temperature by mixing the CuO nanoparticles with a predetermined ink solvent.
  • the present invention provides a method for reducing a CuO thin film printed on a substrate using the CuO nanoparticle ink to a metallic copper (Cu) thin film through microwave irradiation.
  • the present invention also provides a method for preparing an ink gel pen with the CuO nanoparticle ink.
  • FIG. 1 is a view illustrating a method for preparing copper oxide nanoparticles, thin film deposition, and microwave irradiation according to an embodiment of the present invention.
  • FIG. 2 illustrates a cross-sectional FESEM image and EDX analysis results after microwave irradiation of a thin film spin-coated on a glass substrate with a copper oxide nanoparticle ink according to an embodiment of the present invention
  • (a) spin The figure shows coating deposition, (b) 1 minute microwave irradiation, (c) 2 minutes microwave irradiation, (d) 3 minutes microwave irradiation, and (e) 4 minutes microwave irradiation.
  • FIG. 3 shows low resolution and high resolution surface FESEM images after microwave irradiation on a thin film spin-coated on a glass substrate with a copper oxide nanoparticle ink according to an embodiment of the present invention.
  • 1 minute microwave irradiation (c) 2 minutes microwave irradiation, (d) 3 minutes microwave irradiation and (d) 4 minutes microwave irradiation.
  • FIG. 4 is a graph showing an element composition comparison graph by surface EDX analysis after microwave irradiation of a thin film spin-coated on a glass substrate with a copper oxide nanoparticle ink according to an embodiment of the present invention.
  • FIG. 5 is a graph showing X-ray emission graphs after microwave irradiation on a thin film spin-coated deposited on a glass substrate with a copper oxide nanoparticle ink according to an embodiment of the present invention.
  • FIG. 8 is an electrode diagram of a copper oxide nanoparticle gel pen on a paper substrate according to an embodiment of the present invention.
  • FIGS. 9 and 10 illustrate the electrical resistance of a paper substrate according to one embodiment of the present invention obtained by irradiating microwaves to an electrode made of a copper oxide nanoparticle ink pen using a 2-point probe. Drawing.
  • FIG. 11 is a diagram illustrating electrical resistance measurements and calculations using a 2-point probe of an electrode made of a copper oxide nanoparticle gel pen on a paper substrate according to an embodiment of the present invention.
  • FIG. 12 illustrates surface and cross-sectional FESEM images of structural changes after 1 minute microwave irradiation on an electrode made of a copper oxide nanoparticle gel pen on a paper substrate according to an embodiment of the present invention.
  • (1) One time print (2) Two times continuous printing (3) Three times continuous printing is shown.
  • FIG. 13 is a view showing optical and FESEM images of an electrode made of a gel pen on a paper substrate according to an embodiment of the present invention.
  • One embodiment of the present invention provides a method for preparing CuO nanoparticles by a simple solution method.
  • the CuO nanoparticles are synthesized by a low solution solution using copper acetate as a precursor.
  • NaOH sodium hydroxide
  • ⁇ 5 1> by adding a solvent to the CuO nanoparticles made by the above method to form an electronic ink, depositing it as a thin film, drying the deposited thin film, and depositing the deposited CuO thin film under vacuum It consists of irradiating microwaves and sintering them into Cu thin films. It provides a method for producing a CuO nanoparticle ink comprising the step of homogenizing and sonicating the reaction solution and centrifugation and washing.
  • the step of depositing the CuO nanoparticle ink made by the above method as a thin film the step of drying the deposited thin film, and sintering the deposited CuO thin film by microwave irradiation in a vacuum to form a Cu thin film It consists of steps.
  • FIG. 1 is a diagram showing steps 1 to 3 described above showing a method of synthesizing copper oxide nanoparticles, an electron ink formulation, and a microwave irradiation process.
  • a mixed solution is prepared while stirring 100 ml of 0.02 M copper acetate solution and 0.5 ml of 35% acetic acid aqueous solution at room temperature.
  • Step 1 Stir well the mixture of copper acetate solution and acetic acid solution while heating slowly under reflux reaction (Step 2).
  • the heating temperature of the mixture is preferably set to 90 ° C to 120 ° C, in this embodiment was heated to a temperature of 90 ° C.
  • 0.5 g of metal hydroxide Pal let is added to the mixture.
  • the metal hydroxide may be LiOH, NaOH, K0H, RbOH or CsOH pallet, in this embodiment was added NaOH 3 ⁇ 4lets.
  • step 3 a black solution is produced (step 3). It can be seen that the formation of the CuO nanoparticles is made through such a color change.
  • the temperature reaction time, concentration reaction conditions are only one embodiment, and do not represent all of the technical ideas of the present invention.
  • the resultant was centrifuged at 3000 rpm for 2 minutes and washed with water and ethanol to obtain black colloidal CuO nanoparticles.
  • the size of the obtained CuO nanoparticles is 5 to 8 nm.
  • the ink solvent may be prepared by mixing water, ethanol, ethylene glycol, and polyvinylpyrrolidone, but are not limited thereto.
  • the ink solvent is 30-40, ethanol 6-9w%, EG 22-27w%, and PVP 1-3 ⁇ .
  • CuO nanoparticles and ethylene glycol are prepared in an ink ratio of 1.15: 1.
  • CuO nanoparticles, water, ethanol, ethylene glycol and polyvinylpyrrolidone may be combined with, but not limited to, wt% (mass ratio) of 29.0: 36.4: 7.3: 25.5: 1.8, respectively. .
  • the electronic ink mixture is homogenized at 2000 rpm for 2 minutes in a homogenizer (Thinky ARE-100 Conditon ionizing Mixer).
  • Ethylene glycol acts as a reducing agent to convert CuO to copper.
  • Other glycol-based solvents can be used.
  • the CuO nanoparticle ink makes a thin film by spin coating on a substrate.
  • the substrate to be used may be glass, paper, fiber, silk, polymer, silicon, or the like.
  • CuO Thin film deposition using nanoparticle ink may use spin coating, spray printing, ink pen, ink-jet printing, screen printing, and the like.
  • the deposited thin film is dried to evaporate low boiling solvents such as water and ethanol.
  • microwave irradiation was performed under atmospheric pressure or vacuum.
  • the vacuum pressure range is 1 ⁇ 10—1 to 1 ⁇ 10 Pa, and the vacuum used in one embodiment is 3.5 ⁇ 10 Pa.
  • Vacuum microwave equipment was produced using a microwave oven.
  • Microwave irradiation heats up thin films containing CuO nanoparticles quickly and heats the ethylene glycol present in the thin films to the boiling point. When the boiling point of ethylene glycol is reached, the resulting acetaldehyde (C3 ⁇ 4CH0) is dehydrated. Acetaldehyde converts CuO nanoparticles into pure Cu phase. In order to produce dense, interconnected Cu films, continuous irradiation of microwaves is required. Reduction reaction by microwave is as follows.
  • FIG. 2 is a view showing a cross-sectional FESEM and EDX analysis results after microwave irradiation on a thin film spin-coated on a glass substrate with the CuO nanoparticle ink of the present embodiment.
  • FIG. 3 (a ′ 1) shows that the thickness of the deposited thin film is 4 to 5 ⁇ in the FESEM image of the deposited copper oxide thin film.
  • 2 (a-2) and 2 (a-3) show the elemental composition of the deposited thin film. It shows that the thickness of copper (a-2) and oxygen (a-3) is equal to the thickness of the thin film deposited with 4 to 5 ⁇ .
  • 2 (bl), (b-2) and (b-3) are cross-sectional FESEM and EDX results after 1 minute microwave irradiation of the deposited copper oxide thin film of this example.
  • the upper layer shows a thickness of 0.5 to 0.65iim or less with the reduced and sintered copper phase.
  • the lower layer shows that the CuO layer which was not reduced exists.
  • 2 (cl), (c-2) and (c-3) are cross-sectional FESEM and EDX results after 2 minutes of microwave irradiation on the deposited CuO thin film. As the microwave irradiation time increases, most thin films having a thickness of 1 to 2 mu ⁇ are reduced and sintered to show only the Cu phase (c-2) without the oxygen (0) phase (c ⁇ 3).
  • FIG. 3 shows the reduction and sintering of the Cu metal phase as a result of further increasing the microwave irradiation time.
  • the oxygen element is detected by detecting oxygen contained in the glass substrate.
  • the microwave irradiated for 2 minutes was found to penetrate up to 2 ym of the thin film. Increased microwave irradiation time can reduce and sinter thicker CuO thin films.
  • FIG. 3 shows a low resolution and high resolution surface FESEM image after microwave irradiation in a thin film spin-coated on a glass substrate with CuO nanoparticle ink according to the present embodiment.
  • conductive thin films must have a three-dimensional interconducting path between Cu nanoparticles. The conduction path appears after 1 minute of microwave irradiation.
  • FIG. 3 (a) shows small, spherical nanoparticles.
  • Figure 3 (b) shows the change in nanoparticles continuous and sintered particle shape after 1 minute microwave irradiation.
  • 3 (ce) shows that as the microwave irradiation time increases, the thin film becomes dense and the particles grow in association.
  • FIG. 5 shows an X-ray diffraction graph according to a change in irradiation time after microwave irradiation on a thin film spin-coated on a glass substrate with CuO nanoparticle ink according to the present embodiment.
  • the XRD diffraction peaks observed in the deposited CuO thin film show the CuO monoclinic phase.
  • Other impurities except CuO characteristic peaks or other crystal phase peaks such as copper oxide (I) (Cu 2 0) copper hydroxide (II) (Cu (0H) 2 ) were not observed.
  • the deposited CuO nanoparticles show high purity crystalline.
  • FIG. 6 is an electrical resistance (R) measured by a 4-point probe after microwave irradiation of a thin film spin-coated on a glass substrate with CuO nanoparticle ink according to an embodiment of the present invention (R). ) And (b) resistance (p).
  • the deposited film was ⁇ 10 2 ⁇ . It has an electrical resistance of ⁇ . After 1 minute to 4 minutes of microwave irradiation, the electrical resistance is substantially improved. In cm, the resistance is 2 to 3 times higher than the bulk state.
  • FIG. 7 illustrates a method of applying CuO nanoparticle ink to a gel pen according to the present embodiment, depositing a thin film on a paper substrate, and microwave irradiation.
  • CuO prepared according to the ink formulation of Figure 2 Gel pens are made using old particle ink. Gel pens were used gel pens (Dong-A Co., Ltd.) having a 300 ⁇ tip. Before filling the CuO nanoink, the pen tip of the gel pen is sonicated under water and ethanol to remove the commercial ink. Fill the gel pen with the commercial ink removed from the bottom using a syringe with CuO nanoparticle ink. Gel pens are used to create CuO nanoparticle thin films on paper substrates. The gel pen can be used not only for paper substrates but also for glass, polymer and silicon substrates. The formed CuO thin film is sintered by microwave irradiation in a vacuum state to produce a Cu thin film.
  • FIG. 8 shows an example of an electrode made of CuO nanoparticle gel pen on a paper substrate according to the present embodiment.
  • a 16 mm long, 2 ⁇ wide electrode was prepared with a gel pen to check the performance of the electrode, including its shape and electrical properties.
  • FIGS. 9 and 10 illustrate an electrical resistance measured by a 2-point probe by irradiating microwaves to an electrode made of a CuO nanoparticle ink pen on a paper substrate according to an embodiment of the present invention. It is a figure which shows (R) and (b) resistance degree (p).
  • FIG. 11 shows electrical resistance (R) and resistance (p) measured by a 2-point probe of an electrode manufactured by continuously printing a CuO nanoparticle gel pen on a paper substrate according to the present embodiment. To burn. Each continuous printing method is carried out after 2 minutes of microwave irradiation in a vacuum state. 11 shows that the electrical resistance improves as the number of continuous prints increases. Also, when printing more than 3 times continuously, the resistance is 10 ⁇ . Constant at ⁇ , which is six times higher than the bulk state.
  • FIG. 12 illustrates surface and cross-sectional FESEM images of structural changes after 1 minute microwave irradiation on electrodes made of CuO nanoparticle gel pens on a paper substrate according to an embodiment of the present invention. As the number of consecutive prints increases, the pores formed in the thin film are filled, indicating that a small, dense copper thin film is formed on the paper substrate. Surface and cross-sectional FESEM images support the electrical properties observed so far.
  • FIG. 13 is an optical photograph of an electrode made of a gel pen on a paper substrate according to the present embodiment
  • Electrodes prepared after 1 minute microwave irradiation show the color and uniform printing characteristics of the metal Cu.
  • the present invention is a technique relating to the production of ink and thus the recovery of copper, and is applicable to the production and recycling industry of ink.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Toxicology (AREA)
  • Manufacturing & Machinery (AREA)
  • General Health & Medical Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The present invention relates to the synthesis of copper oxide (CuO) nanoparticles having a particle size of 2-20 nm. The present invention relates to a method for preparing ink by using the CuO nanoparticles and a mixture solvent comprising water, ethanol and ethylene glycol. The ethylene glycol serves as a reducing agent. In addition, in the present invention a thin film is prepared on a substrate by using a mixed CuO nanoparticle ink and a pure copper thin film is formed by irradiating microwaves at different time intervals. When microwaves are irradiated at a CuO ink thin film, prepared by spin coating, for three minutes or more, the film has a resistance of 4.65 μΩ·cm, which is 2-3 times greater than that of a bulk. In the present invention the ink was applied to a gel pen so as to be printed on various substrates. An electrode, which is printed on a paper substrate with the ink pen, was continuously printed three times and microwave-irradiated and has a resistance of 10 μΩ, which is six times greater than that of a bulk.

Description

【명세서】  【Specification】

【발명의 명칭】  [Name of invention]

CuO 나노입자와 그의 잉크 및 마이크로파 조사를 통한 CuO 박막으로부터 Cu 박막으로 환원시키는 이들의 제조방법  CuO nanoparticles and their production method to reduce CuO thin film to Cu thin film through ink and microwave irradiation

【기술분야】  Technical Field

<ι> 본 발명은 산화구리 (CuO) 나노입자를 제조하고, 이를 이용하여 CuO 나노입자 잉크를 제조하는 방법에 관한 것이다. 또한 상기 CuO 나노입자 잉크를 사용하여 기 판에 인쇄한 CuO 박막을 마이크로파의 조사를 통하여 금속 구리 (Cu) 박막으로 환원 시키는 방법에 관한 것이다. 또한 본 발명은 상기 CuO 나노입자 잉크를 사용하는 젤펜 제조 방법에 관한 것이다.  The present invention relates to a method of preparing copper oxide (CuO) nanoparticles and using them to produce CuO nanoparticle ink. The present invention also relates to a method of reducing a CuO thin film printed on a substrate using the CuO nanoparticle ink to a metallic copper (Cu) thin film through microwave irradiation. The present invention also relates to a gel pen manufacturing method using the CuO nanoparticle ink.

【배경기술】 . Background technology .

<2> 높은 품질과 저비용의 전자부품에 대한 세계시장의 수요는 기존의 생산방식 에 비해 빠르고 저렴한 혁신적인 제조기술을 필요로 한다. 기능성 소재의 잉크 인 쇄 (Ink-printing)는 다양한 패턴의 직접 인쇄로 기존의 포토리소그래피 (photolithography) 공정의 단점을 극복하며 저비용의 대안으로 연구 및 사용한다. 잉크 인쇄는 앞으로 전자산업 전도성 회로 제작에 많이 이용될 것이다. 일반적으 로， 전도성 잉크젯 (Ink-jet) 잉크는 잉크의 기본 속성 및 원하는 기능을 제공하는 구성요소의 분산 또는 용해를 결정하는 액체 운반체 (물 또는 유기용매)로 구성한 다. 대부분의 전도성 잉크는 은 (Ag), 금 (Au) 및 백금 (Pt)을 이용하는데 이러한 금 속은 고가이기 때문에 대량생산과 경제성 측면에서 적용에 한계가 있다. 현재 구리 금속은 은， 금 및 백금의 좋은 대체원이다. 구리의 경우 유일한 단점은 쉽게 산화 된다는 점이다.  <2> The global market demand for high quality and low cost electronic components requires innovative manufacturing techniques that are faster and cheaper than conventional production methods. Ink-printing of functional materials overcomes the shortcomings of conventional photolithography processes by direct printing of various patterns and studies and uses them as a low cost alternative. Ink printing will be widely used in the manufacture of conductive circuits for the electronics industry. Generally, conductive ink-jet inks consist of a liquid carrier (water or organic solvent) that determines the dispersion or dissolution of components that provide the basic properties of the ink and the desired function. Most conductive inks use silver (Ag), gold (Au) and platinum (Pt), which are expensive and have limited application in terms of mass production and economics. Currently copper metal is a good substitute for silver, gold and platinum. The only drawback with copper is that it oxidizes easily.

<3> 최근에 구리 나노입자를 제조하는 논문이 보고되고 있다 (R. A. Salkar, P.  <3> Recently, a paper for producing copper nanoparticles has been reported (R. A. Salkar, P.

Jeevanandam, G. Kataby, S. T. Aruna , Yuri Koltypin, 0. Palchik, and A. Gedanken , "Elongated Copper Nanopart icles Coated with a Zwi tter ionic Surfactant" , J. Phys . Chem. B, 2000； David S. Jacob, Isaschar Genish, Lior Klein, and Aharon Gedanken , "Carbon-Coated Core Shell Structured Copper and Nickel Nanopart icles Synthesized in an Ionic Liquid" , J . Phys . Chem. B, 2006； K. Murai , Y. Watanabe, Y. Saito, T. Nakayama, H. Suematsu, W. Jiang, K. Yatsui , K.H. Shim and K. Ni ihara, "Preparation of copper nanopart icles with an organic coating by a pulsed wire discharge method, " J. Ceram. Process . Res., 2007； David B. Pedersen, Shi 1 iang Wang and Septimus H. Liang, "Charge- Transfer -Driven Diffusion Processes in Cu@Cu_0xide CoreShel 1 Nanopart icles： Oxidation of 3.0 + 0.3 nm Diameter Copper Nanopart icles , " J. Phys . Chem. C, 2008)， 황산구리 (CuS04)를 N—비닐피를리딘온 (poly(N-vinylpyrrolidone))과 벤조페논 Jeevanandam, G. Kataby, ST Aruna, Yuri Koltypin, 0. Palchik, and A. Gedanken, "Elongated Copper Nanopart icles Coated with a Zwi tter ionic Surfactant", J. Phys. Chem. B, 2000; David S. Jacob, Isaschar Genish, Lior Klein, and Aharon Gedanken, "Carbon-Coated Core Shell Structured Copper and Nickel Nanopart icles Synthesized in an Ionic Liquid", J. Phys. Chem. B, 2006; K. Murai, Y. Watanabe, Y. Saito, T. Nakayama, H. Suematsu, W. Jiang, K. Yatsui, KH Shim and K. Ni ihara, "Preparation of copper nanopart icles with an organic coating by a pulsed wire discharge method, "J. Ceram. Process. Res., 2007; David B. Pedersen, Shi 1 iang Wang and Septimus H. Liang, "Charge- Transfer-Driven Diffusion Processes in Cu @ Cu_0xide CoreShel 1 Nanopart icles: Oxidation of 3.0 + 0.3 nm Diameter Copper Nanopart icles, "J. Phys. Chem. C, 2008), copper sulfate (CuS0 4 ) (poly (N-vinylpyrrolidone)) and benzophenone

(benzophenone)의 존재하에 253.7nm 파장의 UV 빛으로 광환원하여 구리 나노입자를 제조하는 방법 (Sudhir apoor , Tulsi Mukher j ee , "Photochemical format ion of copper nanopart icles in poly(N-vinylpyrrol idone) , " Chemical Physics Letters , 2003), 구리염 수용액과 환원제를 함유하는 수용액을 반웅시켜서 구리 나노입자를 제조하는 방법 (W. Liu, Xiaobo Wang, Singgou Fu, US Patent 10/997,220), 다른 기 체없이 세틸트리메틸암모늄브로마이드 (cetyltrimethyl ammonium bromide)하에서 하 이드라진 하이드레이트 (hydrazine hydrate)를 사용하여 질산구리 (copper nitrate) 환원하여 순수하고 고순도의 구리 나노입자 제조방법 (Moha隱 ad Vaseema, Kil Mok Lee, Dae Young Kim, Yoon-Bong Hahn, "Parametric study of cost-effective synthesis of crystalline copper nanopart icles and their crystal lographic characterization," Materials Chemistry and Physics , 2011)이 보고되었다. 잉크 인쇄에 웅용하기 위해 구리 나노입자 기반 잉크 배합은 중요하다. 얇은 표면의 산 화물 층으로 공기에 안정적인 수용성 구리 나노입자로 수성기반의 구리 잉크제조 및 잉크젯 인쇄한 것과 수용성 구리잉크의 용매에 의해 안정한 젯팅 (jetting) 결과 에 관한 방법 (Sunho Jeong, Hae Chun Song, Won Woo Lee, Sun Sook Lee, Youngmin Choi , Woni 1 Son, Eui Duk Kim, Choon Hoon Paik, Seok Heon Oh, Beyong-Hwan Ryu, "Stable Aqueous Based Cu Nanopart icle Ink for Printing Well—Defined Highly Conductive Features on a Plastic Substrate, " Langmuir , 2011) , 디치오카르본산 염 (dithiocarbonate)을 치환하여 공기중에 안정한 구리나노입자 잉크를 만드는 방 법 (Naveen Chopra, Peter M. azmaier , Matthew W0RDEN, U.S. Patent No. 11/7,976,733), 환원 금속물 및 환원제를 용액에 분산시켜 기판에 박막을 제작 후 제작된 박막에 펄스자기장 방출 (pulsed electromagnetic emission)에 의해 환원 금 속물질과 환원제가 화학적 반웅하여 전기적 전도성 박막 제작하는 방법 (Pope Dev S, U.S. Patent No. 11/0,262,657), 구리염을 환원시켜 구리나노 입자를 합성하는 것 (Dezelah Charles L, Winter Charles H, Yu Zhengkun , U.S. Patent No. 05/6,887,297), 구리 나노입자의 저온에서 환원 멎 소결과 방법으로 환원제는 포 름산 (formic acid), 아세트산 (acet ic acid) 알코을 (alcohol )류 및 에테르 (ether) (Jae-Woo Joung, In-young Kim, Young-Ah SONG, U.S. Patent No. 12/8206609) , 또 는 구리 같은 금속 잉크를 제논램프 (xenon lamp) 광원으로 광소결 (photosintering )하여 구리 박막의 저항을 측정하는 방법 (Yunjun Li , David Max Roundhi l l , Xue i ng Li , Peter B. Laxton , Hidetoshi Ar imura , Zvi Yaniv, U. S . Patent No . 2013/8404160) 에 관한 연구결과들로서 구리나노 입자잉크를 제조하기 위한 방법에 는 몇가지 단점이 있다. 대부분의 경우 구리나노 입자는 산화방지를 위해 독성화합 물질， 계면활성제 또는 합성후 표면처리가 요구된다. 따라서 액체의 인쇄 및 건조 후 구리나노입자는 절연체로 작용하는 유기안정제 및 산화물로 덮여있다. 입자사이 에 유기물질 및 산화물의 존재 때문에 여과 과정은 제한된다. 전도성 패턴을 얻기 위해 진공소결， 광소결 및 펄스 전자기 소결이 같은 추가적인 인쇄 후 복합처리가 필요하다. 결과적으로 도체 구리 기반 잉크의 제조는 고가이다. (Sudhir apoor, Tulsi Mukher j ee, "Photochemical format ion of copper nanopart icles in poly (N-vinylpyrrol idone)," photoreduced by UV light having a wavelength of 253.7 nm in the presence of (benzophenone). Chemical Physics Letters, 2003), a method for preparing copper nanoparticles by reacting an aqueous solution containing a copper salt solution and a reducing agent (W. Liu, Xiaobo Wang, Singgou Fu, US Patent 10 / 997,220), cetyltrimethyl without other gases Method for producing pure and high purity copper nanoparticles by reducing copper nitrate using hydrazine hydrate under cetyltrimethyl ammonium bromide (Moha 隱 ad Vaseema, Kil Mok Lee, Dae Young Kim, Yoon-Bong Hahn, "Parametric study of cost-effective synthesis of crystalline copper nanoparticles and their crystal lographic characterization," Materials Chemistry and Physics, 2011). Copper nanoparticle based ink formulations are important for use in ink printing. Process for producing aqueous ink-based copper ink and inkjet printing with water-soluble copper nanoparticles with thin surface oxide layer and stable jetting results by solvent of water-soluble copper ink (Sunho Jeong, Hae Chun Song, Won Woo Lee, Sun Sook Lee, Youngmin Choi, Woni 1 Son, Eui Duk Kim, Choon Hoon Paik, Seok Heon Oh, Beyong-Hwan Ryu, "Stable Aqueous Based Cu Nanopart icle Ink for Printing Well—Defined Highly Conductive Features on a Plastic Substrate, "Langmuir, 2011), a method for making copper nanoparticle ink stable in air by substituting dithiocarbonate (Naveen Chopra, Peter M. azmaier, Matthew W0RDEN, US Patent No. 11 / 7,976,733) ), The reducing metal and the reducing agent are dispersed in a solution to make a thin film on the substrate, and then the reducing metal material and the reducing agent are chemically reacted by pulsed electromagnetic emission to produce the thin film. Method for manufacturing conductive thin film (Pope Dev S, US Patent No. 11 / 0,262,657), synthesis of copper nanoparticles by reducing copper salt (Dezelah Charles L, Winter Charles H, Yu Zhengkun, US Patent No. 05 / 6,887,297 Reduction at low temperatures of copper nanoparticles and by sintering and reducing agents are performed by formic acid, acetic acid, alcohols and ethers (Jae-Woo Joung, In-young Kim, Young-Ah SONG, US Patent No. 12/8206609), or photosintering metal ink, such as copper, with a xenon lamp light source (Yunjun Li, David Max Roundhill, Xue Ing Li, Peter B. Laxton, Hidetoshi Imine, Zvi Yaniv, U. S. Patent No. 2013/8404160) As a result, there are some disadvantages to the method for producing copper nanoparticle ink. In most cases, copper nanoparticles require toxic compounds, surfactants or post-synthetic surface treatment to prevent oxidation. Therefore, after printing and drying the liquid, the copper nanoparticles are covered with an organic stabilizer and an oxide that act as an insulator. The filtration process is limited due to the presence of organics and oxides between the particles. Additional post-printing composites, such as vacuum sintering, photosintering and pulsed electromagnetic sintering, are required to obtain conductive patterns. As a result, the production of conductor copper-based inks is expensive.

【발명의 상세한 설명】  [Detailed Description of the Invention]

【기술적 과제】  [Technical problem]

<4> 상술한 문제를 해결하기 위한 본 발명은 저렴한 용액법으로 추가적인 산화문 제가 없는 산화구리 (CuO) 나노입자들을 제조하는 방법을 제공하는 데에 그 목적이 있다. 본 발명은 CuO 나노입자를 사용하여 전자잉크를 제조하는 방법을 제공하는 데에 그 목적이 있다. 또한 인쇄된 CuO 나노입자를 진공 마이크로파 조사를 통하여 구리 나노입자로 변환시키는 데에 그 목적이 있다.  The present invention for solving the above problems is an object of the present invention to provide a method for producing copper oxide (CuO) nanoparticles without additional oxidation problems in an inexpensive solution method. An object of the present invention is to provide a method for producing an electronic ink using CuO nanoparticles. In addition, the purpose is to convert the printed CuO nanoparticles to copper nanoparticles through vacuum microwave irradiation.

<5> 본 발명이 이루고자 하는 기술적 과제들은 이상에서 언급한 기술적 과제들로 제한되지 않으며， 언급되지 않은 또 다른 기술적 과제들은 본 발명의 기재로부터 당해 분야에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있을 것이다.  The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned above will be clearly understood by those skilled in the art from the description of the present invention. Could be.

【기술적 해결방법】  Technical Solution

<6> 상술한 목적을 달성하기 위한 본 발명은 간단한 용액법으로 제조되는 산화구 리 (CuO) 나노입자를 제공한다.  The present invention for achieving the above object provides a copper oxide (CuO) nanoparticles produced by a simple solution method.

<7> 본 발명은 상기 CuO 나노입자에 있어서， 상기 CuO 나노입자는 검은색의 콜로 이드 상태로 5 내지 8 nm의 크기를 특징으로 하는 CuO 나노입자를 제공한다.  The present invention provides the CuO nanoparticles, wherein the CuO nanoparticles are characterized by a size of 5 to 8 nm in a black colloidal state.

<8> 초산 구리 (Copper Acetate) 수용액에 초산 (Acet ic Acid)을 흔합하는 1단계; 상기 1단계의 결과물을 9(rC로 가열하고， 환류 (Ref lux)하는 2단계; 및 상기 2단계 의 결과물을 90°C로 유지하면서 금속수산화물을 첨가하는 3단계; 상기의 반웅액을 초음파처리한 후 원심분리 및 세척하는 제 4단계를 포함하는 것을 특징으로 하는 CuO 나노입자의 제조방법을 제공한다. <8> step 1 of mixing acetic acid with an aqueous solution of copper acetate; 2 steps of heating the resultant of the first step to 9 (rC, reflux; and 3 steps of adding a metal hydroxide while maintaining the resultant of the second step at 90 ° C .; It provides a method for producing CuO nanoparticles comprising the fourth step after centrifugation and washing.

<9> 또한 상기의 방법으로 만들어진 CuO 나노입자에 용매를 첨가하여 전자잉크를 만드는 단계와， 이를 박막으로 증착하는 단계와， 증착된 박막을 건조시키는 단계 와， 증착된 CuO 박막을 진공상태에서 마이크로파를 조사하여 소결시켜 Cu 박막으로 만드는 단계로 구성된다. <9> In addition, by adding a solvent to the CuO nanoparticles made by the above method to make an electronic ink, depositing it as a thin film, drying the deposited thin film, and depositing the deposited CuO thin film in a microwave state Is irradiated and sintered to Cu thin film It is made up of steps.

<ιο> 본 발명은 상기 산화구리 (CuO) 나노입자 제조방법에 있어서， 상기 금속수산 화물은 LiOH, NaOH, KOH, RbOH 또는 CsOH 중에서 선택되는 어느 하나인 것을 특징 으로 하는 CuO나노입자 제조방법을 제공한다.  In the present invention, in the method for preparing copper oxide (CuO) nanoparticles, the metal hydroxide is provided with CuO nanoparticles manufacturing method, characterized in that any one selected from LiOH, NaOH, KOH, RbOH or CsOH. do.

<π> 본 발명은 상기 산화구리 (CuO) 나노입자 제조방법에 있어서， 상기 초산구리 수용액은 0.2M의 농도를 가지며, 상기 제 1단계는 초산 구리 수용액과 초산을 100:0.5의 비율로 흔합하는 것을 특징으로 하는 CuO 나노입자 제조방법을 제공한 다.  <π> In the present invention, the copper oxide (CuO) nanoparticles manufacturing method, the copper acetate solution has a concentration of 0.2M, the first step is to mix the copper acetate solution and acetic acid in a ratio of 100: 0.5 It provides a method for producing CuO nanoparticles, characterized in that.

<12> 본 발명은 상기 CuO 나노입자 제조방법에 있어서， 10 내지 15분간 환류 후 얻어진 검은색 콜로이드 용액을 15분간 초음파 처리하는 것을 특징으로 하는 CuO 나노입자 제조방법을 제공한다.  The present invention provides a method for producing CuO nanoparticles, characterized in that the black colloidal solution obtained after reflux for 10 to 15 minutes in the method of producing CuO nanoparticles is sonicated for 15 minutes.

<13> 본 발명은 상기 CuO 나노입자와 잉크용매를 흔합하여 제조한 전자잉크를 제 공한다.  The present invention provides an electronic ink prepared by mixing the CuO nanoparticles and an ink solvent.

<14> 본 발명은 상기 전자잉크에 있어서， 상기 잉크용매는 물 30-40 wt%, 에탄올  <14> The present invention is the electronic ink, the ink solvent is 30-40 wt% water, ethanol

(Ethanol) 6-9 wt , 에틸렌 글리콜 (Ethylene Glycol, EG) 22-27wt 및 폴리비닐피 로리돈 (polyvinylpyrrolidone, PVP) 1-3 %인 것을 특징으로 하는 전자잉크를 제 공한다.  (Ethanol) 6-9 wt, ethylene glycol (Ethylene Glycol, EG) 22-27wt and polyvinylpyrrolidone (PVP) provides an electronic ink, characterized in that 1-3%.

<15> 본 발명은 상기 전자잉크에 있어서, 상기 CuO나노입자 농도는 25—35 wt% 것 을 특징으로 하는 전자잉크를 제공한다.  The present invention provides the electron ink, wherein the CuO nanoparticle concentration is 25-35 wt% in the electron ink.

<16> 본 발명은 상기 전자잉크에 있어서， 상기 CuO 나노입자 및 잉크용매는 균질 화기 (Thinky ARE- 100 Conditioning Mixer)를 사용하여 균질화하는 것을 특징으로 하는 전자잉크를 제공한다. The present invention provides the electronic ink, wherein the CuO nanoparticles and the ink solvent are homogenized by using a homogenizer (Thinky ARE-100 Conditioning Mixer).

<17> 본 발명은 상기 전자잉크에 있어서， 에틸렌 글리콜이 CuO를 구리로 환원시키 는 환원제 역할을 하는 것을 특징으로 하는 전자잉크를 제공한다. The present invention provides an electron ink, wherein in the electron ink, ethylene glycol serves as a reducing agent for reducing CuO to copper.

<18> 본 발명은 상기 전자잉크에 있어서， 에틸렌 글리콜은 다른 글리콜 (디에틸렌 글리콜， 프로필렌 글리콜) 기반의 용매도 사용할 수 있는 것을 특징으로 하는 전자 잉크를 제공한다. The present invention provides an electronic ink, wherein in the electronic ink, ethylene glycol can also use a solvent based on other glycols (diethylene glycol, propylene glycol).

<19> 본 발명은 상기 전자잉크의 인쇄방법에 있어서， 상기 전자 잉크를 사용한 박 막 증착은 스핀코팅， 스프레이 프린팅， 잉크펜， 잉크젯 프린팅, 스크린 프린팅， 를 -투-를 (R2R), 옵셋 등을 이용할 수 있는 것을 특징으로 하는 전자잉크를 제공한다. In the printing method of the electronic ink, the thin film deposition using the electronic ink is performed by spin coating, spray printing, ink pen, inkjet printing, screen printing, -to- (R2R), offset, etc. It provides an electronic ink, characterized in that can be used.

<20> 본 발명은 상기 전자잉크의 스핀코팅에 의한 박막제조 과정에 있어서， 상기 전자잉크는 유리기판에 스핀코팅으로 증착된 CuO 박막에 진공상태에서 마이크로파 를 조사하는 것을 특징으로 하는 박막제조 과정을 제공한다. In the present invention, in the thin film manufacturing process by spin coating of the electron ink, the electron ink is microwave in a vacuum state on a CuO thin film deposited by spin coating on a glass substrate. It provides a thin film manufacturing process characterized in that to investigate.

<21 > 본 발명은 상기 전자잉크의 박막제조과정에 있어서， 진공 마이크로파 장비는 마이크로파 발생기를 포함하는 장치를 이용하여 제작한 것을 특징으로 하는 장치를 제공한다. The present invention provides a device characterized in that the vacuum microwave equipment is manufactured using a device including a microwave generator in the thin film manufacturing process of the electronic ink.

<22> 본 발명은 상기 진공마이크로파 장비에 있어서， 압력은 대기압 또는 진공 압 력범위는 1 X 10— 1 내지 1 X 10— 5 Pa를 특징으로 하는 장치를 제공한다. <22> The present invention, in the vacuum microwave equipment, the pressure is atmospheric pressure or a vacuum pressure range provides an apparatus that is characterized by 1 X 10- 1 to 1 X 10- 5 Pa.

<23> 본 발명은 상기 진공마이크로파 장비에 있어서， 마이크로파 조사로 CuO 나노 입자를 포함한 박막은 빠르게 가열되고 박막에 존재하는 에틸렌글리콜도 비등점까 지 가열되는 것을 특징으로 하는 장치를 제공한다. In the vacuum microwave equipment, the present invention provides a device characterized in that a thin film including CuO nanoparticles is rapidly heated by microwave irradiation, and ethylene glycol present in the thin film is heated to a boiling point.

<24> 본 발명은 상기 진공마이크로파 장치에 있어서， 상기 비등점까지 가열된 에 틸렌글리콜이 아세트알데히드를 탈수하는 것을 특징으로 하는 장치를 제공한다. <25> 본 발명은 CuO 나노입자 잉크의 환원 과정에 있어서， 상기 아세트알데히드는 The present invention provides an apparatus, wherein in the vacuum microwave apparatus, ethylene glycol heated to the boiling point dehydrates acetaldehyde. <25> In the present invention, the acetaldehyde in the reduction process of the CuO nanoparticle ink

CuO 나노입자를 환원시켜 순수한 구리 상으로 변화하는 것을 특징으로 하는 환원과 정을 제공하다.  Reducing the CuO nanoparticles to provide a reduction process characterized in that the change to a pure copper phase.

<26> 본 발명은 CuO 나노입자 잉크펜의 제작에 있어서, 상기 전자잉크를 300 팁을 갖는 젤펜을 사용하여 제작하는 CuO 나노입자 젤펜 제작을 제공한다.  The present invention provides a preparation of a CuO nanoparticle gel pen for producing a CuO nanoparticle ink pen, wherein the electronic ink is prepared using a gel pen having a 300 tip.

<27> 본 발명은 CuO 나노입자 잉크펜의 제작에 있어서， 상기 CuO 나노입자 젤펜은 종이， 유리， 폴리머 및 실리콘 기판에 웅용되는 특징으로 하는 젤펜을 제공한다.The present invention provides a gel pen characterized in that the CuO nanoparticle gel pen is used for paper, glass, polymer, and silicon substrates.

<28> 본 발명은 CuO 나노입자 젤펜에 있어서， 상기 CuO 나노입자 젤펜으로 종이에 제작하는 전극을 제공한다. In the CuO nanoparticle gel pen, the present invention provides an electrode fabricated on paper with the CuO nanoparticle gel pen.

<29> 본 발명은 CuO 나노입자 젤펜으로 제작한 전극에 있어서， 상기 나노입자 젤 펜으로 제작한 전극에 마이크로파를 조사한 후 54.31 y Q . cm의 저항을 갖는 것을 제공한다.  In the present invention, an electrode made of a CuO nanoparticle gel pen is provided. The electrode made of the nanoparticle gel pen is irradiated with microwaves at 54.31 y Q. to provide a resistance of cm.

<30> 본 발명은 CuO 나노입자 젤펜으로 제작한 전극에 있어서， 상기 마이크로파 조사 시간이 증가할수록 전기저항이 향상되고， 마이크로파 조사시간이 60초 이상일 경우 저항이 일정한 특징의 전극을 제공한다.  According to the present invention, an electrode made of a CuO nanoparticle gel pen has an electric resistance improved as the microwave irradiation time increases, and provides an electrode having a constant resistance when the microwave irradiation time is 60 seconds or more.

<3 i > 본 발명은 CuO 나노입자 젤펜으로 제작한 전극에 있어서， 상기 CuO 나노입자 젤펜으로 연속 인쇄하여 제작한 전극은 연속인쇄 횟수가 증가할수록 전기저항이 개 선되는 특성을 제공한다.  <3 i> In the electrode made of a CuO nanoparticle gel pen, the electrode produced by continuous printing with the CuO nanoparticle gel pen provides a characteristic that the electrical resistance is improved as the number of continuous printing.

<32> 본 발명은 CuO 나노입자 젤펜으로 제작한 전극에 있어서， 상기 CuO 나노입자 젤펜으로 연속 인쇄하여 제작된 전극에 1분간 마이크로파 조사 후， 연속인쇄는 횟 수가 증가 할수록 박막에 형성된 기공이 채워지며 조밀한 구리 박막이 종이 기판위 에 생성되는 특성을 제공한다. In the present invention, in the electrode made of CuO nanoparticle gel pen, after the microwave irradiation to the electrode produced by continuous printing with the CuO nanoparticle gel pen for 1 minute, the continuous printing is filled with pores formed in the thin film as the number of times increases Dense copper thin film on paper substrate Provide the properties that are created in the.

<33>  <33>

【유리한 효과】  Advantageous Effects

<34> 본 발명은 공정이 단순하고， 비용이 저렴한 용액법으로 CuO 나노입자를 제조 하는 방법을 제공한다. 본 발명은 상기 CuO 나노입자를 소정의 잉크용매와 흔합하 여 경제적이고， 환경 친화적이고， 장기적으로 산화문제가 없고， 상온에서 안정한 잉크를 제조하는 방법을 제공한다. 본 발명은 상기 CuO 나노입자 잉크를 사용하여 기판에 인쇄한 CuO 박막을 마이크로파 조사를 통하여 금속 구리 (Cu) 박막으로 환원 시키는 방법을 제공한다. 또한 본 발명은 상기 CuO 나노입자 잉크로 잉크 젤펜을 제조하는 방법을 제공한다.  The present invention provides a method for producing CuO nanoparticles by a solution method having a simple process and low cost. The present invention provides a method for producing an ink which is economical, environmentally friendly, long-term oxidation-free, and stable at room temperature by mixing the CuO nanoparticles with a predetermined ink solvent. The present invention provides a method for reducing a CuO thin film printed on a substrate using the CuO nanoparticle ink to a metallic copper (Cu) thin film through microwave irradiation. The present invention also provides a method for preparing an ink gel pen with the CuO nanoparticle ink.

【도면의 간단한 설명】  [Brief Description of Drawings]

<35> 도 1은 본 발명의 일실시예에 따른 산화구리 나노입자의 제조방법， 박막증착 및 마이크로파 조사 과정을 나타낸 도면이다.  FIG. 1 is a view illustrating a method for preparing copper oxide nanoparticles, thin film deposition, and microwave irradiation according to an embodiment of the present invention.

<36> 도 2는 본 발명의 일실시예에 따른 산화구리 나노입자 잉크로 유리기판에 스 핀코팅 증착된 박막에 마이크로파 조사 후 단면 FESEM 이미지 및 이에 대웅되는 EDX 분석 결과를 나타낸 것으로 (a) 스핀코팅 증착， (b) 1분 마이크로파 조사, (c) 2분 마이크로파 조사， (d) 3분 마이크로파 조사 및 (e) 4분 마이크로파 조사 결과 를 나타내는 도면이다.  FIG. 2 illustrates a cross-sectional FESEM image and EDX analysis results after microwave irradiation of a thin film spin-coated on a glass substrate with a copper oxide nanoparticle ink according to an embodiment of the present invention (a) spin The figure shows coating deposition, (b) 1 minute microwave irradiation, (c) 2 minutes microwave irradiation, (d) 3 minutes microwave irradiation, and (e) 4 minutes microwave irradiation.

<37> 도 3은 본 발명의 일실시예에 따른 산화구리 나노입자 잉크로 유리기판에 스 핀코팅 증착된 박막에 마이크로파 조사후의 저해상도 및 고해상도 표면 FESEM 이미 지를 나타낸 것으로 (a) 증착， (b) 1분 마이크로파 조사， (c) 2분 마이크로파 조 사， (d) 3분 마이크로파조사 및 (d) 4분 마이크로파 조사 결과를 나타내는 도면이 다.  3 shows low resolution and high resolution surface FESEM images after microwave irradiation on a thin film spin-coated on a glass substrate with a copper oxide nanoparticle ink according to an embodiment of the present invention. 1 minute microwave irradiation, (c) 2 minutes microwave irradiation, (d) 3 minutes microwave irradiation and (d) 4 minutes microwave irradiation.

<38> 도 4는 본 발명의 일실시예에 따른 산화구리 나노입자 잉크로 유리기판에 스 핀코팅 증착된 박막에 마이크로파 조사 후 표면 EDX 분석에 의한 원소 조성 비교 그래프를 나타낸 도면이다.  4 is a graph showing an element composition comparison graph by surface EDX analysis after microwave irradiation of a thin film spin-coated on a glass substrate with a copper oxide nanoparticle ink according to an embodiment of the present invention.

<39> 도 5는 본 발명의 일실시예에 따른 산화구리 나노입자 잉크로 유리기판에 스 핀코팅 증착된 박막에 마이크로파조사 후 X선 희절 그래프를 나타낸 도면이다. FIG. 5 is a graph showing X-ray emission graphs after microwave irradiation on a thin film spin-coated deposited on a glass substrate with a copper oxide nanoparticle ink according to an embodiment of the present invention.

<40> 도 6은 본 발명의 일실시예에 따론 산화구리 나노입자 잉크로 유리기판에 스 핀코팅 증착된 박막에 마이크로파 조사 후 (a) 4침법 (4-point probe)으로 측정한 전기 저항 및 (b) 계산 전기 저항을 나나내는 도면이다. 6 is an electrical resistance measured by a 4-point probe after microwave irradiation of a thin film spin-coated deposited on a glass substrate with a copper oxide nanoparticle ink according to an embodiment of the present invention and ( b ) It is a figure which shows calculation electric resistance.

<41> 도 7은 본 발명의 일실시예에 따른 젤펜에 산화구리 나노입자 잉크 웅용, 종 이 기판에 박막 증착 및 마이크로파 조사 방법을 나타내는 도면이다. 7 is a copper oxide nanoparticles ink for the gel pen according to an embodiment of the present invention, species It is a figure which shows the method of thin film vapor deposition and a microwave irradiation to this board | substrate.

<42> 도 8은 본 발명의 일실시예에 따른 종이 기판에 산화구리 나노입자 젤펜으로 제작하는 전극 도면이다. FIG. 8 is an electrode diagram of a copper oxide nanoparticle gel pen on a paper substrate according to an embodiment of the present invention.

<43> 도 9와 도 10은 본 발명의 일실시예에 따른 종이 기판에 산화구리 나노입자 잉 크펜으로 제작한 전극에 마이크로파를 조사하여 2침법 (2-point probe)으로 전기저 항을 계산한 도면이다. 9 and 10 illustrate the electrical resistance of a paper substrate according to one embodiment of the present invention obtained by irradiating microwaves to an electrode made of a copper oxide nanoparticle ink pen using a 2-point probe. Drawing.

<44> 도 11은 본 발명의 일실시예에 따른 종이 기판에 산화구리 나노입자 젤펜으로 제작된 전극의 2포인트 프로브 (2-point probe)로 전기 저항 측정 및 계산한 도면이 다.  FIG. 11 is a diagram illustrating electrical resistance measurements and calculations using a 2-point probe of an electrode made of a copper oxide nanoparticle gel pen on a paper substrate according to an embodiment of the present invention.

<45> 도 12은 본 발명의 일실시예에 따른 종이 기판에 산화구리 나노입자 젤펜으로 제작된 전극에 1분간 마이크로파 조사 후 구조적 변화에 대한 표면 및 단면 FESEM 이미지를 나타낸 도면이다. ( 1) 1회 인쇄 (2) 2회 연속 인쇄 (3) 3회 연속 인쇄를 나타낸다.  12 illustrates surface and cross-sectional FESEM images of structural changes after 1 minute microwave irradiation on an electrode made of a copper oxide nanoparticle gel pen on a paper substrate according to an embodiment of the present invention. (1) One time print (2) Two times continuous printing (3) Three times continuous printing is shown.

<46> 도 13는 본 발명의 일실시예에 따른 종이 기판에 젤펜으로 제작된 전극의 광 학 및 FESEM 이미지를 나타낸 도면이다.  FIG. 13 is a view showing optical and FESEM images of an electrode made of a gel pen on a paper substrate according to an embodiment of the present invention.

<47>  <47>

<48> <48>

【발명의 실시를 위한 형태】  [Form for implementation of invention]

<49> 본 발명의 일실시예는 간단한 용액법으로 CuO 나노입자를 제조하는 방법을 제공한다.  One embodiment of the present invention provides a method for preparing CuO nanoparticles by a simple solution method.

<50> 상기 CuO 나노입자는 초산구리를 선구 물질로 하여 저은 용액법으로 합성한 다 본 발명의 일실시예는 초산구리 수용액에 초산 수용액을 흔합하는 1단계， 상기 1단계의 결과물을 90°C로 가열하고， 환류 (Ref lux)하는 2단계 및 상기 2단계의 결과 물의 온도가 90°C에 이를 때 수산화나트륨 (NaOH)를 첨가하는 3단계， 상기의 반응 액을 초음파처리한 후 원심분리 및 세척하는 제 4단계를 포함하는 것을 특징으로 하 는 CuO 나노입자의 제조방법을 제공한다. The CuO nanoparticles are synthesized by a low solution solution using copper acetate as a precursor. In one embodiment of the present invention, a step of mixing acetic acid solution in an aqueous copper acetate solution, the resultant of the first step is 90 ° C. Heating to reflux and refluxing step 2 and step 3 adding sodium hydroxide (NaOH) when the temperature of the water reaches 90 ° C., sonicating the reaction solution, followed by centrifugation and It provides a method for producing CuO nanoparticles comprising the fourth step of washing.

<5 1 > 또한 상기의 방법으로 만들어진 CuO 나노입자에 용매를 첨가하여 전자잉크를 만드는 단계와， 이를 박막으로 증착하는 단계와， 증착된 박막을 건조시키는 단계 와， 증착된 CuO 박막을 진공상태에서 마이크로파를 조사하여 소결시켜 Cu 박막으로 만드는 단계로 구성된다. 상기의 반응액을 균질화시키고 초음파처리한 후 원심분리 및 세척하는 단계를 포함하는 것을 특징으로 하는 CuO 나노입자 잉크의 제조방법을 제공한다. <52> 또한 상기의 방법으로 만들어진 CuO 나노입자 잉크를 박막으로 증착하는 단 계와, 증착된 박막을 건조시키는 단계와， 증착된 CuO 박막을 진공상태에서 마이크 로파를 조사하여 소결시켜 Cu 박막으로 만드는 단계로 구성된다. <5 1> In addition, by adding a solvent to the CuO nanoparticles made by the above method to form an electronic ink, depositing it as a thin film, drying the deposited thin film, and depositing the deposited CuO thin film under vacuum It consists of irradiating microwaves and sintering them into Cu thin films. It provides a method for producing a CuO nanoparticle ink comprising the step of homogenizing and sonicating the reaction solution and centrifugation and washing. In addition, the step of depositing the CuO nanoparticle ink made by the above method as a thin film, the step of drying the deposited thin film, and sintering the deposited CuO thin film by microwave irradiation in a vacuum to form a Cu thin film It consists of steps.

<53> 도 1은 상술한 1단계 내지 3단계를 나타내는 도면으로 산화구리 나노입자를 합성하는 방법， 전자잉크를 배합 및 마이크로파 조사 과정을 나타낸다.  FIG. 1 is a diagram showing steps 1 to 3 described above showing a method of synthesizing copper oxide nanoparticles, an electron ink formulation, and a microwave irradiation process.

<54> 본 실시예의 제조방법을 구체적으로 살펴보면 다음과 같다. 100 ml의 0.02 M 초산구리 수용액과 0.5 ml의 35% 초산 수용액을 실온에서 교반하면서 흔합용액을 준비한다. ( 1단계) 초산구리 수용액과 초산 수용액의 흔합물을 환류 반웅기에서 천천히 가열하면서 잘 저어준다 (2단계) . 흔합물의 가열 온도는 90°C 내지 120°C로 하는 것이 바람직하며， 본 실시예에서는 90°C의 온도로 가열하였다. 흔합물의 은도 가 90°C가 되면， 흔합물에 0.5 g의 금속수산화물 팰릿 (Pal let )을 첨가한다. 상기 금속수산화물은 LiOH, NaOH, K0H , RbOH 또는 CsOH 팰릿을 사용할 수 있으며， 본 실 시예에서는 NaOH ¾릿을 첨가하였다. 이때， 검은색의 용액이 생성되는데 (3단계)ᅳ 이러한 색의 변화를 통해 CuO 나노입자의 형성이 이루어지는 것을 확인할 수 있다. 상기 온도 반웅시간， 농도 둥 반웅조건들은 일실시예에 불과할 뿐， 본 발명의 기 술적 사상을 모두 대변하는 것은 아니다. Looking at the manufacturing method of the present embodiment in detail. A mixed solution is prepared while stirring 100 ml of 0.02 M copper acetate solution and 0.5 ml of 35% acetic acid aqueous solution at room temperature. (Step 1) Stir well the mixture of copper acetate solution and acetic acid solution while heating slowly under reflux reaction (Step 2). The heating temperature of the mixture is preferably set to 90 ° C to 120 ° C, in this embodiment was heated to a temperature of 90 ° C. When the silver content of the mixture reaches 90 ° C, 0.5 g of metal hydroxide Pal let is added to the mixture. The metal hydroxide may be LiOH, NaOH, K0H, RbOH or CsOH pallet, in this embodiment was added NaOH ¾lets. At this time, a black solution is produced (step 3). It can be seen that the formation of the CuO nanoparticles is made through such a color change. The temperature reaction time, concentration reaction conditions are only one embodiment, and do not represent all of the technical ideas of the present invention.

<55> 10분 내지 15분의 환류 후에 검은색 콜로이드 용액을 15분간 초음파  <55> Ultrasonic black colloid solution for 15 minutes after reflux for 10 to 15 minutes

(ul trasoni cate) 처리한다. 그 결과물을 3000 rpm에서 2분간 원심분리하고 물과 에 탄올 (Ethanol )로 세척하면 검은색의 콜로이드 상태의 CuO 나노입자가 얻어진다. 얻 어진 CuO 나노입자의 크기는 5 내지 8 nm이다.  (ul trasoni cate) process. The resultant was centrifuged at 3000 rpm for 2 minutes and washed with water and ethanol to obtain black colloidal CuO nanoparticles. The size of the obtained CuO nanoparticles is 5 to 8 nm.

<56> 상기 CuO를 잉크용매와 흔합하여 제조한 전자잉크를 제공한다. 상기 잉크용 매는 물， 에탄올 (Ethanol ) , 에틸렌 글리콜 (Ethylene glycol ) 및 폴리비닐피로리돈 (Polyvinylpyrrol idone)의 흔합으로 제조할 수 있지만 이에 한정되는 것은 아니다. 전자잉크 제조시 잉크용매는 물 30-40 , 에탄올 6-9w%, EG 22-27w%, PVP 1-3^로 흔합한다. CuO 나노입자와 에틸렌클리콜은 1. 15 : 1의 비율로 잉크를 제조한다. 바람 직하게는， CuO 나노입자， 물， 에탄올， 에틸렌글리콜 및 폴리비닐피로리돈이 각각 29.0 : 36.4: 7.3 :25.5 : 1.8의 wt % (질량 비율)로 흔합될 수 있지만， 이에 한정되는 것 은 아니다. 상기 전자잉크 흔합물은 호모게나이저 (Thinky ARE- 100 Condi t ioning Mixer )에서 2분간 2000 rpm으로 균질화 된다. 에틸렌글리콜은 CuO 가 구리로 변환 할 수 있도록 환원제 역할을 하는데, 다른 글리콜 기반의 용매도 사용할 수 있다. An electronic ink prepared by mixing CuO with an ink solvent is provided. The ink solvent may be prepared by mixing water, ethanol, ethylene glycol, and polyvinylpyrrolidone, but are not limited thereto. In preparing electronic ink, the ink solvent is 30-40, ethanol 6-9w%, EG 22-27w%, and PVP 1-3 ^. CuO nanoparticles and ethylene glycol are prepared in an ink ratio of 1.15: 1. Preferably, CuO nanoparticles, water, ethanol, ethylene glycol and polyvinylpyrrolidone may be combined with, but not limited to, wt% (mass ratio) of 29.0: 36.4: 7.3: 25.5: 1.8, respectively. . The electronic ink mixture is homogenized at 2000 rpm for 2 minutes in a homogenizer (Thinky ARE-100 Conditon ionizing Mixer). Ethylene glycol acts as a reducing agent to convert CuO to copper. Other glycol-based solvents can be used.

<57> 상기 CuO 나노입자 잉크는 기판위에 스핀코팅으로 박막을 만든다 . 사용하는 기판은 유리， 종이， 섬유， 실크， 폴리머， 실리콘 등을 사용할 수 있다. 상기 CuO 나노입자 잉크를 사용한 박막 증착은 스핀코팅， 스프레이 프린팅， 잉크펜， 잉크젯 프린팅 (Ink-jet printing), 스크린 프린팅 (screen printing) 등을 이용할 수 있다. 증착된 박막은 물, 에탄올과 같은 비등점이 낮은 용매를 증발시키기 위해 건조시킨 다. 증착된 CuO 박막을 Cu 박막으로 만들기 위해 대기압 또는 진공상태에서 마이크 로파 조사 한다. 진공 압력 범위는 1X10— 1 내지 1X10 Pa 이며， 일실시예에서 사 용한 진공은 3.5X10 Pa이다. 진공 마이크로파 장비는 가전용 전자레인지를 이용 하여 제작하였다. 마이크로파 조사로 CuO 나노입자를 포함한 박막은 빠르게 가열되 고 박막에 존재하는 에틸렌글리콜도 비등점까지 가열된다. 에틸렌 글리콜의 비등점 에 도달하면 생성되는 아세트알데히드 (C¾CH0)를 탈수한다. 아세트알데히드는 CuO 나노입자를 환원시켜 순수한 Cu상으로 변환한다. 조밀하고 서로 연결되는 Cu 박막 을 만들기 위해 마이크로파의 지속적인 조사가 필요하다. 마이크로파에 의한 환원 반웅은 다음과 같다. The CuO nanoparticle ink makes a thin film by spin coating on a substrate. The substrate to be used may be glass, paper, fiber, silk, polymer, silicon, or the like. CuO Thin film deposition using nanoparticle ink may use spin coating, spray printing, ink pen, ink-jet printing, screen printing, and the like. The deposited thin film is dried to evaporate low boiling solvents such as water and ethanol. In order to make the deposited CuO thin film into Cu thin film, microwave irradiation was performed under atmospheric pressure or vacuum. The vacuum pressure range is 1 × 10—1 to 1 × 10 Pa, and the vacuum used in one embodiment is 3.5 × 10 Pa. Vacuum microwave equipment was produced using a microwave oven. Microwave irradiation heats up thin films containing CuO nanoparticles quickly and heats the ethylene glycol present in the thin films to the boiling point. When the boiling point of ethylene glycol is reached, the resulting acetaldehyde (C¾CH0) is dehydrated. Acetaldehyde converts CuO nanoparticles into pure Cu phase. In order to produce dense, interconnected Cu films, continuous irradiation of microwaves is required. Reduction reaction by microwave is as follows.

<58> 2CH20HCH20H→2CH3CH0+2H20 ( i ) <58> 2CH 2 0HCH 2 0H → 2CH 3 CH0 + 2H 2 0 (i)

<59> 2CH3CHO+CuO→Cu0+CH3COCOCH3+H20 .(ii) 2CH 3 CHO + CuO → Cu 0 + CH 3 COCOCH 3 + H 2 0. (Ii)

<60> 도 2는 본실시예의 CuO 나노입자 잉크로 유리기판에 스핀코팅 증착된 박막에 마이크로파 조사 후 단면 FESEM 및 이에 대웅되는 EDX 분석 결과를 나타낸 도면이 다. 도 3(aᅳ 1)는 증착된 산화구리 박막의 FESEM 이미지로 증착된 박막의 두께가 4 내지 5 μπι임을 나타낸다. 도 2(a-2) 및 도 2(a-3)는 증착된 박막의 원소조성을 나타 낸다. 구리 (a-2)와 산소 (a-3)의 두께가 4 내지 5μπι로 증착된 박막의 두께와 동일 함을 나타낸다. 도 2(b-l), (b-2) 및 (b-3)는 본 실시예의 증착된 산화구리 박막에 1분간 마이크로파를 조사 후 단면 FESEM 및 EDX 결과이다. 상층부는 환원 및 소결 된 구리 상으로 0.5 내지 0.65iim 이하의 두께를 나타낸다. 하층부에는 환원되지 못한 CuO층이 존재함을 나타낸다. 도 2(c-l), (c-2) 및 (c-3)는 증착된 CuO 박막에 2분간 마이크로파를 조사 후 단면 FESEM 및 EDX 결과이다. 마이크로파 조사 시간이 증가함에 따라， 1 내지 2μπι두께를 갖는 박막은 대부분 환원 및 소결되어 산소 (0) 상 (cᅳ 3) 없이 Cu상 (c-2)만 나타낸다. 도 3(d-e)는 마이크로파 조사 시간을 더 증가 시킨 결과 Cu 금속 상의 환원 및 소결됨을 나타낸다. 산소 원소가 검출 되는 것은 유리기판에 포함된 산소가 검출되는 것이다. 2분간 조사한 마이크로파는 박막의 2 ym 까지 침투할 수 있음이 확인 되었다. 마이크로파 조사 시간의 증가로 더 두꺼 운 CuO박막을 환원 및 소결 할 수 있다. <6 i > 도 3은 본 실시예에 따른 CuO 나노입자 잉크로 유리기판에 스핀코팅 증착된 박막에 마이크로파 조사후의 저해상도 및 고해상도 표면 FESEM 이미지를 나타낸다. 일반적으로 전도성 박막은 Cu 나노입자 간 3차원 상호 전도 경로가 있어야 한다. 전도 경로는 1분간 마이크로파 조사 후 부터 나타난다. 도 3(a)는 작고 구형의 나노 입자들을 나타낸다. 도 3(b)는 1분간 마이크로파를 조사한 후 나노입자가 연속적이 며 소결된 입자 형상으로 변화를 나타낸다. 도 3(c-e)는 마이크로파 조사 시간 증가 할수록 박막은 조밀하고 입자들은 연합하여 성장함을 나타낸다. 2 is a view showing a cross-sectional FESEM and EDX analysis results after microwave irradiation on a thin film spin-coated on a glass substrate with the CuO nanoparticle ink of the present embodiment. FIG. 3 (a ′ 1) shows that the thickness of the deposited thin film is 4 to 5 μπι in the FESEM image of the deposited copper oxide thin film. 2 (a-2) and 2 (a-3) show the elemental composition of the deposited thin film. It shows that the thickness of copper (a-2) and oxygen (a-3) is equal to the thickness of the thin film deposited with 4 to 5μπι. 2 (bl), (b-2) and (b-3) are cross-sectional FESEM and EDX results after 1 minute microwave irradiation of the deposited copper oxide thin film of this example. The upper layer shows a thickness of 0.5 to 0.65iim or less with the reduced and sintered copper phase. The lower layer shows that the CuO layer which was not reduced exists. 2 (cl), (c-2) and (c-3) are cross-sectional FESEM and EDX results after 2 minutes of microwave irradiation on the deposited CuO thin film. As the microwave irradiation time increases, most thin films having a thickness of 1 to 2 mu πι are reduced and sintered to show only the Cu phase (c-2) without the oxygen (0) phase (c ᅳ 3). 3 (de) shows the reduction and sintering of the Cu metal phase as a result of further increasing the microwave irradiation time. The oxygen element is detected by detecting oxygen contained in the glass substrate. The microwave irradiated for 2 minutes was found to penetrate up to 2 ym of the thin film. Increased microwave irradiation time can reduce and sinter thicker CuO thin films. FIG. 3 shows a low resolution and high resolution surface FESEM image after microwave irradiation in a thin film spin-coated on a glass substrate with CuO nanoparticle ink according to the present embodiment. In general, conductive thin films must have a three-dimensional interconducting path between Cu nanoparticles. The conduction path appears after 1 minute of microwave irradiation. 3 (a) shows small, spherical nanoparticles. Figure 3 (b) shows the change in nanoparticles continuous and sintered particle shape after 1 minute microwave irradiation. 3 (ce) shows that as the microwave irradiation time increases, the thin film becomes dense and the particles grow in association.

<62> 도 4는 본실시예에 따른. CuO 나노입자 잉크로 유리기판에 스핀코팅 증착된 박 막에 마이크로파 조사 후 표면 EDX 분석에 의한 원소 조성 비교 그래프를 나타낸 도면이다. 1분간 마이크로파 조사 후 표면 원소 조성은 90 % 이상의 Cu 상과 7 내 지 8 %의 산소 상이 검출되었다. 에틸렌글리콜에 의한 탄소 (C)가 1.7 % 검출 되었 다. 긴 시간 마이크로파를 조사할 경우 탄소 및 산소의 상이 없이 100%의 Cu 상이 검출 되었다.  4 is according to this embodiment. A graph showing element composition comparison by surface EDX analysis after microwave irradiation on a thin film spin-coated on a glass substrate with CuO nanoparticle ink. After 1 minute of microwave irradiation, more than 90% Cu phase and 7-8% oxygen phase were detected. 1.7% carbon (C) was detected by ethylene glycol. When irradiated with microwaves for a long time, 100% of Cu phases were detected without phases of carbon and oxygen.

<63> 도 5는 본 실시예에 따른 CuO 나노입자 잉크로 유리기판에 스핀코팅 증착된 박막에 마이크로파 조사 후 조사시간 변화에 따른 X선 회절 그래프를 나타낸다. 증 착된 CuO 박막에서 관찰된 XRD 회절 피크는 CuO 단사정계 상을 나타낸다. CuO 특성 피크를 제외한 다른 불순물 또는 산화구리 ( I ) (Cu20) 수산화구리 ( I I ) (Cu(0H)2)같은 다른 결정상 피크들은 관찰되지 않았다. 증착된 CuO 나노 입자는 고순도의 결정질 임을 나타낸다. 1분 내지 4분의 마이크로파를 조사한 후 모든 회절 피크는 2 Θ = 43.26 , 50.2 및 74.4로 큐빅상 순수 Cu의 평면인 ( 111)， (200) , (220) 상의 결과이 다. 강하고 날카로운 피크는 Cu 나노입자의 높은 결정질 및 소결이 잘 되었음을 나 타낸다. FIG. 5 shows an X-ray diffraction graph according to a change in irradiation time after microwave irradiation on a thin film spin-coated on a glass substrate with CuO nanoparticle ink according to the present embodiment. The XRD diffraction peaks observed in the deposited CuO thin film show the CuO monoclinic phase. Other impurities except CuO characteristic peaks or other crystal phase peaks such as copper oxide (I) (Cu 2 0) copper hydroxide (II) (Cu (0H) 2 ) were not observed. The deposited CuO nanoparticles show high purity crystalline. After irradiating microwaves for 1 to 4 minutes, all diffraction peaks are the results on (111), (200) and (220) planes of cubic pure Cu, with 2Θ = 43.26, 50.2 and 74.4. Strong, sharp peaks indicate good crystallinity and good sintering of the Cu nanoparticles.

<64> 도 6은 본 발명의 일실시예에 따른 CuO 나노입자 잉크로 유리기판에 스핀코팅 증착된 박막에 마이크로파 조사 후 (a) 4침법 (4-point probe)으로 측정한 전기 저 항 (R) 및 (b) 저항도 ( p )를 나나내는 도면이다. 마이크로파 조사 박막의 전기 저항 도는 다음 식을 이용하여 계산한다. p = RA/L , 여기서 R, A 및 L은 각각 저항， 증 착된 박막의 넓이 및 길이를 나타낸다. 증착된 박막은 ~102Ω . αιι의 전기 저항을 갖 는 것을 나타낸다. 1분 내지 4분간 마이크로파를 조사 후 전기저항은 실질적으로 향상되고, 3분 이상 조사할 경우 전기저항이 4.65 Q . cm로 bulk 상태보다 2 내지 3 배 높은 저항을 나타낸다. FIG. 6 is an electrical resistance (R) measured by a 4-point probe after microwave irradiation of a thin film spin-coated on a glass substrate with CuO nanoparticle ink according to an embodiment of the present invention (R). ) And (b) resistance (p). The electrical resistivity of the microwave irradiation thin film is calculated using the following equation. p = RA / L, where R, A and L represent the resistivity, the width and length of the deposited thin film, respectively. The deposited film was ~ 10 2 Ω. It has an electrical resistance of αιι. After 1 minute to 4 minutes of microwave irradiation, the electrical resistance is substantially improved. In cm, the resistance is 2 to 3 times higher than the bulk state.

<65> ᅳ도 7은 본실시예에 따른 젤펜에 CuO 나노입자 잉크 응용， 종이 기판에 박막 증착 및 마이크로파 조사 방법을 나타낸다. 도 2의 잉크배합에 따라 제조된 CuO 나 노입자 잉크를 사용하여 젤펜을 제작한다. 젤펜은 300 μ ηι 팁을 갖는 젤 펜 (동아제 품)을 사용하였다. CuO 나노잉크를 채우기 전에 젤펜의 통과 팁을 물과 에탄올 하 에서 초음파처리 하여 상용잉크를 제거한다. 상용잉크가 제거된 젤펜에 CuO 나노입 자 잉크를 주사기를 사용하여 바닥부터 채워준다. 종이기판에 CuO 나노입자 박막을 작성하는데 젤펜을 사용한다. 제작된 젤펜은 종이기판뿐 아니라 유리, 폴리머， 실 리콘 기판에도 사용 가능하다. 작성된 CuO 박막은 진공상태에서 마이크로파 조사에 의해 소결되어 Cu 박막이 제작된다. 7 illustrates a method of applying CuO nanoparticle ink to a gel pen according to the present embodiment, depositing a thin film on a paper substrate, and microwave irradiation. CuO prepared according to the ink formulation of Figure 2 Gel pens are made using old particle ink. Gel pens were used gel pens (Dong-A Co., Ltd.) having a 300 μηι tip. Before filling the CuO nanoink, the pen tip of the gel pen is sonicated under water and ethanol to remove the commercial ink. Fill the gel pen with the commercial ink removed from the bottom using a syringe with CuO nanoparticle ink. Gel pens are used to create CuO nanoparticle thin films on paper substrates. The gel pen can be used not only for paper substrates but also for glass, polymer and silicon substrates. The formed CuO thin film is sintered by microwave irradiation in a vacuum state to produce a Cu thin film.

<66> 도 8은 본 실시예에 따른 종이 기판에 CuO 나노입자 젤펜으로 제작하는 전극 의 예를 나타낸다. 길이 16 mm , 폭 2隱의 전극을 젤펜으로 작성하여 형태， 전기적 특성 등 전극의 성능을 확인한다.  FIG. 8 shows an example of an electrode made of CuO nanoparticle gel pen on a paper substrate according to the present embodiment. A 16 mm long, 2 隱 wide electrode was prepared with a gel pen to check the performance of the electrode, including its shape and electrical properties.

<67> 도 9와 도 10은 본 발명의 일실시예에 따른 종이 기판에 CuO 나노입자 잉크펜 으로 제작한 전극에 마이크로파를 조사하여 (a) 2침법 (2-point probe)으로 측정한 전기 저항 (R) 및 (b) 저항도 ( p )를 나타내는 도면이다. 작성된 전극의 저항도 ( p ) 는 다음 식으로 계산된다. p = RA/L , 여기서 R, A 및 L은 각각 전극의 저항， 넓이 및 길이를 나타낸다. 작성된 전극에 10초간 마이크로파 조사 후 저항은 ~ 363. 12 Ω . αη이다. 20 내지 120초 마이크로파 조사 후 전기저항은 향상되고, 60초 이후로 는 일정하다. 저항은 - 54.31 Ω . ατι로 구리의 전기비저항에 32배 높게 나타난다. 9 and 10 illustrate an electrical resistance measured by a 2-point probe by irradiating microwaves to an electrode made of a CuO nanoparticle ink pen on a paper substrate according to an embodiment of the present invention. It is a figure which shows (R) and (b) resistance degree (p). The resistance p of the prepared electrode is calculated by the following equation. p = RA / L, where R, A and L represent the resistance, width and length of the electrode, respectively. After 10 seconds of microwave irradiation on the electrode, the resistance is ~ 363. 12 Ω. αη. After 20 to 120 seconds microwave irradiation, the electrical resistance is improved, it is constant after 60 seconds. The resistance is-54.31 Ω. ατι, which is 32 times higher than the electrical resistivity of copper.

<68> 도 11은 본 실시예에 따른 종이 기판에 CuO 나노입자 젤펜으로 연속 인쇄하여 제작한 전극의 2침법 (2-point probe)으로 측정한 전기 저항 (R) 및 저항도 ( p )를 나 타낸다. 각 연속 인쇄 방법은 진공 상태에서 2분간 마이크로파 조사 후 진행된다. 도 11은 연속 인쇄 횟수가 증가할수록 전기저항이 개선됨을 나타낸다. 또한 3회 이 상 연속 인쇄 할 경우 저항은 10 Ω . ατι로 일정하고， 이 값은 벌크 (Bulk) 상태보다 6배 높은 값이다. FIG. 11 shows electrical resistance (R) and resistance (p) measured by a 2-point probe of an electrode manufactured by continuously printing a CuO nanoparticle gel pen on a paper substrate according to the present embodiment. To burn. Each continuous printing method is carried out after 2 minutes of microwave irradiation in a vacuum state. 11 shows that the electrical resistance improves as the number of continuous prints increases. Also, when printing more than 3 times continuously, the resistance is 10 Ω. Constant at ατι, which is six times higher than the bulk state.

<6 > 도 12은 본 발명의 일실시예에 따른 종이 기판에 CuO 나노입자 젤펜으로 제작 된 전극에 1분간 마이크로파 조사 후 구조적 변화에 대한 표면 및 단면 FESEM 이미 지를 나타낸다. 연속 인쇄 횟수가 증가 할수록 박막에 형성된 기공이 채워지며 작 고 조밀한 구리 박막이 종이 기판위에 생성되는 것을 나타낸다. 표면 및 단면 FESEM 이미지는 지금까지 관찰된 전기적 특성을 뒷받침 한다.  FIG. 12 illustrates surface and cross-sectional FESEM images of structural changes after 1 minute microwave irradiation on electrodes made of CuO nanoparticle gel pens on a paper substrate according to an embodiment of the present invention. As the number of consecutive prints increases, the pores formed in the thin film are filled, indicating that a small, dense copper thin film is formed on the paper substrate. Surface and cross-sectional FESEM images support the electrical properties observed so far.

<70> 도 13는 본 실시예에 따른 종이 기판에 젤펜으로 제작된 전극의 광학 사진 및  13 is an optical photograph of an electrode made of a gel pen on a paper substrate according to the present embodiment;

FESEM 이미지를 나타낸다. 1분간 마이크로파 조사 후 작성된 전극은 금속 Cu의 색 과 균일한 인쇄 특징을 나타낸다.  Represents a FESEM image. Electrodes prepared after 1 minute microwave irradiation show the color and uniform printing characteristics of the metal Cu.

<71 > 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미 로 한정해서 해석되어서는 아니 되며， 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다. 본 명세서에 기재된 실시예와 도면에 도시된 구성은 본 발명의 가장 바람직한 일실시예에 불과할 뿐이고， 본 발명의 기술적 사상을 모 두 대변하는 것은 아니므로， 본 출원시점에 있어서 이 들을 대체할 수 있는 다양한 균등물과 변형예 들이 있을 수 있다. As used in this specification and claims, the terms or words used herein have a conventional or dictionary meaning It should not be construed as limited to, but should be construed as meaning and concept corresponding to the technical idea of the present invention. Configurations shown in the embodiments and drawings described herein are only one of the most preferred embodiments of the present invention, and do not represent all of the technical idea of the present invention, which can be replaced at the time of the present application There may be various equivalents and variations.

【산업상 이용가능성】  Industrial Applicability

<72> 본 발명은 잉크의 생산 및 그에 따른 구리의 회수에 관한 기술로서， 잉크의 생산 및 재활용 산업에 이용가능하다.  The present invention is a technique relating to the production of ink and thus the recovery of copper, and is applicable to the production and recycling industry of ink.

<73>  <73>

<74> <74>

Claims

【청구의 범위】 [Range of request] 【청구항 11  [Claim 11 초산구리 수용액과 초산 수용액을 실온에서 교반하여 흔합용액을 준비하는 제 1단계와， 초산구리 수용액과 초산 수용액의 흔합물을 환류 반웅기에서 가열하면 서 교반하는 제 2단계와. 상기 흔합물에 금속수산화물 팰릿을 첨가하여 검은색의 콜 로이드 형태의 용액을 생성시키는 제 3단계와， 상기의 반응액을 초음파처리한 후 원 심분리 및 세척하는 제 4단계를 포함하는 것을 특징으로 하는 CuO 나노입자의 제조 방법.  A first step of preparing a mixed solution by stirring the copper acetate aqueous solution and the aqueous acetic acid solution at room temperature, and a second step of stirring the mixed mixture of the copper acetate aqueous solution and the acetic acid aqueous solution in a reflux reactor. And adding a metal hydroxide pallet to the mixture to produce a black colloidal solution, and a fourth step of centrifuging and washing the ultrasonically reacted reaction solution. CuO nanoparticles manufacturing method. 【청구항 2]  [Claim 2] 제 1항에 있어서， CuO 나노입자는 0.02M 초산구리 수용액 100ml에 초산 0.5ml를 흔 합하여 교반하에 천천히 90 °C로 가열하는 것을 특징으로 하는 CuO 나노입자의 제 조방법 . The method for producing CuO nanoparticles according to claim 1, wherein the CuO nanoparticles are mixed with 100 ml of 0.02 M aqueous copper acetate solution and 0.5 ml of acetic acid and slowly heated to 90 ° C. under stirring. 【청구항 3]  [Claim 3] 제 1항에 있어서， 금속수산화물 팰릿은 LiOH , NaOH , K0H , RbOH 또는 CsOH의 팰릿 중에서 선택된 어느하나인 것을 특징으로 하는 CuO 나노입자의 제조방법. The method of claim 1, wherein the metal hydroxide pallet is any one selected from among a pallet of LiOH, NaOH, K0H, RbOH or CsOH. 【청구항 4】  [Claim 4] 제 1항에 있어서， 상기 온도가 90°C에 도달 후 0.4—0.6 g 금속수산화물 팰렛을 첨 가하여 CuO 나노입자를 포함한 검은색 콜로이드 용액을 얻는 것을 특징으로 하는 CuO 나노입자의 제조방법 . The method for producing CuO nanoparticles according to claim 1, wherein after the temperature reaches 90 ° C., a 0.4-0.6 g metal hydroxide pallet is added to obtain a black colloidal solution including CuO nanoparticles. 【청구항 5】  [Claim 5] 제 1항에 있어서， 콜로이드 형태의 CuO 나노입자는 10분 내지 15분간 90 °C에서 환 류 후 15분간 초음파처리하는 것을 특징으로 하는 CuO 나노입자의 제조방법 . The method of claim 1, wherein the colloidal CuO nanoparticles are sonicated for 15 minutes after refluxing at 90 ° C. for 10 minutes to 15 minutes. 【청구항 6]  [Claim 6] 제 1항에 있어서, 상기 CuO 나노입자를 1-3분간 2500-3500rpm에서 1-3회 원심분리 하여 증류수 또는 에탄을로 세척하는 것을 특징으로 하는 CuO 나노입자의 제조방 The method for preparing CuO nanoparticles according to claim 1, wherein the CuO nanoparticles are centrifuged 1-3 times at 2500-3500 rpm for 1-3 minutes to wash with distilled water or ethane. 【청구항 7] [Claim 7] 제 1항에 있어서， 초산소다와 초산을 균일하게 분산시켜 CuO 나노입자의 형성에 방 해되는 침전물을 분쇄시키는 것을 특징으로 하는 CuO 나노입자 제조방법. The method for producing CuO nanoparticles according to claim 1, wherein the precipitate which is prevented from forming CuO nanoparticles is pulverized by dispersing sodium acetate and acetic acid uniformly. 【청구항 8]  [Claim 8] CuO와 초산을 주성분으로 반웅시켜 만들어진 CuO 나노입자.  CuO nanoparticles made by reacting CuO and acetic acid as main components. 【청구항 9】 제 8항에 있어서， CuO 나노입자는 용액법으로 만들어진 5nm 내지 8歷의 직경을 갖 는 것을 특징으로 하는 CuO 나노입자. [Claim 9] The CuO nanoparticles of claim 8, wherein the CuO nanoparticles have a diameter of 5 nm to 8 μs made by a solution method. 【청구항 10】  [Claim 10] 제 1항 내지 제 9항 중 어느 한 항에 의해 만든 CuO 나노입자와 잉크 용매를 흔합하 여 균질화한 후 전자잉크를 만드는 것을 특징으로 하는 CuO 나노입자 전자잉크의 제조방법. A method for producing a CuO nanoparticle electronic ink, wherein the CuO nanoparticles according to any one of claims 1 to 9 and an ink solvent are mixed and homogenized to form an electronic ink. 【청구항 111  [Claim 111] 제 10항에 있어서， 잉크용매는 물 3()-40w%, 에탄을 6-9\ , EG 22-27w%, PVP l-3w 로 구성되는 것을 특징으로 하는 CuO 나노입자 전자잉크의 제조방법. The method of claim 10, wherein the ink solvent comprises water 3 ()-40w%, ethane 6-9 \, EG 22-27w%, PVP 1-3w. 【청구항 12】  [Claim 12] 제 10항에 있어서, CuO 나노입자는 25-35 %로 구성되는 것을 특징으로 하는 CuO 나 노입자 전자잉크의 제조방법법. The method of claim 10, wherein the CuO nanoparticles comprise 25-35%. 【청구항 13】  [Claim 13] 제 10항에 있어서， 상기 잉크가 균질기로 1—3분간 150으 2500 rpm에서 균질화 하는 것을 특징으로 하는 CuO나노입자 전자잉크의 제조방법. The method of manufacturing a CuO nanoparticle electronic ink according to claim 10, wherein the ink is homogenized at 150 rpm and 2500 rpm for 1 to 3 minutes with a homogenizer. 【청구항 14]  [Claim 14] 제 10항에 있어서， 에틸렌 클리콜이 CuO로부터 Cu로 변환시키는 환원제로 작용하는 것을 특징으로 하는 CuO나노입자 전자잉크의 제조방법. The method for producing CuO nanoparticle electron ink according to claim 10, wherein the ethylene glycol acts as a reducing agent for converting CuO to Cu. 【청구항 15]  [Claim 15] 제 10항에 의해 만든 CuO 나노입자 전자잉크. CuO nanoparticle electronic ink made by claim 10. 【청구항 16】  [Claim 16] 제 10항에 의해 만들어진 CuO 나노입자 전자 잉크를 프린트하여 박막상태로 증착하 는 단계와， 증착된 박막을 건조시키는 단계와ᅤ 증착된 CuO 박막을 진공상태에서 마 이크로파를 조사하여 소결시켜 Cu 박막으로 만드는 단계로 구성되는 것을 특징으로 하는 Cu 박막의 제조방법 . Printed CuO nanoparticle electronic ink made in accordance with claim 10 and depositing in a thin film state, drying the deposited thin film and ᅤ sintered CuO thin film by microwave irradiation in a vacuum state to Cu thin film Method for producing a Cu thin film, characterized in that consisting of steps to make. 【청구항 17]  [Claim 17] 제 16항에 있어서， CuO 나노입자의 전자 잉크가 35ᅳ 45초간 150()-2500rpm으로 스핀 코팅하여 기판에 두꺼운 박막을 증착하는 것을 특징으로 하는 Cu 박막의 제조방법 . 17. The method of claim 16, wherein the CuO nanoparticle electronic ink is spin-coated at 150 ()-2500 rpm for 35 s 45 seconds to deposit a thick thin film on the substrate. 【청구항 18] [Claim 18] 제 16항에 있어서， 높은 표면 저항을 갖는 종이 기판 위에 잉크펜으로 증착된 CuO 나노입자 전자잉크의 CuO를 Cu로 변환시키는 것을 특징으로 하는 Cu박막의 제조방 17. The method of claim 16, wherein CuO of CuO nanoparticle electron ink deposited with an ink pen on a paper substrate having high surface resistance is converted to Cu. 【청구항 19] [Claim 19] 제 16항에 있어서， 증착된 CuO 박막을 Cu 박막으로 만들기 위해 압력은 대기 압 또는 진공 범위 1X10_1 내지 1X10_5 Pa 에서 마이크로파인 것을 특징으로 하는 Cu박막의 제조방법 . 17. The method of claim 16, to make the deposited thin film of a Cu thin film CuO pressure method for manufacturing a Cu thin film, characterized in that microwaves in the air pressure or vacuum range 1X10 to 1X10 _5 _1 Pa. 【청구항 20】  [Claim 20] 제 16항에 있어서， 증착된 박막에 잔존하는 낮은 비등점을 갖는 용매의 증발을 위 해 주위 분위기에서부터 건조되는 것을 특징으로 하는 Cu박막의 제조방법. 17. The method of claim 16, wherein the Cu thin film is dried from an ambient atmosphere for evaporation of a solvent having a low boiling point remaining in the deposited thin film. 【청구항 21】 제 16항에 있어서， 진공 압력 범위는 1X10— 1 내지 1X1으 5 Pa 에서 진공마이크로파 를 조사하는 것을 특징으로 하는 Cu 박막의 제조방법 . [Claim 21] The method for producing a Cu thin film according to claim 16, wherein the vacuum pressure range is irradiated with vacuum microwave at 5 Pa of 1 × 10—1 to 1 × 1 . 【청구항 22]  [Claim 22] 제 16항에 있어서， 구리상으로 소결은 2분간 마이크로파 조사로 박막의 2 im 두께 까지 침투하는 기판에 환원시키는 것을 특징으로 하는 Cu 박막의 제조방법 . The method for producing a Cu thin film according to claim 16, wherein the sintering to copper phase is reduced to a substrate which penetrates up to 2 im thickness of the thin film by microwave irradiation for 2 minutes. 【청구항 23]  [Claim 23] 제 16항에 있어서， 진공 마이크로파 장치는 400 내지 1,000와트 (W)의 힘을 갖는 마 이크로파 장치에 의해 설계된 진공 마이크로파 조사 장치를 이용하는 것을 특징으 로 하는 Cu 박막의 제조방법 . 17. The method of manufacturing a Cu thin film according to claim 16, wherein the vacuum microwave device uses a vacuum microwave irradiation device designed by a microwave device having a force of 400 to 1,000 watts (W). 【청구항 24】  [Claim 24] 제 16항에 있어서， 전극이 10초간 마이크로파 조사 후 363.12μ Ω.αιι 저항을 갖는 것을 특징으로 하는 Cu 박막의 제조방법 . The method of claim 16, wherein the electrode has a resistance of 363.12 μΩ · αιι after 10 seconds of microwave irradiation. 【청구항 25]  [Claim 25] 제 16항에 있어서， 마이크로파 조사로 박막에서 CuO로부터 Cu로 변환하는 동안 기 공 발생으로 인해 높은 표면 저항을 갖는 것을 특징으로 하는 Cu 박막의 제조방법.The method of claim 16, wherein the microwave thin film has a high surface resistance due to pore generation during the conversion from CuO to Cu in the thin film by microwave irradiation. 【청구항 26】 [Claim 26] 제 16항에 의해 만든 Cu 박막 Cu thin film made by claim 16
PCT/KR2013/006945 2013-07-29 2013-08-01 CuO NANOPARTICLES, INK THEREOF, AND METHOD FOR PREPARING CU THIN FILM BY REDUCING CuO THIN FILM THROUGH MICROWAVE IRRADIATION Ceased WO2015016404A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020130089525A KR101582637B1 (en) 2013-07-29 2013-07-29 Fabrication of CuO Nanoparticles and Thereof Ink and Microwave-Irradiated Reduction of CuO Films into Metallic Cu films
KR10-2013-0089525 2013-07-29

Publications (1)

Publication Number Publication Date
WO2015016404A1 true WO2015016404A1 (en) 2015-02-05

Family

ID=52431919

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2013/006945 Ceased WO2015016404A1 (en) 2013-07-29 2013-08-01 CuO NANOPARTICLES, INK THEREOF, AND METHOD FOR PREPARING CU THIN FILM BY REDUCING CuO THIN FILM THROUGH MICROWAVE IRRADIATION

Country Status (2)

Country Link
KR (1) KR101582637B1 (en)
WO (1) WO2015016404A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104698054A (en) * 2015-04-07 2015-06-10 天津理工大学 Non-enzymic glucose sensor of modified nanometer copper oxide screen-printed electrode
CN110342564A (en) * 2019-07-28 2019-10-18 陕西理工大学 A kind of laminated structure CuO nanometers of optical-thermal conversion materials and preparation method thereof
US10995010B1 (en) 2020-06-26 2021-05-04 King Saud University Synthesis of copper oxide nanoparticles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060112025A (en) * 2005-04-26 2006-10-31 주식회사 잉크테크 Metal ink composition
US20090181184A1 (en) * 2007-05-24 2009-07-16 Pope Dave S Method for Reducing Thin Films on Low Temperature Substrates
KR101008090B1 (en) * 2003-03-05 2011-01-13 인튠 써큐츠 오와이 Method of manufacturing an electrically conductive pattern
WO2013076999A1 (en) * 2011-11-25 2013-05-30 Showa Denko K.K. Conductive pattern formation method

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011034016A1 (en) * 2009-09-16 2011-03-24 日立化成工業株式会社 Copper metal film, method for producing same, copper metal pattern, conductive wiring line using the copper metal pattern, copper metal bump, heat conduction path, bonding material, and liquid composition
JP5713181B2 (en) * 2011-01-27 2015-05-07 日立化成株式会社 LIQUID COMPOSITION FOR PRINTING, CONDUCTIVE WIRING OBTAINED BY USING THE SAME, METHOD FOR FORMING THE SAME, HEAT CONDUCTIVE CIRCUIT, JOINT

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101008090B1 (en) * 2003-03-05 2011-01-13 인튠 써큐츠 오와이 Method of manufacturing an electrically conductive pattern
KR20060112025A (en) * 2005-04-26 2006-10-31 주식회사 잉크테크 Metal ink composition
US20090181184A1 (en) * 2007-05-24 2009-07-16 Pope Dave S Method for Reducing Thin Films on Low Temperature Substrates
WO2013076999A1 (en) * 2011-11-25 2013-05-30 Showa Denko K.K. Conductive pattern formation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
VASEEM, M. ET AL.: "Copper oxide quantum dot ink for inkjet-driven digitally controlled high mobility field effect transistors", J. MATER. CHEM. C, vol. 1, 24 January 2013 (2013-01-24), pages 2112 - 2120 *
ZHU, J. ET AL.: "Highly dispersed CuO nanoparticles prepared by a novel quick-precipitation method", MATERIALS LETTERS, vol. 58, 2004, pages 3324 - 3327 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104698054A (en) * 2015-04-07 2015-06-10 天津理工大学 Non-enzymic glucose sensor of modified nanometer copper oxide screen-printed electrode
CN110342564A (en) * 2019-07-28 2019-10-18 陕西理工大学 A kind of laminated structure CuO nanometers of optical-thermal conversion materials and preparation method thereof
US10995010B1 (en) 2020-06-26 2021-05-04 King Saud University Synthesis of copper oxide nanoparticles
US11718537B2 (en) 2020-06-26 2023-08-08 King Saud University Synthesis of copper oxide nanoparticles

Also Published As

Publication number Publication date
KR20150014182A (en) 2015-02-06
KR101582637B1 (en) 2016-01-07

Similar Documents

Publication Publication Date Title
Saidina et al. Recent development of graphene-based ink and other conductive material-based inks for flexible electronics
JP4431543B2 (en) Wiring board manufacturing method using Ag-Pd alloy nanoparticles
CN103947305B (en) Conductive pattern forming method and the conductive pattern formation compositionss forming conductive pattern by light irradiation or microwave heating
TWI655090B (en) Transparent electrode and method of manufacturing same
US10563080B2 (en) Core-shell nanostructures and related inks, films and methods
KR100905399B1 (en) Conductive ink composition comprising metal nanoparticles and nanoglass frits for excellent conductivity and improved adhesion to glass and ceramic substrates
CN109790409B (en) Copper inks and conductive solderable copper traces made therefrom
Li et al. Inkjet Printing of Perovskites for Breaking Performance–Temperature Tradeoffs in Fabric‐Based Thermistors
Wang et al. Functional inks for printable energy storage applications based on 2 D materials
TW201343810A (en) Liquid composition, metallic film and conductor wiring, and fabricating method of metallic film
JP5772539B2 (en) Method for producing copper oxide paste and metallic copper layer
CN113409990B (en) A kind of flexible conductive film and preparation method thereof
JP6562196B2 (en) Copper fine particle sintered body and method for producing conductive substrate
WO2015016404A1 (en) CuO NANOPARTICLES, INK THEREOF, AND METHOD FOR PREPARING CU THIN FILM BY REDUCING CuO THIN FILM THROUGH MICROWAVE IRRADIATION
KR101280119B1 (en) Micropatterning of graphene sheets by inkjet printing and its wideband dipole-antenna application
Sui et al. Engineering the surface morphology of inkjet printed Ag by controlling solvent evaporation during plasma conversion of AgNO 3 inks
WO2018212345A1 (en) Method for producing conductor, method for producing wiring board, and composition for forming conductor
KR101319559B1 (en) Manufacturing method for coating layer having graphene
JP5849641B2 (en) Method for producing copper oxide particles
KR20160119551A (en) Composition for forming conductive copper pattern by light sintering including carbon nanostructures, method for preparing conductive copper pattern by light sintering, and electronic device including the conductive copper pattern prepared therefrom
Rama et al. Conductive silver inks and its applications in printed and flexible electronics
CN109937189A (en) Cuprous oxide particle, its manufacturing method, light slug type composition, using the light slug type composition conductive film forming method and cuprous oxide particle paste
JP6175304B2 (en) Copper composite particles, copper paste containing the same, and circuit board manufacturing method using the same
JP2013196881A (en) Method for forming electrical conduction pattern, and composition for electrical conduction pattern formation by light irradiation or microwave heating
KR20150098844A (en) Method for manufacturing of core-shell nanoparticles and the core-shell nanoparticles thereby

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13890380

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13890380

Country of ref document: EP

Kind code of ref document: A1