WO2003069649A1 - Electrode, emetteur d'electrons et dispositif les utilisant - Google Patents

Electrode, emetteur d'electrons et dispositif les utilisant Download PDF

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Publication number
WO2003069649A1
WO2003069649A1 PCT/JP2002/005964 JP0205964W WO03069649A1 WO 2003069649 A1 WO2003069649 A1 WO 2003069649A1 JP 0205964 W JP0205964 W JP 0205964W WO 03069649 A1 WO03069649 A1 WO 03069649A1
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WO
WIPO (PCT)
Prior art keywords
film
boron
carbon
electron
electrode according
Prior art date
Application number
PCT/JP2002/005964
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English (en)
Japanese (ja)
Inventor
Takashi Sugino
Masaki Kusuhara
Masaru Umeda
Original Assignee
Kabushiki Kaisha Watanabe Shoko
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 Kabushiki Kaisha Watanabe Shoko filed Critical Kabushiki Kaisha Watanabe Shoko
Priority to JP2003568680A priority Critical patent/JPWO2003069649A1/ja
Publication of WO2003069649A1 publication Critical patent/WO2003069649A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J3/00—Details of electron-optical or ion-optical arrangements or of ion traps common to two or more basic types of discharge tubes or lamps
    • H01J3/02—Electron guns
    • H01J3/021—Electron guns using a field emission, photo emission, or secondary emission electron source
    • 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

Definitions

  • the present invention relates to an electrode and an electron-emitting device utilizing electron emission from a thin film.
  • Cold cathodes can be applied to field emission displays, electron beam exposure machines, microwave traveling wave tubes, imaging devices, and the like. Further, it can be used as an electron source of a material evaluation device such as an Auger electron spectrometer using an electron beam. Further, the light-emitting element can be used for a lighting device or a display lamp, and can be used for various applications. Conventionally, research and development has been conducted on electron emitters called spindt type, which have a spire shape made of metal or silicon as a cold cathode. There is a demand for device reliability, and improvements in the characteristics of Spindt-type cold cathodes and research and development of new cold cathode materials are underway.
  • Diamond, aluminum nitride, and boron nitride have attracted attention as materials having a negative electron affinity. Electron emission is observed in the field, and it is expected to be applied to field emission displays. However, there was a problem about the spatial stability of the electron emission characteristics from these carbon nanotubes and carbon nanofibers. Further low-voltage operation and high-current operation are desired in the future.
  • the present invention has been made in view of the above situation, and an object of the present invention is to provide a cold cathode having electron emission characteristics superior to conventional ones. Disclosure of the invention
  • the electrode of the present invention has a film on a base material capable of supplying electrons, the film has an electric field, and has a state density capable of tunneling electrons from the base material. I do.
  • the electric field in the film is formed by a negative charge in the one material and a positive charge in the film.
  • the positive charges in the film are generated by any of an amorphous region, a crystal grain boundary, and the presence of impurity atoms.
  • a film having a thickness of 30 nm or less and an electron affinity of 4.0 eV or less is provided on the surface. It is to be noted that the thinner the film is, the more preferable it is. The effect becomes remarkable at 10 nm or less, and 3 to 5 nm is preferable in consideration of the production cost.
  • the electron affinity is preferably 3.5 eV or less. The smaller the electron affinity is, the more preferable it is.
  • the film is any one of a compound of a group II and a nitrogen atom, or an oxide containing boron nitride carbon, boron carbide, carbon nitride, or boron.
  • Boron nitride (BN), aluminum nitride (AIN), and indium nitride (InN) are examples of binary compounds of group III atoms and nitrogen atoms, and these are binary compounds. Can also be used.
  • the above-described film includes any one of atoms of silicon, zeolite, phosphorus, oxygen, and lithium. When such an atom is contained, it has an effect of increasing the Fermi level.
  • the content is preferably 0.001% to 1% in atom%, more preferably 0.01% to 0.1%.
  • hydrogen is present on the surface of the film.
  • the effect of reducing electron affinity is achieved.
  • a hydrogen plasma treatment may be performed after the film is deposited.
  • the film is present on a surface of a substrate having irregularities or a spire shape. If the membrane has irregularities or a spire shape, inside the membrane and on the membrane surface The effect of increasing the electric field strength by the unevenness or the spire-shaped portion in the above is achieved.
  • the invention is characterized in that the film is present on the surface of a carbon nanotube or a carbon nanofiber. In this case, the effect of further increasing the electric field strength in the film and on the film surface is achieved.
  • the electron emission device of the present invention is characterized in that the electrode is provided as a cathode. Further, the plasma display of the present invention is characterized in that the electrodes are used as electrodes of a discharge cell.
  • the electron-emitting device of the present invention When the electron-emitting device of the present invention is used for a field emission display, a low-voltage operation and a clear image can be realized.
  • an electron beam exposure apparatus with high resolution and improved throughput can be realized.
  • the electron-emitting device of the present invention is used for a microwave traveling wave tube, a high output microwave output can be obtained.
  • the electron-emitting device of the present invention when used in a material evaluation device using an electron beam, an improvement in evaluation accuracy can be realized.
  • the electrode of the present invention is used for an electrode of a light-emitting element.
  • the electrode of the present invention is used for a light-emitting element, clear light emission with high luminance can be obtained, and high-quality illumination and display can be realized.
  • FIG. 1 is a sectional view showing Embodiment 1 of the electron-emitting device of the present invention.
  • FIG. 2 is a sectional view showing Embodiment 2 of the electron-emitting device of the present invention.
  • FIG. 3 is a sectional view showing Embodiment 3 of the electron-emitting device of the present invention.
  • FIG. 4 is a sectional view showing Embodiment 4 of the electron-emitting device of the present invention.
  • FIG. 5 is a cross-sectional view showing Example 5 of the light emitting device of the present invention.
  • FIG. 6 is a sectional view showing Example 6 of the organic light emitting device of the present invention.
  • the electrode and the electron-emitting device according to the present invention are a conventional Spindt-type cold cathode made of silicon-molybdenum, a cold cathode made by providing irregularities on the surface of another metal or a semiconductor substrate, and a carbon nanotube on a metal substrate.
  • a film corresponding to the present invention is provided with a thickness of 50 nm or less on a cold cathode on which a carbon nanofiber is produced, and on a flat substrate made of metal or semiconductor.
  • the thin film of the present invention may be provided. By doing so, it is possible to provide a flat-type electron emission device that is effective in improving the electron emission characteristics and reliability of the cold cathode described above and that is easy to manufacture.
  • FIG. 1 is a schematic sectional view of an electron-emitting device according to a first embodiment of the present invention.
  • the electron-emitting device of the first embodiment includes a substrate 1, a boron nitride thin film 2, a SiO x film 3, an extraction electrode 4, an anode electrode 5, power supplies 6, 7, and a power source electrode 8.
  • silicon was used as the substrate 1.
  • a 10 nm-thick boron nitride thin film 2 was deposited thereon by plasma-assisted chemical vapor deposition (CVD) using boron trichloride and nitrogen gas.
  • the boron nitride thin film 2 was doped with iodine atoms at a concentration of 1 ⁇ 10 18 cm_3.
  • a TiO x thin film 3 is formed on the boron nitride thin film 2 by 800 nm, and Ti (20 nm) / Au (500 nm) is formed by electron beam evaporation as a metal for the extraction electrode 4. I do.
  • the extraction electrode 4 was grounded, a bias was applied to each of the cathode electrode 8 and the anode electrode 5, and the emission current was measured at a degree of vacuum of 8.times.10.sup.- 7 Torr or less.
  • the anode voltage was kept constant at 500 V, and the cathode voltage was changed. Electron emission started when 10 V was applied to the force source electrode 8, and a high emission current of 0.1 mA was obtained when 30 V was applied.
  • a 10 nm-thick boron nitride thin film is deposited on a flat silicon substrate by the above-mentioned method, and the electron emission characteristics are kept constant at 125 m between the boron nitride thin film and the anode electrode 5 without forming the extraction electrode 4.
  • the surface roughness of the film was evaluated. A surface roughness of 0.3-0.7 nm was evaluated for a flat silicon substrate surface, and a surface roughness of 0.6-1.2 nm was evaluated for a 10-nm-thick boron nitride film. .
  • the effective potential barrier height is evaluated to be about 0.6 eV, and the present invention makes it possible to significantly reduce the effective potential barrier height. A reduction in the electron emission threshold electric field can be expected.
  • boron nitride film was used, but all materials according to the present invention can be used other than boron nitride.
  • the boron nitride film was synthesized by plasma-assisted CVD.
  • various manufacturing methods such as metal organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), and sputtering were used. Can be used.
  • boron nitride thin film 2 doped with zeo impurities was used, a boron nitride thin film 3 doped with atoms of donor impurities such as lithium, oxygen, and silicon can also be used. Similar impurities can be used for compounds consisting of a group III atom and a nitrogen atom other than boron nitride.
  • silicon was used as the substrate material, but other conductors and semiconductors such as metal, gallium arsenide, indium phosphide, silicon carbide, and gallium nitride can be used.
  • Ti / Au is used as the metal for the extraction electrode 4
  • various metals can be used instead of Cr and Au instead of Ti.
  • any metal that can form an ohmic electrode can be used as the metal for the cathode electrode 8
  • the substrate itself is used as the cathode electrode. be able to.
  • FIG. 2 is a schematic sectional view of an electron-emitting device according to a second embodiment of the present invention.
  • Spindt spire shape is formed on the silicon substrate 1, an electron emitting device boron carbon nitride film is provided et the of the present invention, the substrate 2 1, boron carbon nitride film 22, S i O x film 23, the extraction electrode 24, an anode electrode 25, power supplies 26 and 27, a cathode electrode 28, and a spire shape 29.
  • the boron nitride carbon thin film 22 of the present invention is formed on the spire portion 29.
  • Boron carbon nitride thin film 22 (composition ratio, boron 0.4, carbon 0.2, nitrogen 0.4) was deposited to a thickness of 10 nm by plasma-assisted chemical vapor deposition using boron trichloride, methane, and nitrogen gas. .
  • the boron nitride carbon thin film 22 was doped with iodine atoms at a concentration of 1 ⁇ 10 18 cm ⁇ 3 .
  • a 1 (500 nm) was electron beam evaporated as a force source electrode 28 on the back surface of the silicon substrate 1.
  • the metal plate serving as the anode electrode 25 is opposed to the spire portion 29 having the boron nitride carbon thin film 22 in the vacuum chamber, and the interval is 1 25 im And Grounded extraction electrode 24, in addition to each Baia scan the Chikarasoichido electrode 2 8 and the anode electrode 2 5 was measured emission current at 8 X 1 0 7 T 0 rr following vacuum.
  • the anode voltage was kept constant at 500 V, and the force sword voltage was varied. By applying 20 V to the force source electrode 28, a high emission current of 0.1 mA was obtained.
  • boron nitride carbon thin film is used, but other materials described above including boron nitride can also be used.
  • FIG. 3 is a schematic sectional view of an electron-emitting device according to a third embodiment of the present invention.
  • the electron-emitting device of Example 3 has a silicon substrate 31 on which an n-type gallium nitride layer 30 is formed, a boron nitride carbon thin film 32, a Si x film 33, an extraction electrode 34, an anode electrode 35, a power supply 36, and 37.
  • the force sword electrode 38 is constituted.
  • a wafer obtained by growing a silicon-added n-type gallium nitride layer 30 by 1 m on an n-type silicon substrate 31 (111) surface by metal organic chemical vapor deposition is used as a substrate.
  • Hydrogen plasma is generated by microwaves to treat the surface of the gallium nitride layer 30.
  • the flat surface of the gallium nitride layer 30 changes to a surface having irregularities of several tens nm.
  • a boron-nitride carbon thin film 32 (composition ratio, boron 0.4, carbon 0.2, nitrogen 0.4) was formed to a thickness of 10 nm by plasma-assisted chemical vapor synthesis using boron trichloride, methane, and nitrogen gas. Accumulated.
  • the boron nitride carbon thin film 32 was doped with iodine atoms at a concentration of 1 ⁇ 10 18 cm ⁇ 3 .
  • Ti (20 nm) / Au (500 nm) is formed as a metal for the extraction electrode 34 by an electron beam evaporation method.
  • Grounded extraction electrode 3 4 and each added server Iasu force cathode electrode 3 8 and the anode electrode 35 was measured emission current at degree of vacuum of 8 X 1 0- 7 T 0 rr .
  • the anode voltage was kept constant at 500 V and the force source voltage was varied. By applying 30 V to the force source electrode 38, a high emission current of 0.1 mA was obtained.
  • the uneven surface is formed by the hydrogen plasma treatment, but a gas containing oxygen, chlorine, fluorine, or the like can be used as a gas for generating plasma for forming the unevenness on the surface.
  • RF power can be used to generate plasma, and applying a bias to the sample during plasma processing is effective in controlling the surface shape.
  • FIG. 4 is a schematic sectional view of an electron-emitting device according to a fourth embodiment of the present invention.
  • This is an electron emission device in which carbon nanofibers 40 are formed on a metal substrate 41 and a boron nitride carbon film of the present invention is provided.
  • Carbon nanofibers 40 are formed on a metal substrate 41, and a boron nitride carbon thin film 42 of the present invention is formed thereon.
  • Boron carbon nitride thin film 42 (composition ratio, boron 0.4, carbon 0.2, nitrogen 0.4) was deposited to a thickness of 10 nm by plasma-assisted chemical vapor deposition using boron trichloride, methane, and nitrogen gas. .
  • the boron nitride thin carbon film 4 2 was added Iou atom concentration of 1 X 1 0 1 8 c m_ 3.
  • 800 nm of S i ⁇ x thin film 43 was placed on the boron nitride carbon thin film 42, and T i (20 nm) / Au (500 nm) was used as the metal for extraction electrode 44 by electron beam. It is formed by a vapor deposition method.
  • the metal for the extraction electrode 44 and S The I_ ⁇ x thin film 4 3 is removed by etching, to form a window with a diameter of 5 m.
  • the metal plate to be the anode electrode 45 is made to face the boron nitride carbon thin film 42 in a vacuum chamber.
  • Grounded extraction electrode 4 4, the metal substrate 4 1 and cathodes when cathode electrode, and each of the bias added to the metal substrate 4 1 and the anode electrode 4 5, 8 X 1 0- 7 T orr degree of vacuum below in emission current was measured.
  • the anode voltage was kept constant at 500 V, and the force source voltage was changed. By applying 10 V to the metal substrate 41, a high emission current of 0.1 mA was obtained.
  • Example 2 as described in Example 1, the compound of the group III atom and the nitrogen atom, the oxide containing nitrogen-boron-carbon, boron carbide, carbon nitride, carbon-nitride was used as the material of the electron-emitting portion as described in Example 1. Any of these materials can be used. Further, in Examples 1 to 4, two or more electron-emitting portions can be manufactured on the same substrate to realize an array.
  • FIG. 5 is a schematic sectional view of a light emitting device using an electron-emitting device according to a fifth embodiment of the present invention.
  • This is a light emitting device (lamp) in which carbon nanofibers 50 are formed on a metal substrate 51 and the boron nitride carbon film of the present invention is provided.
  • the substrate 51, the boron nitride carbon thin film 52, the extraction electrode It consists of 54, an anode electrode 55, a power source electrode 58, a phosphor 510, and a glass tube 511.
  • a carbon nanofiber 50 is formed on a metal substrate 51, and a boron nitride carbon thin film 52 of the present invention is formed thereon.
  • the boron nitride carbon thin film 4 was doped with iodine atoms at a concentration of 1 ⁇ 10 18 cm ⁇ 3 .
  • the extraction electrode 54 on the mesh is attached, placed in a glass tube 511 in which the anode electrode 55 is formed on the phosphor 510, and vacuum-sealed. By applying 400 V to the extraction electrode 54 with respect to the force source electrode 58 and applying 10 kV to the anode electrode 55, a current of 500 A was obtained, and light emission was observed.
  • FIG. 6 does not show a schematic sectional view of an organic light emitting device using an electrode according to the sixth embodiment of the present invention.
  • An anode 62 is formed on a glass substrate 61 using an ITO transparent electrode, and a hole transport layer 63 and a light emitting layer 64 are formed thereon using an organic thin film. It consists of a boron oxide thin film 66 and a metal (lithium or magnesium) 67 with a small work function.
  • the cathode of the present invention the efficiency of electron injection can be improved, and an organic light-emitting device with improved light-emitting characteristics can be obtained.
  • the emission current was measured in the same manner as in the fourth embodiment using stainless steel fibers or fiber pieces instead of the carbon nanofibers 40 formed on the metal substrate 41 of the fourth embodiment of the present invention. The same characteristics as in the example were obtained.
  • a fiber or a fiber piece formed by boron and nitrogen is used to reduce the emission current as in the fourth embodiment. As a result of measurement, higher characteristics were obtained than in the fourth example.
  • an electron emission device having any one of a film of a compound of a group III atom and a nitrogen atom having an electric field, boron nitride carbon, boron carbide, carbon nitride, and an oxide containing boron is used.
  • Low voltage operation and high current operation are possible, and the effect of the present invention is further enhanced by having the film of the present invention on a substrate having a concave-convex ⁇ spire shape, or on a carbon nanotube or a carbon nanofiber.
  • the performance is also improved. This provides a high-performance electron emission device, which is effective as a key device of a display device, an electron beam exposure machine, an imaging device, a light emitting element, and a material evaluation device using an electron beam.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Cold Cathode And The Manufacture (AREA)
  • Electrodes For Cathode-Ray Tubes (AREA)

Abstract

Emetteur d'électrons haute performance capable d'émettre des électrons à basse tension et luminance élevée, ce qui permet d'améliorer davantage la caractéristique d'émission d'électrons d'une cathode froide de type Spindt, d'un nanotube de carbone ou d'une nanofibre de carbone. Cet émetteur d'électrons constitue un composant de base d'un écran plat, d'un imageur, d'un dispositif à faisceau électronique, d'un tube à ondes progressives micro-ondes ou d'un illuminateur. La fabrication de cet émetteur d'électrons consiste à créer un film présentant un champ électrique, dont l'épaisseur est inférieure à 50 nm et l'affinité pour les électrons inférieure à 4 eV, sur une cathode froide de type Spindt, un nanotube de carbone, une nanofibre de carbone ou un substrat métallique ou semi-conducteur possédant une surface irrégulière. Ce film est constitué par un composé atomique de nitrure et d'un élément du groupe III, tel que nitrure d'aluminium, nitrure de bore, nitrure d'aluminium-bore, nitrure d'aluminium gallium ou nitrure de bore-gallium, nitrure de bore-carbone, carbone de bore, nitrure de carbone ou un oxyde contenant bore.
PCT/JP2002/005964 2002-02-18 2002-06-14 Electrode, emetteur d'electrons et dispositif les utilisant WO2003069649A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007053129A (ja) * 2005-08-15 2007-03-01 Nikon Corp 電子銃及び電子線露光装置。

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000348599A (ja) * 1999-06-02 2000-12-15 Sharp Corp 電界放出電子源及びその製造方法
EP1081767A2 (fr) * 1999-09-03 2001-03-07 Sel Semiconductor Energy Laboratory Co., Ltd. Dispositif d'affichage électroluminescent et méthode de fabrication
JP2002015659A (ja) * 2000-06-30 2002-01-18 Takashi Sugino 電子放出装置
JP2002042663A (ja) * 2000-07-24 2002-02-08 Sony Corp 交流駆動型プラズマ表示装置及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000348599A (ja) * 1999-06-02 2000-12-15 Sharp Corp 電界放出電子源及びその製造方法
EP1081767A2 (fr) * 1999-09-03 2001-03-07 Sel Semiconductor Energy Laboratory Co., Ltd. Dispositif d'affichage électroluminescent et méthode de fabrication
JP2002015659A (ja) * 2000-06-30 2002-01-18 Takashi Sugino 電子放出装置
JP2002042663A (ja) * 2000-07-24 2002-02-08 Sony Corp 交流駆動型プラズマ表示装置及びその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007053129A (ja) * 2005-08-15 2007-03-01 Nikon Corp 電子銃及び電子線露光装置。

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