WO1999005692A1 - Electron emitter - Google Patents
Electron emitter Download PDFInfo
- Publication number
- WO1999005692A1 WO1999005692A1 PCT/US1998/013377 US9813377W WO9905692A1 WO 1999005692 A1 WO1999005692 A1 WO 1999005692A1 US 9813377 W US9813377 W US 9813377W WO 9905692 A1 WO9905692 A1 WO 9905692A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electron emitter
- oxide
- passivation layer
- field emission
- emission device
- Prior art date
Links
Classifications
-
- 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
-
- 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
- H01J1/3042—Field-emissive cathodes microengineered, e.g. Spindt-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
- H01J29/04—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
- H01J2201/30403—Field emission cathodes characterised by the emitter shape
- H01J2201/30426—Coatings on the emitter surface, e.g. with low work function materials
Definitions
- the present invention pertains to the area of field emission devices and, more particularly, to coatings applied to the surfaces of the electron emitter structures of field emission devices.
- the electron emitter structures are Spindt-tip structures made from molybdenum
- the emission- enhancing coating is a metal that is selected for its low work function, which is less than that of the molybdenum.
- the surface work function of molybdenum is about 4.6 eV.
- Prior art emission-enhancing coatings are known to be made from a pure metal selected from the following: sodium, calcium, barium, cesium, titanium, zirconium, hafnium, platinum, silver, and gold. Also known are emission-enhancing coatings made from the carbides of hafnium and zirconium. These prior art coatings are known to improve the emission current characteristics of field emission electron emitters.
- the surfaces of the electron emitter structures react with oxygen-containing, gaseous species contained within the device, thereby transforming the surfaces of the electron emitter structures to an oxide of the metal.
- oxygen-containing, gaseous species contained within the device e.g., water vapor, oxygen, carbon dioxide, and carbon monoxide are present in amounts sufficient to cause appreciable oxidation of the molybdenum emitter surfaces during the operation of the device.
- the changing characteristics of the surfaces of the electron emitter structures result in emission current instabilities.
- molybdenum oxide the oxide of the metal from which electron emitter structures are typically made, has a work function that is greater than that of pure molybdenum, resulting in electron emission characteristics that are inferior to those of the pure molybdenum surface.
- FIG.l is a cross-sectional view of a first embodiment of a field emission device in accordance with the invention.
- FIGs.2 and 3 are cross-sectional views of a second embodiment of a field emission device in accordance with the invention.
- FIG.4 is a cross-sectional view of a third embodiment of a field emission device in accordance with the invention.
- FIGs.5 and 6 are cross-sectional views of a fourth embodiment of a field emission device in accordance with the invention.
- the invention is for a field emission device having electron emitter structures that are coated with a passivation layer.
- the passivation layer is chemically and thermodynamically more stable than prior art coatings.
- the passivation layer is resistant to oxidation during the operation of the field emission device.
- the passivation layer is preferably made from an oxide Most preferably, the oxide has a work function that is less than or equal to the work function of the electron emitter structuie
- the passivation layer is preferably made from an oxide being selected from a group consisting of the oxides of Ba, Ca, Sr, In, Sc, Ti, Ir, Co. Sr, Y, Zr, Ru, Pd, Sn. Lu, Hf.
- Exemplary oxides for use in the passivation layer of an electron emitter of the invention are BaO, Ba 3 WO 6 , CaO, SrO, In 2 O ⁇ Sc 2 O 3 , TiO, IrO 2 , Y 2 O , ZrO 2 , RuO 2 , PdO, SnO 2 .
- FIG 1 is a cross-sectional view of a field emission device (FED) 100 configured in accordance with the invention
- FED 100 includes a substrate 1 10, which is made from a hard material, such as glass, quartz, and the like
- a cathode 1 12 is disposed on substrate 1 10 and is made from a conductive material, such as molybdenum, aluminum, and the like
- Cathode 1 12 is formed using a convenient deposition process, such as sputtering, electron beam evaporation, and the like
- a dielectric layer 114 is formed on cathode 1 12 using standard deposition techniques, such as plasma-enhanced chemical vapor deposition
- Dielectric layer 114 is made from a dielectric material, such as silicon dioxide, silicon nitride, and the
- FED 100 has a passivation layer 120, which is disposed on electron emitter structures 118, gate electrodes 1 16, and dielectric layer 1 14
- An electron emitter 121 is defined by electron emitter structure 1 18 and the portion of passivation layer 120 that is formed thereon
- Passivation layer 120 is made from a material that is chemically and thermodynamically stable within the vacuum environment of FED 100 The chemical and thermodynamic stability of passivation layer 120 provides stable electron emission from electron emitter 121.
- passivation layer 120 is chemically and thermodynamically more stable than electron emitter structure 118
- passivation layer 120 is resistant to oxidation during the operation of FED 100
- passivation layer 120 has a greater resistance to oxidation than the material comprising electron emitter structures 1 18
- passivation layer 120 is made from a material having a work function that is less than the work function of the material from which electron emitter structures 118 are made
- passivation layer 120 has an electrical resistance that is high enough to avoid electrical shorting between gate electrodes 116
- passivation layer 120 can be made from an oxide that has a high resistivity, such as the lanthanide oxides
- passivation layer 120 can be made from a conductive oxide if passivation layer 120 is made very thin (a monolayer to about 100 nanometers), so that the sheet resistance is high enough to mitigate electrical shorting problems between gate electrodes 116
- a passivation layer in accordance with the invention is preferably made from an oxide Most preferably, it is made from an oxide that has a surface work function that is less than that of the material from which electron emitter structure 1 18 is made.
- electron emitter structure 118 is made from molybdenum, which has a surface work function of about 4 6 eV
- Table 1 below tabulates representative values of the work functions of selected oxides, which are contemplated for use in a passivation layer in accordance with the invention
- the work function data of Table 1 is extracted from the Handbook of Thermionic Properties by V.S Fomenko, Plenum Press, New York, 1966
- the work function of a particular surface depends, in part, upon the configuration of the lattice plane at the emissive surface
- some of the oxides listed in Table 1 have corresponding thereto several values for the work function
- the oxides of the lanthanide rare earth elements (La 2 O 3 , Ce O 3 ,
- Pr 2 O 3 , etc. have surface work functions that are less than that of molybdenum. These oxides also have resistivities that are high enough to prevent electrical shorting between gate electrodes 116. Thus, they are suitable for use in passivation layer 120.
- Passivation layer 120 may be realized by performing a blanket, normal (90° with respect to the plane of the cathode plate) deposition of the oxide from the gas phase. This method is useful for oxides that can be deposited using standard vapor deposition techniques, such as evaporation, electron beam evaporation, sputtering, plasma-enhanced chemical vapor deposition, and the like.
- Passivation layer 120 may also be deposited using a liquid carrier, as is described in greater detail with reference to FIGs. 4 - 6.
- the oxide is dispersed into the liquid carrier to form a liquid mixture.
- the liquid mixture is deposited onto the surface of the cathode plate, thereby coating electron emitter structures 118 and the surfaces of gate electrodes 116 and dielectric 114.
- the liquid carrier is then selectively removed.
- an organometallic precursor which contains the metallic element of the oxide, may be employed.
- the organometallic precursor is dispersed into the liquid carrier, and converted to the oxide during a plasma ashing step, which is utilized to selectively remove the liquid carrier. No sacrificial layer, which is described with respect to FIGs. 4 - 6, is required in the fabrication of the embodiment of FIG.1.
- the thickness of a passivation layer in accordance with the invention is predetermined to provide electron emission from a selected surface.
- thinner films can be employed to enhance electron emission from a surface 123 of electron emitter structure 118.
- a thin film can include one monolayer of material.
- Thicker films can be employed to provide electron emission from the passivation layer.
- Such thick films define the surface of the electron emitter, and electrons are emitted from this surface.
- passivation layer 120 has a thickness that is preferably between 50 - 500 angstroms, so that a surface 125 of electron emitter 121 is defined by passivation layer 120.
- FED 100 is operated by applying to cathode 112, gate electrodes 116, and anode 122 predetermined potentials suitable for effecting electron emission, which is indicated by an arrow 124 in FIG.l, from electron emitters 121.
- An electron emitter in accordance with the invention is also contemplated for use in field emission devices having electrode configurations other than a triode configuration.
- the electron emitter of the invention can be employed in a diode field emission device, or in devices having additional focusing electrodes.
- the passivation layer is disposed on electron emitter structures 1 18; none of the passivation layer is disposed between gate electrodes 116.
- This particular configuration is depicted in FIGs.2 and 3. It is particularly useful for oxides that have resistivities that are lower than those of the oxides contemplated for use in the embodiment of FIG.1.
- FIGs.2 and 3 are cross-sectional views of a field emission device (FED) 200 in accordance with the invention.
- FED 200 field emission device
- FED 200 can be made by first forming a sacrificial layer 226 on gate electrodes 116 and dielectric layer 114.
- Sacrificial layer 226 is made from a sacrificial material, which is capable of being selectively removed subsequent to the deposition of passivation layer 220.
- Sacrificial layer 226 is preferably made from a metal selected from a group consisting of aluminum, zinc, copper, tin, titanium, vanadium, and silver. .
- Sacrificial layer 226 is formed by employing an angled deposition, to mitigate deposition of the sacrificial material onto the walls of emitter well 115 and surfaces 123.
- passivation layer 220 is deposited onto the cathode plate by performing a blanket, normal (90° with respect to the plane of the cathode plate) deposition of the oxide from the gas phase.
- This method is useful for oxides that can be deposited using standard vapor deposition techniques, such as evaporation, electron beam evaporation, sputtering, plasma-enhanced chemical vapor deposition, and the like.
- the thickness of passivation layer 220 is within a range of about 50 - 500 angstroms, so that a surface 225 is defined by the oxide of passivation layer 220, and so that electron emission is from passivation layer 220.
- the combination of electron emitter structure 118 and that portion of passivation layer 220 disposed thereon defines an electron emitter 221.
- sacrificial layer 226 is selectively removed, as by a convenient selective etch process.
- anode 122 is assembled with the cathode plate, as depicted in FIG.3.
- Exemplary conductive oxides that are preferably deposited by the method described with reference to FIGs.2 and 3 are ln 2 0 3 , IrO 2 , RuO 2 , PdO, SnO 2 ⁇ ReO 3 , In 2 O 3 :SnO 2 , BaTiO 3 , BaCuO x , Bi 2 Sr 2 CaCu 2 O , YBa 2 Cu 3 0 7 . , SrRuO 3 , where x is an integer.
- oxides contemplated for use in the passivation layer of an electron emitter of the invention are not conveniently deposited by standard vapor deposition techniques. These oxides include, but are not limited to, RuO 2 and ReO Methods that are particularly useful for the deposition of these types of oxides are described below with reference to FIGs.4 - 6.
- FIG.4 depicts a structure formed in the fabrication of a FED 300, which is configured in accordance with the invention.
- the emission-enhancing oxide or a precursor thereof is first dispersed within a liquid carrier.
- the liquid carrier is an organic spreading liquid medium.
- the organic spreading liquid medium is a liquid organic material, such as an alcohol, acetone, or other organic solvent, which is capable of being selectively removed from a passivation layer 320 subsequent to its deposition onto the cathode plate.
- the liquid mixture is applied to the surface of the cathode plate by a convenient deposition method, such as roll-coating, spin-on coating, and the like.
- the liquid mixture coats electron emitter structures 1 18 and sacrificial layer 226.
- the organic spreading liquid medium is removed therefrom.
- the removal of the organic spreading liquid medium is achieved by an ashing procedure, which includes the step of burning the organic spreading liquid medium by exposure to a plasma.
- an electron emitter 321 which includes electron emitter structure 118 and the coating of the emission-enhancing oxide formed thereon, is realized.
- sacrificial layer 226 is selectively removed by a selective etching procedure.
- the cathode plate is assembled with an anode (not shown).
- the thickness of the final, emission-enhancing coating is determined by the concentration of the emission-enhancing oxide or precursor thereof in the organic spreading liquid medium.
- a low concentration can be used to form a very thin coating.
- a very thin coating results in a surface 325 of electron emitter 321, which is defined by the oxide and electron emitter structure 118.
- a very thin coating may include one monolayer of the emission-enhancing oxide.
- the concentration is predetermined so that the final coating is thick enough to define surface 325 of electron emitter 321. In this latter configuration, electron emission is only from the oxide coating. This configuration is particularly useful for emission-enhancing oxides having work functions that are less than that of electron emitter structure 1 18.
- the thickness of these thicker coatings is greater than about 100 angstroms.
- the precursor of the emission-enhancing oxide is converted to the corresponding emission- enhancing oxide subsequent to the deposition of the liquid mixture onto the cathode plate.
- An exemplary precursor is an organometallic material, the metallic chemical element of which forms an oxide that is an emission-enhancing material.
- the metallic chemical element of the precursor is converted to the emission-enhancing oxide during the step of removing the organic spreading liquid medium. Specifically, during the plasma ashing step, the metallic chemical element of the organometallic material is oxidized.
- an organometallic precursor useful for the formation of ruthenium oxide is dodecacarbonyltriruthenium [Ru 3 (CO) ⁇ 2 ] or ruthenium(III)2,4-pentanedionate [Ru(CsH 7 O 2 ) 3 ]; an organometallic precursor useful for the formation of rhenium oxide is decacarbonyldirhenium [Re 2 (CO) ⁇ 0 ]-
- the method described with reference to FIG.4 can also be utilized to fabricate the configuration illustrated in FIG.1 when the resistivity of the final oxide coating is high enough to avoid electrically shorting gate electrodes 116.
- the sacrificial layer is omitted.
- Certain emission-enhancing oxides that can be deposited using a liquid carrier, such as described with reference to FIG.4, are conductive enough to result in electrical shorting problems if they are deposited on or proximate to the surfaces of dielectric layer 1 14 that define emitter wells 115. These conductive emission-enhancing oxides can also be selectively deposited onto electron emitter structures 118 by a method in accordance with the invention, as described with reference to FIGs.5 and 6.
- FIGs.5 and 6 Illustrated in FIGs.5 and 6 are cross-sectional views of a FED 400 having a passivation layer 420, which contains a conductive emission-enhancing oxide.
- Passivation layer 420 is formed by first dispersing the conductive emission-enhancing oxide into a liquid, negative photoresist material. This mixture is deposited onto the cathode plate by a convenient liquid deposition method, such as roll-coating, spin-on coating, and the like. This deposition step generally coats sacrificial layer 226 and electron emitter structures 1 18. However, some of the deposited material may form a foot portion 422 at the base of each of emitter wells 115 and/or may be deposited along the walls defining emitter wells 115.
- these portions of the deposited material may result in electrical shorting problems between cathode 112 and gate electrodes 1 16, due to the relatively low resistivity of the conductive emission-enhancing oxide.
- These portions of the deposited material can be removed by first photo-exposing the cathode plate to collimated UV light, which is directed toward the cathode plate in a direction generally normal to the plane of the cathode plate.
- the collimated UV light is indicated by a plurality of arrows 424 in FIG.5.
- the upper protruding portion of the structure defining each of emitter wells 115 masks from the UV light foot portion 422 and any material deposited on the walls of emitter wells 115.
- passivation layer 420 is developed, thereby removing the portions of passivation layer 420 that were not photo-exposed, as illustrated in FIG.6. Then, the negative resist is removed from passivation layer 420, as by plasma ashing. In this manner an electron emitter 421. which includes electron emitter structure 1 18 and the emission- enhancing oxide formed thereon, is realized.
- sacrificial layer 226 is removed. Subsequent to the removal of sacrificial layer 226, the cathode plate is assembled with an anode (not shown). Examples of conductive emission-enhancing oxides that can be deposited in the manner described with reference to FIGs. 5 and 6 include RuO 2 , PdO, SnO 2 , ReO 3 , and IrO 2 .
- the thickness of the final configuration of passivation layer 420 is determined in a manner similar to that described with reference to FIG.4.
- the oxide defines a surface 425 of electron emitter 421.
- the invention is for a field emission device having electron emitter structures that are coated with a passivation layer, which is chemically and thermodynamically more stable than prior art coatings.
- the passivation layer is preferably made from an oxide selected from a group consisting of the oxides of Ba, Ca, Sr. In, Sc, Ti, Ir, Co, Sr, Y, Zr, Ru, Pd, Sn, Lu, Hf, Re, La. Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy. Ho, Er, Tm. Yb, Th, and combinations thereof.
- a field emission device of the invention provides more stable electron emission, a longer device lifetime, a lower operating voltage for a specified emission current, reduced shorting problems between individual gate electrodes and between gate electrodes and cathode electrodes, and less stringent vacuum requirements than prior art field emission devices.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98931663A EP0928494B1 (en) | 1997-07-28 | 1998-06-26 | Electron emitter |
DE69828578T DE69828578T2 (en) | 1997-07-28 | 1998-06-26 | ELECTRON EMITTER |
JP11509828A JP2001501358A (en) | 1997-07-28 | 1998-06-26 | Electron emitter |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/901,734 US6091190A (en) | 1997-07-28 | 1997-07-28 | Field emission device |
US08/901,734 | 1997-07-28 |
Publications (1)
Publication Number | Publication Date |
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WO1999005692A1 true WO1999005692A1 (en) | 1999-02-04 |
Family
ID=25414724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/013377 WO1999005692A1 (en) | 1997-07-28 | 1998-06-26 | Electron emitter |
Country Status (8)
Country | Link |
---|---|
US (1) | US6091190A (en) |
EP (1) | EP0928494B1 (en) |
JP (1) | JP2001501358A (en) |
KR (1) | KR100561325B1 (en) |
CN (1) | CN1237270A (en) |
DE (1) | DE69828578T2 (en) |
TW (1) | TW374193B (en) |
WO (1) | WO1999005692A1 (en) |
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WO2001054155A2 (en) * | 2000-01-18 | 2001-07-26 | Motorola, Inc. | Field emission device |
JP2001357773A (en) * | 2000-04-26 | 2001-12-26 | Samsung Sdi Co Ltd | Electric field emission array utilizing carbon nanotube and its manufacturing method |
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JP2000123711A (en) * | 1998-10-12 | 2000-04-28 | Toshiba Corp | Electric field emission cold cathode and manufacture thereof |
US6410101B1 (en) * | 2000-02-16 | 2002-06-25 | Motorola, Inc. | Method for scrubbing and passivating a surface of a field emission display |
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JP2013101946A (en) * | 2012-12-26 | 2013-05-23 | Tohoku Univ | Manufacturing method of cathode body |
JP6582655B2 (en) * | 2015-07-14 | 2019-10-02 | 株式会社リコー | Field effect transistor, display element, image display device, and system |
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- 1998-06-26 CN CN98801204A patent/CN1237270A/en active Pending
- 1998-06-26 WO PCT/US1998/013377 patent/WO1999005692A1/en active IP Right Grant
- 1998-06-26 DE DE69828578T patent/DE69828578T2/en not_active Expired - Fee Related
- 1998-06-26 KR KR1019997002617A patent/KR100561325B1/en not_active IP Right Cessation
- 1998-06-26 JP JP11509828A patent/JP2001501358A/en active Pending
- 1998-07-07 TW TW087110976A patent/TW374193B/en active
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Cited By (3)
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WO2001054155A2 (en) * | 2000-01-18 | 2001-07-26 | Motorola, Inc. | Field emission device |
WO2001054155A3 (en) * | 2000-01-18 | 2002-08-08 | Motorola Inc | Field emission device |
JP2001357773A (en) * | 2000-04-26 | 2001-12-26 | Samsung Sdi Co Ltd | Electric field emission array utilizing carbon nanotube and its manufacturing method |
Also Published As
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KR20000068641A (en) | 2000-11-25 |
DE69828578D1 (en) | 2005-02-17 |
KR100561325B1 (en) | 2006-03-16 |
EP0928494A1 (en) | 1999-07-14 |
JP2001501358A (en) | 2001-01-30 |
CN1237270A (en) | 1999-12-01 |
DE69828578T2 (en) | 2005-12-29 |
US6091190A (en) | 2000-07-18 |
EP0928494B1 (en) | 2005-01-12 |
TW374193B (en) | 1999-11-11 |
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