WO2009084764A1 - Method of manufacturing superconducting tape using continuous nano-dots formation and calcination - Google Patents

Method of manufacturing superconducting tape using continuous nano-dots formation and calcination Download PDF

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Publication number
WO2009084764A1
WO2009084764A1 PCT/KR2008/000372 KR2008000372W WO2009084764A1 WO 2009084764 A1 WO2009084764 A1 WO 2009084764A1 KR 2008000372 W KR2008000372 W KR 2008000372W WO 2009084764 A1 WO2009084764 A1 WO 2009084764A1
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Prior art keywords
superconducting
nanodots
precursor solution
thin film
precursor
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PCT/KR2008/000372
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French (fr)
Inventor
Jai-Moo Yoo
Kook-Chae Chung
Young-Kuk Kim
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Korea Institute Of Machinery & Materials
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Publication of WO2009084764A1 publication Critical patent/WO2009084764A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
    • H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
    • H10N60/0324—Processes for depositing or forming copper oxide superconductor layers from a solution
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
    • H10N60/0828—Introducing flux pinning centres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a method for manufacturing a superconducting tape, and more particularly to a method of manufacturing a superconducting tape by continuous processes of nanodot formation, precursor coating and calcination.
  • Superconducting tapes must have high critical current values even in a high magnetic field in order to be useful.
  • a magnetic field which has penetrated into superconducting materials moves in accordance with the Lorentz force upon the application of an electric current to induce an electric field, thus causing a loss of electricity.
  • flux pinning centers are introduced into superconducting materials to capture a magnetic field such that the magnetic field does not move, electrical loss can be reduced and the critical current in a magnetic field can be increased.
  • a method for introducing flux pinning centers comprises making columnar defects in superconducting materials by irradiation with high-energy neutral particles or heavy ions. Because this method requires a strong particle accelerator, it entails enormous process costs, and the large-scale application thereof is limited due to spatial constraints.
  • the present invention provides a method of manufacturing a superconducting tape using the continuous processes of nanodot formation, precursor coating and calcination, the method comprising the steps of: spraying a precursor solution for forming nanodots through a nozzle, and coating a buffer layer-coated metal substrate released from a reel with the sprayed precursor solution; heat-treating the sprayed precursor solution to form nanodots; continuously performing a process of coating with a superconducting precursor solution and a calcination process on the buffer layer having the nanodots formed thereon, thus manufacturing a superconducting precursor thin film; and heat- treating the superconducting precursor thin film to form a superconducting thin film and inducing defects in the superconducting thin film.
  • the defects induced in the superconducting thin film are columnar defects formed on the nanodots.
  • the precursor solution sprayed through the nozzle may be converted to nanopowder through a heat-treatment furnace before coating.
  • a carrier or reactive gas may be introduced into a region into which the precursor solution is sprayed.
  • the carrier or reactive gas may be argon or oxygen gas.
  • the precursor solution for forming nanodots may be coated by electrospraying, and the step of coating with the precursor solution may be carried out in a state in which the metal substrate is wound about a cylinder.
  • nanodots by electrospraying and the deposition of a superconducting layer by organic chemical vapor deposition are continuously performed on the surface of a metal substrate covered with a buffer layer, and columnar defects are induced in the superconducting layer deposited on the nanodots.
  • Nanodots formed using an expensive vacuum system have a height of less than 10 nm, whereas nanodots formed using an electrospraying process which is widely used for surface coating and mass analysis can have a height of more than 100 nm.
  • the electrospraying process according to the present invention is advantageous for inducing columnar defects in a superconducting material and is a liquid-phase deposition method. Accordingly, the electrospraying process can be applied continuously with an organic chemical vapor process for coating a superconducting layer.
  • FIG. 1 is a cross-sectional view illustrating a method for manufacturing a superconducting tape according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view illustrating a method for manufacturing a superconducting tape according to another embodiment of the present invention.
  • FIG. 3 is a conceptual view showing a method for manufacturing a superconducting tape.
  • FIGS. 4a to 5c explain examples of the present invention.
  • FIG. 1 is a cross-sectional view illustrating a method for manufacturing a superconducting tape according to an embodiment of the present invention.
  • the inventive method of manufacturing a superconducting tape by continuous processes of nanodot formation and calcination comprises four steps as follows:
  • a precursor solution for forming nanodots is sprayed through a nozzle and coats a buffer layer-coated metal substrate released from a reel (step 1).
  • the precursor solution sprayed in step 1 is heat-treated to form nanodots (step 2).
  • a superconducting precursor solution is continuously coated on the buffer layer on which the nanodots were formed in step 2, and the coated solution is calcined, thus manufacturing a superconducting precursor thin film (step 3).
  • the superconducting precursor thin film is converted to a superconducting thin film by heat treatment, and defects in the superconducting thin film are induced (step 4). As shown in FIG.
  • a syringe containing a precursor solution for forming nanodots is compressed by a pump 1 , and the precursor solution is pushed out into a nozzle.
  • the pushed precursor solution is positively charged, because the nozzle is applied with a high DC voltage 3.
  • the precursor solution is sprayed through the nozzle, it is present in the form of positively charged droplets 4.
  • the positively charged precursor solution droplets are attracted to and deposited on a metal substrate 6 coated with a negatively charged buffer layer.
  • the solvent of the deposited precursor solution droplets is evaporated in a heat-treatment furnace 5 while leaving only nanoparticles, thus forming nanodots (see FIG. 3a).
  • the metal substrate 6 coated with the buffer layer having the nanodots formed thereon is continuously subjected to a coating process 9 with a superconducting precursor solution and a calcination process 10, thus making a superconducting precursor thin film.
  • the superconducting thin film is heat-treated at high temperature (more than about 600 "C) to form a superconducting thin film, and columnar defects on the nanodots in the superconducting thin film are induced.
  • FIG. 2 is a cross-sectional view illustrating a method for manufacturing a superconducting tape according to another embodiment of the present invention.
  • a heat- treatment furnace 15 for evaporating the solvent before the precursor solution reaches the metal substrate 6 coated with the negatively charged buffer layer after spraying from the syringe is provided.
  • FIGS. 3a to 3c are conceptual views showing a method for manufacturing a superconducting tape.
  • a buffer layer 200 is formed on a metal substrate 100, and nanodots 300 are formed on the buffer layer 200.
  • a superconducting precursor thin film 400 covering the nanodots 300 is formed.
  • the superconducting precursor thin film 400 is converted to a superconducting thin film 400a, and columnar defects 500 are formed on the nanodots 300 in the superconducting thin film 400a.
  • the superconducting thin film 400 has a thickness of 1 ⁇ m. [Example 1]
  • a CeO2 buffer layer was deposited on single-crystalline YSZ (Yttria Stabilized Zirconia), and then nanodots were formed on the buffer layer under the following conditions: Precursor for forming nanodots: Zr-precursor, 0.01 M;
  • Solution injection rate 0.001 ul/min; and Deposition time: 3 min.
  • FIG. 4a shows an AFM photograph of the surface having the ZrO2 nanodots formed thereon.
  • FIG. 4b shows analysis results for a section indicated by the arrow in FIG. 4a.
  • the nanodots had an average diameter of about 200 ran, a height of about 140 nm and a density of about 6/ ⁇ m2.
  • nanodots could be formed by electrospraying.
  • a process of coating with a superconducting precursor solution and a calcination process were performed on the substrate having the nanodots formed thereon.
  • FIG. 4c shows an XRD diffraction curve of the superconducting thin film. As can be seen therein, the excellent growth of crystals in the superconducting thin film was shown, and the nanodots did not influence the overall growth of crystals.
  • the superconducting thin film had a critical current of 118 A/cm -width and a critical current density of 1.6 MA/cirf.
  • Nanodots were formed on a metal substrate coated with a buffer layer under the following conditions.
  • the structure of the buffer layer-coated metal substrate was Ni-5%W/Y2O3/YSZ/CeO2, and the nanodots were formed on the CeO2 layer as the uppermost layer by electrospraying.
  • Precursor for forming nanodots BZO-precursor
  • Solvent used methanol; Voltage applied: 4277 volts; Current: 78 nA;
  • FIG. 5 a shows an AFM photograph of the surface having the nanodots formed thereon. If the nanodots were agglomerated, they were distributed at a size of less than about 1 ⁇ m, and most of the nanodots had an diameter of about 200 nm, a height of about 100 nm and a density of about 2.2/ ⁇ m2 (see FIG. 5b). As shown in FIGS. 1 and 2, a process of coating with a superconducting precursor solution and a calcination process were performed on the substrate having the nanodots formed thereon.
  • FIG. 5c shows an XRD diffraction curve of the superconducting thin film. As can be seen therein, the excellent growth of crystals in the superconducting thin film was shown, and the nanodots did not influence the overall growth of crystals.
  • the superconducting thin film had a critical current of 17.5 A/cm-width and a critical current density of 0.3 MA/ ⁇ tf.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)

Abstract

A method of manufacturing a superconducting tape by continuous processes of nanodot formation, precursor coating and calcinations is provided. The method comprises: spraying a precursor solution for forming nanodots through a nozzle, and coating a buffer layer-coated metal substrate released from a reel with the sprayed precursor solution; heat-treating the sprayed precursor solution to form nanodots; continuously performing a process of coating with a superconducting precursor solution and a calcination process on the buffer layer having the nanodots formed thereon, thus manufacturing a superconducting precursor thin film; and heat-treating the superconducting precursor thin film to form a superconducting thin film and inducing defects in the superconducting thin film.

Description

METHOD OF MANUFACTURING SUPERCONDUCTING TAPE USING CONTINUOUS NANO-DOTS FORMATION AND CALCINATION
Technical Field
The present invention relates to a method for manufacturing a superconducting tape, and more particularly to a method of manufacturing a superconducting tape by continuous processes of nanodot formation, precursor coating and calcination.
Background Art
Superconducting tapes must have high critical current values even in a high magnetic field in order to be useful. Generally, a magnetic field which has penetrated into superconducting materials moves in accordance with the Lorentz force upon the application of an electric current to induce an electric field, thus causing a loss of electricity. For this reason, when flux pinning centers are introduced into superconducting materials to capture a magnetic field such that the magnetic field does not move, electrical loss can be reduced and the critical current in a magnetic field can be increased.
A method for introducing flux pinning centers, widely known to date, comprises making columnar defects in superconducting materials by irradiation with high-energy neutral particles or heavy ions. Because this method requires a strong particle accelerator, it entails enormous process costs, and the large-scale application thereof is limited due to spatial constraints.
Disclosure Technical Problem
It is an object of the present invention to provide a method of manufacturing a superconducting tape exhibiting improved critical current properties, using continuous processes of nanodot formation, precursor coating and calcination.
Technical Solution To achieve the above object, the present invention provides a method of manufacturing a superconducting tape using the continuous processes of nanodot formation, precursor coating and calcination, the method comprising the steps of: spraying a precursor solution for forming nanodots through a nozzle, and coating a buffer layer-coated metal substrate released from a reel with the sprayed precursor solution; heat-treating the sprayed precursor solution to form nanodots; continuously performing a process of coating with a superconducting precursor solution and a calcination process on the buffer layer having the nanodots formed thereon, thus manufacturing a superconducting precursor thin film; and heat- treating the superconducting precursor thin film to form a superconducting thin film and inducing defects in the superconducting thin film.
The defects induced in the superconducting thin film are columnar defects formed on the nanodots. The precursor solution sprayed through the nozzle may be converted to nanopowder through a heat-treatment furnace before coating.
A carrier or reactive gas may be introduced into a region into which the precursor solution is sprayed. The carrier or reactive gas may be argon or oxygen gas. The precursor solution for forming nanodots may be coated by electrospraying, and the step of coating with the precursor solution may be carried out in a state in which the metal substrate is wound about a cylinder.
Advantageous Effects
According to an embodiment of the present invention, in order to induce columnar defects serving as flux pinning centers in a superconducting material, the formation of nanodots by electrospraying and the deposition of a superconducting layer by organic chemical vapor deposition are continuously performed on the surface of a metal substrate covered with a buffer layer, and columnar defects are induced in the superconducting layer deposited on the nanodots. Nanodots formed using an expensive vacuum system have a height of less than 10 nm, whereas nanodots formed using an electrospraying process which is widely used for surface coating and mass analysis can have a height of more than 100 nm. Thus, the electrospraying process according to the present invention is advantageous for inducing columnar defects in a superconducting material and is a liquid-phase deposition method. Accordingly, the electrospraying process can be applied continuously with an organic chemical vapor process for coating a superconducting layer.
Description of Drawings
FIG. 1 is a cross-sectional view illustrating a method for manufacturing a superconducting tape according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view illustrating a method for manufacturing a superconducting tape according to another embodiment of the present invention.
FIG. 3 is a conceptual view showing a method for manufacturing a superconducting tape.
FIGS. 4a to 5c explain examples of the present invention.
Best Mode
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so as to enable those skilled in the art to carry out the present invention. However, the present invention is not limited to the embodiments set forth herein and can be embodied in other forms. Rather, the embodiments set forth herein are provided so that the disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
In the figures, each element may be exaggeratingly shown for clarity. Throughout the specification, a similar reference numeral denotes a similar element.
FIG. 1 is a cross-sectional view illustrating a method for manufacturing a superconducting tape according to an embodiment of the present invention.
The inventive method of manufacturing a superconducting tape by continuous processes of nanodot formation and calcination comprises four steps as follows:
A precursor solution for forming nanodots is sprayed through a nozzle and coats a buffer layer-coated metal substrate released from a reel (step 1). The precursor solution sprayed in step 1 is heat-treated to form nanodots (step 2). A superconducting precursor solution is continuously coated on the buffer layer on which the nanodots were formed in step 2, and the coated solution is calcined, thus manufacturing a superconducting precursor thin film (step 3). The superconducting precursor thin film is converted to a superconducting thin film by heat treatment, and defects in the superconducting thin film are induced (step 4). As shown in FIG. 1 , a syringe containing a precursor solution for forming nanodots is compressed by a pump 1 , and the precursor solution is pushed out into a nozzle. The pushed precursor solution is positively charged, because the nozzle is applied with a high DC voltage 3. Thus, when the precursor solution is sprayed through the nozzle, it is present in the form of positively charged droplets 4. Then, the positively charged precursor solution droplets are attracted to and deposited on a metal substrate 6 coated with a negatively charged buffer layer.
The solvent of the deposited precursor solution droplets is evaporated in a heat-treatment furnace 5 while leaving only nanoparticles, thus forming nanodots (see FIG. 3a). Then, the metal substrate 6 coated with the buffer layer having the nanodots formed thereon is continuously subjected to a coating process 9 with a superconducting precursor solution and a calcination process 10, thus making a superconducting precursor thin film. Then, the superconducting thin film is heat-treated at high temperature (more than about 600 "C) to form a superconducting thin film, and columnar defects on the nanodots in the superconducting thin film are induced.
FIG. 2 is a cross-sectional view illustrating a method for manufacturing a superconducting tape according to another embodiment of the present invention. In the embodiment of FIG. 2, unlike the embodiment of FIG. 1, a heat- treatment furnace 15 for evaporating the solvent before the precursor solution reaches the metal substrate 6 coated with the negatively charged buffer layer after spraying from the syringe is provided.
FIGS. 3a to 3c are conceptual views showing a method for manufacturing a superconducting tape. As shown in FIG. 3a, a buffer layer 200 is formed on a metal substrate 100, and nanodots 300 are formed on the buffer layer 200. As shown in FIG. 3b, a superconducting precursor thin film 400 covering the nanodots 300 is formed. As shown in FIG. 3c, the superconducting precursor thin film 400 is converted to a superconducting thin film 400a, and columnar defects 500 are formed on the nanodots 300 in the superconducting thin film 400a. The superconducting thin film 400 has a thickness of 1 μm. [Example 1]
A CeO2 buffer layer was deposited on single-crystalline YSZ (Yttria Stabilized Zirconia), and then nanodots were formed on the buffer layer under the following conditions: Precursor for forming nanodots: Zr-precursor, 0.01 M;
Solvent used: methanol;
Voltage applied: 4200 volts;
Current: 15O nA;
Solution injection rate: 0.001 ul/min; and Deposition time: 3 min.
The diameter, height and density of the formed ZrO2 nanodots can be analyzed by atomic force microscopy. FIG. 4a shows an AFM photograph of the surface having the ZrO2 nanodots formed thereon. FIG. 4b shows analysis results for a section indicated by the arrow in FIG. 4a. As can be seen in FIG. 4a, the nanodots had an average diameter of about 200 ran, a height of about 140 nm and a density of about 6/μm2. Also, it could be seen that nanodots could be formed by electrospraying. A process of coating with a superconducting precursor solution and a calcination process were performed on the substrate having the nanodots formed thereon. After completion of the calcination process, the substrate having the nanodots formed thereon was heat-treated at high temperature to form a superconducting thin film, and columnar defects were induced on the nanodots in the superconducting thin film. FIG. 4c shows an XRD diffraction curve of the superconducting thin film. As can be seen therein, the excellent growth of crystals in the superconducting thin film was shown, and the nanodots did not influence the overall growth of crystals. The superconducting thin film had a critical current of 118 A/cm -width and a critical current density of 1.6 MA/cirf.
[Example 2]
Nanodots were formed on a metal substrate coated with a buffer layer under the following conditions. The structure of the buffer layer-coated metal substrate was Ni-5%W/Y2O3/YSZ/CeO2, and the nanodots were formed on the CeO2 layer as the uppermost layer by electrospraying.
Precursor for forming nanodots: BZO-precursor;
Solvent used: methanol; Voltage applied: 4277 volts; Current: 78 nA;
Solution injection rate: 0.001 ul/min; and
Deposition time: 3 min.
The diameter, height and density of the formed BaZrO3 nanodots can be analyzed by atomic force microscopy. FIG. 5 a shows an AFM photograph of the surface having the nanodots formed thereon. If the nanodots were agglomerated, they were distributed at a size of less than about 1 μm, and most of the nanodots had an diameter of about 200 nm, a height of about 100 nm and a density of about 2.2/μm2 (see FIG. 5b). As shown in FIGS. 1 and 2, a process of coating with a superconducting precursor solution and a calcination process were performed on the substrate having the nanodots formed thereon. After completion of the calcination process, the substrate having the nanodots formed thereon was heat- treated at high temperature to form a superconducting thin film, and columnar defects were induced on the nanodots in the superconducting thin film. FIG. 5c shows an XRD diffraction curve of the superconducting thin film. As can be seen therein, the excellent growth of crystals in the superconducting thin film was shown, and the nanodots did not influence the overall growth of crystals. The superconducting thin film had a critical current of 17.5 A/cm-width and a critical current density of 0.3 MA/αtf.

Claims

Claims :
1. A method of manufacturing a superconducting tape using the continuous processes of nanodot formation, precursor coating and calcination, the method comprising the steps of: spraying a precursor solution for forming nanodots through a nozzle, and coating a buffer layer-coated metal substrate released from a reel with the sprayed precursor solution; heat-treating the sprayed precursor solution to form nanodots; continuously performing a process of coating with a superconducting precursor solution and a calcination process on the buffer layer having the nanodots formed thereon, thus manufacturing a superconducting precursor thin film; and heat-treating the superconducting precursor thin film to form a superconducting thin film and inducing defects in the superconducting thin film.
2. The method of Claim 1, wherein the defects induced in the superconducting thin film are columnar defects formed on the nanodots.
3. The method of Claim 1, which further comprises, before the step of coating with the precursor solution, a step of converting the sprayed precursor solution to nanopowder through a heat-treatment furnace.
4. The method of Claim 1, wherein a carrier or reactive gas is introduced into a region into which the precursor solution is sprayed.
5. The method of Claim 4, wherein the carrier or reactive gas is argon or oxygen gas.
6. The method of Claim 1, wherein the precursor solution for forming nanodots is coated by electrospraying, and the step of coating the precursor solution is carried out in a state in which the metal substrate was wound about a cylinder.
PCT/KR2008/000372 2008-01-03 2008-01-21 Method of manufacturing superconducting tape using continuous nano-dots formation and calcination WO2009084764A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103123938A (en) * 2011-11-18 2013-05-29 财团法人工业技术研究院 Optical passivation film, method for manufacturing same, and solar cell
WO2021100969A1 (en) * 2019-11-20 2021-05-27 주식회사 서남 Superconducting layer exfoliation method and exfoliation apparatus therefor

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Publication number Priority date Publication date Assignee Title
JP2004071410A (en) * 2002-08-07 2004-03-04 Fujikura Ltd Forming method and its device of stabilized layer
JP2004200098A (en) * 2002-12-20 2004-07-15 Chubu Electric Power Co Inc Manufacturing method of oxide superconductive wire rod
US20040235670A1 (en) * 2001-06-19 2004-11-25 Crisan Ioan Adrian Superconducting thin film having columnar pin retaining center using nano-dots
KR20070087340A (en) * 2006-02-23 2007-08-28 한국기계연구원 Method of manufacturing superconducting tapes using batch-type calcination and annealing process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040235670A1 (en) * 2001-06-19 2004-11-25 Crisan Ioan Adrian Superconducting thin film having columnar pin retaining center using nano-dots
JP2004071410A (en) * 2002-08-07 2004-03-04 Fujikura Ltd Forming method and its device of stabilized layer
JP2004200098A (en) * 2002-12-20 2004-07-15 Chubu Electric Power Co Inc Manufacturing method of oxide superconductive wire rod
KR20070087340A (en) * 2006-02-23 2007-08-28 한국기계연구원 Method of manufacturing superconducting tapes using batch-type calcination and annealing process

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103123938A (en) * 2011-11-18 2013-05-29 财团法人工业技术研究院 Optical passivation film, method for manufacturing same, and solar cell
TWI448431B (en) * 2011-11-18 2014-08-11 Ind Tech Res Inst Optical passivation film and manufacturing thereof and solar cell
WO2021100969A1 (en) * 2019-11-20 2021-05-27 주식회사 서남 Superconducting layer exfoliation method and exfoliation apparatus therefor

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