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WO2022092425A1 - Émetteur de rouleau de feuille de nanotubes de carbone présentant une stabilité structurelle améliorée, son procédé de fabrication et dispositif d'émission de champ l'utilisant - Google Patents

Émetteur de rouleau de feuille de nanotubes de carbone présentant une stabilité structurelle améliorée, son procédé de fabrication et dispositif d'émission de champ l'utilisant Download PDF

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Publication number
WO2022092425A1
WO2022092425A1 PCT/KR2020/018527 KR2020018527W WO2022092425A1 WO 2022092425 A1 WO2022092425 A1 WO 2022092425A1 KR 2020018527 W KR2020018527 W KR 2020018527W WO 2022092425 A1 WO2022092425 A1 WO 2022092425A1
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WIPO (PCT)
Prior art keywords
carbon nanotube
nanotube sheet
emitter
sheet roll
structural stability
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Ceased
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PCT/KR2020/018527
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English (en)
Korean (ko)
Inventor
정영진
송현준
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Soongsil University
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Soongsil University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02—Main electrodes
    • H01J1/30—Cold cathodes, e.g. field-emissive cathode
    • H01J1/304—Field-emissive cathodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
    • H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2201/00—Electrodes common to discharge tubes
    • H01J2201/30—Cold cathodes
    • H01J2201/304—Field emission cathodes
    • H01J2201/30446—Field emission cathodes characterised by the emitter material
    • H01J2201/30453—Carbon types
    • H01J2201/30469—Carbon nanotubes (CNTs)

Definitions

  • the present invention relates to a carbon nanotube emitter, and more particularly, to a carbon nanotube sheet roll emitter with improved structural stability by winding the carbon nanotube sheet to form a roll.
  • Field emission refers to a phenomenon in which electrons are quantum-mechanically tunneled as the potential barrier of the cathode surface becomes thin when an electric field is applied to the surfaces of two materials (anode and cathode) in a vacuum.
  • an anode material having a nano structure that is, a nano electron source.
  • the field emission characteristics of the nanoelectron source show excellent properties as the structural anisotropy (Aspect Ratio) increases and the chemical stability increases.
  • Carbon nanotubes a material in which two-dimensional graphene is rolled in a tube form, is an excellent nanoelectron source material optimized for the above requirements. It not only has a structure of a high aspect ratio, which is difficult to do, but also has great thermal and mechanical stability. Accordingly, when a voltage is applied at a distance, a high electric field is induced at the tip of the CNT, and quantum mechanical tunneling of electrons occurs very easily in response to this, so the CNT can be used as a high-performance electron source. there is.
  • Korean Patent No. 10-1992745 structural stability and electron emission efficiency were improved by arranging carbon nanotube fibers (yarn) in parallel and pressing them to make a sheet, and then forming a tube shape to manufacture a field emission device.
  • the tube-shaped field emission device is very weak because carbon nanotube fibers (yarn) are coupled to each other through ⁇ - ⁇ interaction, and is very vulnerable to repulsion by electrons generated at the tip of the field emission device.
  • An object of the present invention is to provide a carbon nanotube sheet roll emitter that is structurally stable while solving the problems of the prior art and having excellent field emission characteristics, and a method for manufacturing the same.
  • Another object of the present invention is to provide a field emission device that is structurally stable and can be used stably even at high output.
  • an embodiment of the present invention provides a carbon nanotube sheet roll emitter.
  • the carbon nanotube sheet roll emitter includes a carbon nanotube sheet roll on which a carbon nanotube sheet is wound around a central axis, wherein the carbon nanotube sheet is formed by bonding a plurality of carbon nanotube bundles to each other through a covalent bond. It may be characterized by
  • the plurality of carbon nanotube bundles of the carbon nanotube sheet may be characterized in that they are arranged with a certain directionality.
  • the central axis and the arrangement direction of the carbon nanotube bundles may be characterized in that they form an angle of -45° to 45°.
  • the carbon nanotube sheet roll may have a length of 1 ⁇ m to 1 m.
  • the carbon nanotube sheet roll may have a cross-sectional diameter of 1 ⁇ m to 30 cm.
  • the carbon nanotube sheet roll may be one in which a bent portion of the carbon nanotube sheet roll has a sharp tip.
  • another embodiment of the present invention provides a carbon nanotube sheet roll emitter.
  • the carbon nanotube sheet roll emitter may further include, in the carbon nanotube sheet roll emitter according to an embodiment of the present invention, a conductive member coupling part formed to surround the lower surface of the carbon nanotube sheet roll. may be doing
  • the carbon nanotube sheet roll emitter is wound together with the carbon nanotube sheet of the carbon nanotube sheet roll on the carbon nanotube sheet roll emitter according to an embodiment of the present invention to form the carbon nanotube sheet roll. It may be characterized by further comprising a; conductive member coupling portion formed surrounding the lower surface.
  • the height of the remaining portions except for the height portion occupied by the conductive member coupling portion and the total height of the carbon nanotube sheet roll emitter have a length ratio of 1:5 to 9:10 It may be characterized by
  • the conductive member coupling part is in the form of a metal thin film or a metal wire including any one or more metals selected from the group consisting of tungsten, zinc, nickel, copper, silver, aluminum, gold, platinum, tin, and stainless steel. it could be
  • the conductive member coupling part may include an inorganic paste having conductive properties.
  • another embodiment of the present invention provides a method of manufacturing a carbon nanotube sheet roll emitter.
  • the manufacturing method of the carbon nanotube sheet roll emitter includes the steps of preparing a carbon nanotube sheet; and manufacturing the carbon nanotube sheet roll emitter by winding the prepared carbon nanotube sheet around a central axis to form a roll shape.
  • the carbon nanotube sheet may be characterized in that it is formed by bonding a plurality of carbon nanotube bundles to each other through a covalent bond.
  • winding a sheet composed of carbon nanotube bundles to prepare a carbon nanotube sheet so that the carbon nanotube bundles have a certain direction; may be characterized in that it includes .
  • the winding direction of the carbon nanotube sheet and the central axis may be manufactured to form an angle of -45° to 45°.
  • the carbon nanotube sheet roll emitter is manufactured by placing a conductive member on the lower end of the carbon nanotube sheet and winding it together to form a roll shape.
  • another embodiment of the present invention provides a field emission device.
  • the field emission device may include a carbon nanotube sheet roll emitter according to an embodiment of the present invention.
  • a carbon nanotube sheet roll emitter that has excellent field emission characteristics and is structurally stable, and a method for manufacturing the same.
  • FIG. 1 is a schematic diagram schematically showing the structure of a carbon nanotube sheet roll emitter according to an embodiment of the present invention.
  • FIG. 2 is a photograph showing the carbon nanotube sheet of the present invention.
  • FIG. 3 is a schematic diagram schematically illustrating a rolling angle formed by a central axis of a carbon nanotube sheet roll emitter and an arrangement direction of carbon nanotube bundles according to an embodiment of the present invention.
  • FIG. 4 is a schematic diagram schematically showing the structure of a carbon nanotube sheet roll emitter according to another embodiment of the present invention.
  • FIG. 5 is a schematic diagram schematically showing the structure of a carbon nanotube sheet roll emitter according to another embodiment of the present invention.
  • FIG. 6 is a flowchart schematically illustrating a method for manufacturing a carbon nanotube sheet roll emitter of the present invention.
  • FIG. 7 is a diagram schematically illustrating a manufacturing process of a carbon nanotube sheet according to an embodiment of the present invention.
  • a carbon nanotube sheet roll emitter according to an embodiment of the present invention will be described.
  • 'bundle' as used in the present invention, unless otherwise stated, means that units of a plurality of carbon nanotubes are arranged side by side in substantially the same orientation in the longitudinal direction of the units, or twisted after being arranged, or It refers to a secondary shape in the form of an entangled, bundle or rope.
  • FIG. 1 is a schematic diagram schematically showing the structure of a carbon nanotube sheet roll emitter according to an embodiment of the present invention.
  • FIG. 2 is a photograph showing the carbon nanotube sheet of the present invention.
  • the carbon nanotube sheet 10 is a carbon nanotube sheet wound around a central axis A. including rolls,
  • the carbon nanotube sheet 10 may be characterized in that a plurality of carbon nanotube bundles 11 are bonded to each other through a covalent bond.
  • the ⁇ - ⁇ interaction is a weak bond, and there is a problem in that the bond is not sufficient to withstand the repulsive force between electrons emitted from the tip along the carbon nanotube fiber and to maintain the structural stability of the emitter.
  • the inventors of the present invention construct an emitter using a carbon nanotube sheet formed by tightly connecting carbon nanotube bundles to each other by a covalent bond, and roll the carbon nanotube sheet around a central axis to form a roll
  • the carbon nanotube sheet roll emitter of the present invention was constructed to have
  • the carbon nanotube sheet roll emitter of the present invention uses a sheet made of a carbon nanotube bundle connected by a covalent bond stronger than the conventional ⁇ bond, and thus has improved structural stability.
  • the structural stability of the carbon nanotube sheet was further maximized.
  • the plurality of carbon nanotube bundles 11 of the carbon nanotube sheet 10 may be characterized in that they are arranged with a certain directionality.
  • the rolling angle ⁇ may be characterized in that it has a value of -45° to 45°.
  • FIG 3 is a schematic diagram schematically illustrating a rolling angle ⁇ formed between the central axis A of the carbon nanotube sheet roll emitter 100 and the arrangement direction of the carbon nanotube bundles 11 according to an embodiment of the present invention. am.
  • the mechanical properties of the carbon nanotube sheet roll emitter 100 can be adjusted.
  • the carbon nanotube bundles 11 are tilted to form a predetermined rolling angle ⁇ , so that the carbon nanotube sheet roll emitter 100 responds better to the force acting in the lateral direction. It can be adjusted to withstand it.
  • the rolling angle ⁇ preferably has a value of -45° to 45°.
  • the carbon nanotube bundles 11 in the field emission device are inclined too much with respect to the longitudinal direction of the field emission device. It is undesirable because the field emission effect from the tube end is reduced.
  • the rolling angle ⁇ preferably has a value of -45° to 45°.
  • the carbon nanotube sheet roll may have a length (L) of 1 ⁇ m to 1 m.
  • the carbon nanotube sheet for producing the emitter can be freely manufactured to have a desired size, thereby forming an emitter of a desired length, and also the carbon nanotube fiber strands Since the carbon nanotube sheet is structurally stable in a rolled form, it can be formed to have a sufficiently long length.
  • the carbon nanotube sheet roll may have a cross-sectional diameter (D) of 1 ⁇ m to 30 cm.
  • the carbon nanotube sheet roll emitter of the present invention may be formed to have a sufficient cross-sectional diameter by controlling the number of rolling of the carbon nanotube sheet.
  • a carbon nanotube sheet roll emitter according to another embodiment of the present invention will be described.
  • FIG. 4 is a schematic diagram schematically showing the structure of a carbon nanotube sheet roll emitter according to another embodiment of the present invention.
  • the carbon nanotube sheet roll emitter 100 has a pointed tip 13 formed by bending the central portion of the carbon nanotube sheet 10 roll toward the top. Characterized in that, it may be characterized in that electrons are emitted from the tip (13).
  • the pointed end 13, which is a bent portion of the carbon nanotube sheet roll, is a side of the carbon nanotube sheet roll, that is, a portion corresponding to the sidewall of the carbon nanotube.
  • the tip and sidewall of carbon nanotubes have a slight difference in work function, there is a significant difference in thermal stability.
  • the tip of the carbon nanotube has a large field enhancement factor, so the electron emission voltage (turn-on voltage) is lower than that of the sidewall, but it has a characteristic that it is easily decomposed by heat because of its high activity.
  • the sidewall of the carbon nanotube since the sidewall of the carbon nanotube has higher thermal stability than the tip, it has an advantage in terms of lifespan characteristics as a field emission device.
  • the carbon nanotube sheet roll emitter is formed in a bent form at the center and fixed on the substrate so that the sharp tip, which is the bent part, is facing up, so that the advantage of the sidewall of the carbon nanotube is utilized and the disadvantages are reduced. Available. Whether to use the carbon nanotube sheet roll by bending it as an emitter can be selected according to the current density and voltage to be used.
  • a carbon nanotube sheet roll emitter according to another embodiment of the present invention will be described.
  • FIG. 5 is a schematic diagram schematically showing the structure of a carbon nanotube sheet roll emitter according to another embodiment of the present invention.
  • the carbon nanotube sheet roll emitter 100 is a conductive member formed in the carbon nanotube sheet roll emitter according to an embodiment of the present invention, surrounding the lower surface of the carbon nanotube sheet roll.
  • the coupling portion 20 may be characterized in that it further includes.
  • the carbon nanotube sheet roll emitter 100 is wound together with the carbon nanotube sheet 10 of the carbon nanotube sheet roll on the carbon nanotube sheet roll emitter according to an embodiment of the present invention.
  • the carbon nanotube sheet roll may be characterized in that it further includes a conductive member coupling portion 20 formed while surrounding the lower surface.
  • the carbon nanotube sheet 10 may be characterized in that a plurality of carbon nanotube bundles 11 are bonded to each other through a covalent bond.
  • the carbon nanotube sheet roll emitter 100 may be fixed to the substrate through the conductive member coupling part 20 or the emitter may be directly fixed to the substrate.
  • the fixation to the substrate may be through conductive adhesive or welding.
  • the carbon nanotube sheet roll emitter 100 may be fixed so that the central axis A is perpendicular to the substrate.
  • a cross-section of a portion of the carbon nanotube sheet roll emitter 100 in which the conductive member coupling portion 20 is formed may have a shape as shown in FIG. 5 .
  • the height (L1) of the remaining portion except for the height (L2) portion occupied by the conductive member coupling part 20 and the carbon nanotube sheet roll emitter (100) may be characterized in that it has a length ratio of 1:5 to 9:10.
  • the total height of the carbon nanotube sheet roll emitter 100 is L
  • the predetermined height formed by the conductive member coupling portion is L2
  • the conductive member is combined among the entirety of the carbon nanotube sheet roll emitter 100 . If the height of the portion other than the predetermined portion formed by the addition is L1, L, L1, and L2 may be characterized in that they satisfy Equation 1 below.
  • a carbon nanotube sheet composed of a carbon nanotube bundle connected to each other by a covalent bond is formed in a roll shape to constitute a structurally stable emitter, so that the length of the portion exposed from the conductive member coupling portion is greater than the overall length. It has features that can be formed to have a sufficient length ratio of 1:5 to 9:10.
  • the conductive member coupling portion 20 is in the form of a metal thin film or a metal wire containing any one or more metals selected from the group consisting of tungsten, zinc, nickel, copper, silver, aluminum, gold, platinum, tin, and stainless steel. it could be
  • the conductive member coupling portion 20 may be made of an inorganic paste having conductive properties.
  • the inorganic paste having the conductive property a known conductive inorganic paste prepared including a metal, an inorganic reaction system, and an organic vehicle for imparting the conductive property may be used.
  • FIG. 6 is a flowchart schematically illustrating a method for manufacturing a carbon nanotube sheet roll emitter of the present invention.
  • the method of manufacturing a carbon nanotube sheet roll emitter of the present invention includes the steps of preparing a carbon nanotube sheet (S100); and manufacturing a carbon nanotube sheet roll emitter by winding the prepared carbon nanotube sheet around a central axis to form a roll (S200).
  • the carbon nanotube sheet may be characterized in that it is formed by bonding a plurality of carbon nanotube bundles to each other through a covalent bond.
  • FIG. 7 is a diagram schematically illustrating a manufacturing process of a carbon nanotube sheet according to an embodiment of the present invention.
  • the carbon nanotube is wound on the aggregate so that the carbon nanotube bundles 11 have a constant direction to prepare the carbon nanotube sheet 10 . to do; and preparing a carbon nanotube sheet by cutting the formed carbon nanotube sheet 10 by a desired predetermined length.
  • a raw material solution composed of a carbon source, a catalyst, and a cocatalyst may be synthesized while being supplied into a high-temperature synthesis furnace together with a transport gas.
  • a carbon source an organic solvent such as acetone, ethanol and butanol is mainly used, and metallocene such as ferrocene and nickellocene is used as a catalyst, and thiophene is used as a cocatalyst (Thiophene) or carbon disulfide (CS2) can be used.
  • the composition of the raw material solution for synthesizing the carbon nanotubes may vary depending on the carbon nanotubes to be manufactured.
  • ferrocein may be in a ratio of 0.1 to 4.0 wt%, and thiophene in a ratio of 0.05 to 3.0 wt%.
  • the transport gas fed together is hydrogen or nitrogen gas, 300 to 4,000 sccm, and the temperature of the electric furnace may be synthesized in the range of 800 to 1500 degrees.
  • the orientation direction of the carbon nanotube bundle and the central axis may be manufactured to form an angle of -45° to 45°.
  • the mechanical properties of the carbon nanotube sheet roll emitter can be adjusted.
  • the carbon nanotube bundles are tilted and rolled at a predetermined rolling angle, so that the carbon nanotube sheet roll emitter can be adjusted to better withstand the force acting in the lateral direction.
  • the angle preferably has a value of -45° to 45°.
  • the carbon nanotube bundles in the field emission device are inclined too much in the longitudinal direction, so that the field emission effect from the end of the carbon nanotube is reduced.
  • the angle preferably has a value of -45° to 45°.
  • a conductive material is placed on the lower end of the carbon nanotube sheet and then wound together to manufacture the carbon nanotube sheet roll emitter.
  • the conductive material may be wound together with the sheet in the form of a metal thin film or metal wire to form the emitter,
  • the emitter may be formed by being applied on the carbon nanotube sheet in the form of a conductive inorganic paste and then wound together with the sheet.
  • a field emission device according to another embodiment of the present invention will be described.
  • the field emission device may include a carbon nanotube sheet roll emitter according to an embodiment of the present invention.
  • the field emission device may include: a substrate; and a carbon nanotube sheet roll emitter positioned on the substrate.
  • the carbon nanotube sheet roll emitter may be a carbon nanotube sheet roll according to an embodiment of the present invention.
  • the carbon nanotube sheet roll emitter may be fixed on the substrate through a conductive material, and more specifically, may be coupled through a conductive adhesive or welding so that the central axis is perpendicular to the substrate.
  • the carbon nanotube sheet roll emitter is threaded between the nets of the substrate to intersect with the net of the substrate or welded, and then to the upper surface of the substrate.
  • a field emission device may be formed by cutting the exposed carbon nanotube sheet roll emitter into a plane parallel to the upper surface to expose a cross-section.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Cold Cathode And The Manufacture (AREA)

Abstract

Un mode de réalisation de la présente invention concerne un émetteur de rouleau de feuille de nanotubes de carbone présentant une stabilité structurelle améliorée, son procédé de fabrication, et un dispositif d'émission de champ l'utilisant. L'émetteur de rouleau de feuille de nanotubes de carbone comprend un rouleau de feuille de nanotubes de carbone dans lequel une feuille de nanotubes de carbone est enroulée autour de l'axe central du rouleau de feuille de nanotubes de carbone, la feuille de nanotubes de carbone étant formée par combinaison d'une pluralité de faisceaux de nanotubes de carbone les uns avec les autres par liaison covalente. Selon un mode de réalisation de la présente invention, il y a un effet dans lequel un émetteur qui est structurellement stable et peut être utilisé de façon stable même à une sortie élevée peut être fourni.
PCT/KR2020/018527 2020-10-28 2020-12-17 Émetteur de rouleau de feuille de nanotubes de carbone présentant une stabilité structurelle améliorée, son procédé de fabrication et dispositif d'émission de champ l'utilisant Ceased WO2022092425A1 (fr)

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KR1020200141058A KR102488299B1 (ko) 2020-10-28 2020-10-28 구조적 안정성이 향상된 탄소나노튜브 시트 롤 이미터, 이의 제조방법 및 이를 이용한 전계 방출 소자
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KR101962215B1 (ko) * 2018-11-30 2019-03-26 어썸레이 주식회사 일 방향으로 정렬된 얀을 포함하는 탄소나노튜브 시트를 제조하는 방법 및 이에 의해 제조된 탄소나노튜브 시트

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