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WO1997036693A1 - Procede permettant de modifier le travail d'extraction par implantation d'ion - Google Patents

Procede permettant de modifier le travail d'extraction par implantation d'ion Download PDF

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Publication number
WO1997036693A1
WO1997036693A1 PCT/US1997/006168 US9706168W WO9736693A1 WO 1997036693 A1 WO1997036693 A1 WO 1997036693A1 US 9706168 W US9706168 W US 9706168W WO 9736693 A1 WO9736693 A1 WO 9736693A1
Authority
WO
WIPO (PCT)
Prior art keywords
implanted
work function
implantation
ion implantation
forming
Prior art date
Application number
PCT/US1997/006168
Other languages
English (en)
Inventor
Ronald G. Musket
Medhi Balooch
Wigbert J. Siekhaus
Original Assignee
The Regents Of The University Of California
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 The Regents Of The University Of California filed Critical The Regents Of The University Of California
Priority to JP9535630A priority Critical patent/JP2000508110A/ja
Priority to EP97922305A priority patent/EP0904159A4/fr
Publication of WO1997036693A1 publication Critical patent/WO1997036693A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/48—Ion implantation
    • 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
    • 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 relates to electron emitters, particularly to modifying the work function of an electron emitter, and more particularly to a process using ion implantation to reduce or increase the work function of electron emitting surfaces.
  • an electron emitter surface e.g., semiconductor, metal, alloy or compound
  • reducing the work function of the emitters reduces the grid operating voltage thereof, thereby permitting construction of the displays with lower power requirements, higher image resolution, and increased brightness.
  • increasing the work function of some surfaces functions to suppress undesirable emission of electrons.
  • the emission of electrons by a material can be modified by adding dopant materials to that of the electron emitter.
  • Ion implantation is commonly used to dope materials in a uniform manner laterally. Additionally, ion implantation can be used to control the composition as a function of depth via multiple implants using different energies and an appropriate fluence (ions/cm ⁇ ) at each energy.
  • a further object of the invention is to provide a process for modifying the work function of electron emitters. Another object of the invention is to provide a process to modify emitter work functions by ion implantation.
  • a further object of the invention is to provide a process involving ion implantation of selected species to either increase or reduce the work function of electron emitters.
  • Another object of the invention is to provide a process for modifying the work function of an electron emitter by low-energy implantation of chosen elements below the surface of the emitter, and segregation of the implanted species to the emitting surface using thermal treatment in a controlled environment.
  • a further object of the invention is to provide a process for modifying electron emitter work function by producing thin layers of an implanted species on top of the emitter surface, or forming a compound or alloy layer at the surface of the emitter.
  • Another object of the invention is to provide a process for forming a low work function layer through ion implantation in a reactive gas environment to form a layer consisting of elements of the implant, the substrate and the gas.
  • the invention is directed to modifying the work function of electron emitters by ion implantation.
  • the work function of the surface is modified, either increased or decreased, by creating a work function modifying layer of implanted ions at the surface, by implanting the ions and by binding the ions to the surface.
  • the ions are implanted below the surface, at a depth determined mainly by the ion energy.
  • the ions may be bound at the surface, e.g. by exposure to an oxidizing or other reactive atmosphere, or by compounding or alloying the elements, to form the work function modifying layer from the elements of the substrate, implant, and/or gas.
  • the electron emitter with implanted ions may be, if needed, subjected to heat treatment to segregate the ions, i.e. cause ion diffusion toward the surface, where the ions may be similarly bound, compounded or alloyed at the surface to form the work function modifying layer.
  • the present invention which utilizes ion implantation, whereby the work function of electron emitters can be modified, either decreased or increased, depending on the implanted species, the initial emitter material, and the controlled environment (vacuum, reactive gases, atmospheric air) in which the ion implantation and post-implant heat treatment are carried out.
  • the process of this invention results in either thin layers of the implanted species on top of the emitter surfaces, or the formation of compounds or alloy layers at the surface of the emitters. This enables enhancement or suppression of electron emission from surfaces, such as in vacuum micro-electronics. For example, implantation of alkali elements (alkali metals) into a silicon or molybdenum surface with exposure to oxygen-bearing gases forms a compound surface layer resulting in reduction of the work function of the silicon and molybdenum surfaces.
  • a first embodiment of this invention involves: 1) low- energy ion implantation of selected elements below the surface of electron emitters, 2) segregation of the implanted species to the emitting surfaces using thermal treatment in a controlled environment (e.g., vacuum, or reactive gases including atmospheric air), and 3) formation of a work function modifying layer, made of either: a) thin layers of the implanted species on top of the emitter surfaces, or b) compounds or alloy layers at the surfaces of the emitters. Depending on the implanted species, the initial emitter material, and the controlled environment, these layers could either increase or decrease the work function of the emitter.
  • a controlled environment e.g., vacuum, or reactive gases including atmospheric air
  • a second embodiment is similar to the first except that it essentially omits step 2) segregation of the implanted species to the surface.
  • This embodiment can be used when the ion implantation is sufficiently near the surface to permit formation of the work function modifying layer.
  • the work function modifying layer can be formed by several processes, including 1) direct implantation of the ions into a surface oxide or other compound or alloy on the material, 2) implantation of the ions in the presence of a partial pressure of a reactive gas (e.g. oxidizing gas), and 3) modification, including oxidation, of the surface after implantation.
  • a reactive gas e.g. oxidizing gas
  • reducing the work function in silicon and molybdenum surfaces by forming a compound or alloy layer can be accomplished using implanted alkali elements (alkali metals), i.e., Li, Na, K, Rb and Cs, and exposure to oxygen-bearing gases.
  • alkali elements i.e., Li, Na, K, Rb and Cs
  • Figs. 1A-C illustrate processing steps for changing work function by ion implantation followed by segregation of the implanted ions.
  • Figs. 2A,B illustrate alternate processing steps for changing work function by low energy ion implantation without segregation of the implanted ions.
  • Fig. 3 shows the work function of silicon as a function of implanted 35 keV cesium ion fluence.
  • Fig. 4 shows both cesium concentration at the surface and work function as a function of annealing temperature for one fluence of Fig. 3.
  • the invention is directed to a process to modify the work function of electron emitters, and enables enhancement or suppression of electron emission from surfaces.
  • a work function modifying layer is formed at the electron emitting surface by ion implantation and immobilization of the implanted atoms at the surface.
  • the immobilized atoms decrease or increase the work function, depending on the atoms.
  • the atoms are immobilized by binding the atoms to the surface or by forming compounds or alloys at the surface.
  • the immobilized layer of atoms leads to a stable, changed work function of the surface.
  • the invention includes various related embodiments for preparing a low (or high) work function electron emitting surface. There are two basic steps in all embodiments, implantation and formation of the work function modifying layer.
  • the two steps can be performed essentially simultaneously.
  • Various specific treatment steps can be used to form the work function modifying layer, including preparing (e.g., oxidizing) the surface of the material prior to implantation, performing the implantation in a reactive (e.g. oxidizing) environment, or treating (e.g., oxidizing) the surface after implantation.
  • the implantation step can also be carried out under various controlled conditions (e.g. gaseous environment). In some embodiments it is also necessary to diffuse or segregate the implanted element to the surface.
  • a first step shown in Fig. IA, low-energy implantation of ions of chosen elements is done with a mean depth of penetration below at least one atom layer of the surface of an electron emitter at temperatures at which the implanted species is not mobile in the host material and at depths such that essentially all the implanted element is inside the surface of the material.
  • the implanted element concentration profile has a peak at a depth Rp.
  • the implanted species are segregated (diffused) to the emitting surfaces using thermal treatment in a controlled environment and a work function modifying layer is formed.
  • a work function modifying layer is formed.
  • the as-implanted material from Fig. IA is heated in a controlled environment of oxidizing or other reactive gases (e.g. chlorine), including atmospheric air, to diffuse and to segregate the implanted element near the surface by forming a compound or alloy layer at the surface.
  • the work function modifying layer formed of a compound or alloy of the implanted species, the host material, and the gas environment, has a thickness Xi.
  • the as-implanted material from Fig. IA is heated in a vacuum or other environment free of significant reactive gases to cause the implanted element to diffuse and to segregate at the surface.
  • the implanted element forms a thin layer on top of the host material, and /or can also form a compound or alloy layer with the elements present in the host material, including, for example, oxygen present initially in a surface oxide.
  • the work function modifying layer formed of a layer of the implanted species, or of a compound or alloy of the implanted species and the host material, has a thickness X 2 .
  • the implantation can also be done at depths such that all the implanted element is essentially inside the surface of the host material, but at temperatures at which the implanted element and /or desirable elements of the gaseous environment are mobile in the host material and can diffuse and segregate during the implantation process itself. Thus the intermediary product of Fig. IA is not formed. If the implantation is done in a reactive environment as described above with Fig. IB, a similar compound or alloy work function modifying layer as shown in Fig. IB is formed. If the implantation is done in a vacuum or nonreactive environment as described above with Fig. IC, a similar thin layer of implanted element or alloy or compound as shown in Fig. IC is formed.
  • the segregated implanted ion layer thus leads to either: a) thin layers of the implanted species on top of the emitter surfaces, or b) the formation of compounds or alloy layers at the surfaces of the emitters. Depending on the implanted species, the initial emitter material, and the controlled environment, these layers will either increase or decrease the work function of the emitter.
  • a work function modifying layer is formed without the need to carry out the segregation step.
  • Low- energy implantation of ions of chosen elements is done closer to the surface of an electron emitter than in the above embodiments by using lower energy ions, and a work function modifying layer is formed by a variety of specific techniques.
  • a compound (e.g., oxide) layer of thickness X 3 is present on the host material before implantation.
  • the implanted element is all essentially within the initially present surface compound and forms a compound or alloy layer, of thickness X 3 , with the compound and the other elements in the host material.
  • Post-implant heating or annealing may help to homogenize this alloy or compound layer, changing depth profile 10 to depth profile 12, as shown in Fig. 2A.
  • the host material may not have an initial compound (e.g., oxide) layer, and the implantation may be carried out in the presence of a partial pressure of a desirable (e.g., oxidizing) gas.
  • the implanted element is concentrated at the surface, either by low energy implantation or by higher energy implantation followed by removal of the top surface of the host material by sputtering or other suitable process.
  • the implantation process itself may sputter away the top surface and /or enhance the diffusion of the desirable gas elements.
  • An alloy or compound layer with depth profile 14 is thus formed, which can be further heated or annealed to form depth profile 16, as shown in Fig. 2B.
  • ions can be similarly implanted into a material with no surface compound (e.g. oxide) and without a reactive atmosphere.
  • Post-implant reaction e.g., oxidation
  • reactive e.g., oxygen
  • the implanted ion layer thus leads to the formation of compounds or alloy layers at the surfaces of the emitters.
  • these layers will either increase or decrease the work function of the emitter.
  • the thermal treatment should occur during vacuum preparation, assembly, and sealing of the display.
  • An example of such a process is the implantation of cesium into silicon or a metal followed by thermal treatment in a vacuum leading to segregation between a fraction of an atomic monolayer and a few atomic monolayers of cesium to the surface of the silicon or metal.
  • the work function can be reduced by forming compound or alloy surface layers involving implanted alkali metals and oxygen.
  • the work function of surfaces e.g., silicon and molybdenum
  • alkali metals i.e., Li, Na, K, Rb, and Cs
  • This compound surface layer forms the work function modifying layer. Ion implantation techniques are well known in the art and thus a description thereof is deemed unnecessary.
  • the compound surface layer consisting of the implanted alkali (metal) element, the elements of the surface of the material into which the ions were implanted, and oxygen or other desirable elements can be obtained by several processes, including 1) direct implantation of the alkali element into a surface oxide (e.g., silicon-oxide) on the material, 2) implantation of the alkali element in the presence of a partial pressure of an oxidizing or other desirable gas (e.g., oxygen at 10"5 torr), and 3) oxidation of the surface after implantation.
  • Oxidation of the implanted surface can be obtained by exposure of the surface to oxygen bearing gases at appropriate pressures (e.g., O2 and H2O in atmospheric air) and temperatures (e.g. room temperature).
  • the work function of this compound surface layer has been shown to be stable during prolonged exposures (e.g., weeks) to atmospheric air and during heating in vacuum to temperatures up to 450°C .
  • Figure 4 shows both Cs atomic percentage at the surface and work function as a function of temperature for Cs implanted into Si(100) with a dose of 9x10*6 Cs/cm 2 with annealing for a half hour at each temperature. In this case, sputtering during implantation resulted in an increased Cs concentration in the surface layer.
  • the work function of silicon can be increased by ion implantation of elements such as carbon.
  • the present invention enables enhancement or suppression of electron emission from the surfaces of micro-electronic devices. This is accomplished by ion implantation followed if necessary by segregation in a controlled environment using thermal treatment.
  • a work function modifying layer is formed by binding the implanted atoms, including alloy or compound formation, during or after implantation.
  • the process can be carried out by ion implantation in electron emitting metal surfaces such as molybdenum, platinum and nickel.
  • other elements such as barium and calcium can be implanted.
  • Implantation is carried out at ion energies of about 20 eV - 35 keV, and more particularly 1-35 keV.
  • Ion implant doses will generally fall in the range of about 5x10*4 t 0 about 1x10*? ions/cm 2 .
  • Ion implant temperatures may range from as low as -196°C (liquid N2) to 500°C.
  • Gaseous environments, such as O2 and H2O, during implant may range from about 10"** - 10"* Torr.
  • Post-implant treatment may be done at temperatures ranging from about 20°C - 500°C.
  • Post- implant ambients during anneals or oxidation can include IO" 9 - 10 " * Torr vacuum, atmospheric air, noble gases at atmospheric pressure, and O2 or H2O in N2 or other nonreactive gas.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Cold Cathode And The Manufacture (AREA)

Abstract

Il est possible de modifier le travail d'extraction d'émetteurs d'électrons en constituant une couche de modification à la surface d'émission d'électrons par une implantation ionique de faible énergie, dans un environnement maîtrisé, en plaçant des éléments sélectionnés sous la surface des émetteurs d'électrons, du césium implanté dans du silicium (100) selon quatre dosages différents par exemple. Il arrive parfois que des espèces implantées le soient assez profondément pour ne pas réagir avec l'air ambiant durant le traitement ultérieur à basse température. On isole alors des espèces implantées dans les surfaces d'émission en traitant les émetteurs, à des températures élevées, sous vide et/ou dans une atmosphère de gaz réactifs. Les ions implantés modifient superficiellement le travail d'extraction, via les minces couches d'espèces implantées sur le dessus des surfaces émettrices, ou via des couches à base de composés ou d'alliages à la surface des émetteurs. Selon la nature des espèces implantées, celle du matériau émetteur initial et de l'environnement, ces couches sont susceptibles, soit d'accroître le travail d'extraction de l'émetteur, soit le faire se réduire.
PCT/US1997/006168 1996-04-01 1997-03-28 Procede permettant de modifier le travail d'extraction par implantation d'ion WO1997036693A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP9535630A JP2000508110A (ja) 1996-04-01 1997-03-28 イオン注入を用いた仕事関数の変更方法
EP97922305A EP0904159A4 (fr) 1996-04-01 1997-03-28 Procede permettant de modifier le travail d'extraction par implantation d'ion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62525996A 1996-04-01 1996-04-01
US08/625,259 1996-04-01

Publications (1)

Publication Number Publication Date
WO1997036693A1 true WO1997036693A1 (fr) 1997-10-09

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PCT/US1997/006168 WO1997036693A1 (fr) 1996-04-01 1997-03-28 Procede permettant de modifier le travail d'extraction par implantation d'ion

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EP (1) EP0904159A4 (fr)
JP (1) JP2000508110A (fr)
TW (1) TW400553B (fr)
WO (1) WO1997036693A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999045560A1 (fr) * 1998-03-04 1999-09-10 Koninklijke Philips Electronics N.V. Tube electronique comprenant une source de cesium
JP2009152645A (ja) * 2009-04-06 2009-07-09 Canon Inc 電子ビーム照明装置、および該照明装置を用いた電子ビーム露光装置
RU2399114C1 (ru) * 2009-07-20 2010-09-10 Федеральное государственное образовательное учреждение высшего профессионального образования Санкт-Петербургский государственный университет (СПбГУ) Способ изготовления многослойного полевого эмиттера
US8058159B2 (en) 2008-08-27 2011-11-15 General Electric Company Method of making low work function component

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005064636A1 (fr) * 2003-12-25 2005-07-14 Matsushita Electric Industrial Co., Ltd. Matiere emettrice d'electrons et emetteur d'electrons comportant ladite matiere
JP2009016233A (ja) * 2007-07-06 2009-01-22 Kyoto Univ 電界放出型電子源の製造方法

Citations (5)

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Publication number Priority date Publication date Assignee Title
US3678325A (en) * 1969-03-14 1972-07-18 Matsushita Electric Industrial Co Ltd High-field emission cathodes and methods for preparing the cathodes
US4749904A (en) * 1986-01-20 1988-06-07 U.S. Philips Corporation Cathode ray tube with an ion trap including a barrier member
US5258685A (en) * 1991-08-20 1993-11-02 Motorola, Inc. Field emission electron source employing a diamond coating
US5306529A (en) * 1991-01-08 1994-04-26 Kabushiki Kaisha Kobe Seiko Sho Process for forming an ohmic electrode on a diamond film involving heating in a vacuum atmosphere
US5463271A (en) * 1993-07-09 1995-10-31 Silicon Video Corp. Structure for enhancing electron emission from carbon-containing cathode

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3678325A (en) * 1969-03-14 1972-07-18 Matsushita Electric Industrial Co Ltd High-field emission cathodes and methods for preparing the cathodes
US4749904A (en) * 1986-01-20 1988-06-07 U.S. Philips Corporation Cathode ray tube with an ion trap including a barrier member
US5306529A (en) * 1991-01-08 1994-04-26 Kabushiki Kaisha Kobe Seiko Sho Process for forming an ohmic electrode on a diamond film involving heating in a vacuum atmosphere
US5258685A (en) * 1991-08-20 1993-11-02 Motorola, Inc. Field emission electron source employing a diamond coating
US5463271A (en) * 1993-07-09 1995-10-31 Silicon Video Corp. Structure for enhancing electron emission from carbon-containing cathode

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
APPL. PHYS. LETT., 10 April 1995, Vol. 66, No. 15, GIRARDEAU-MONTAUT et al., "Enhancement of Photoelectric Emission Sensitivity of Tungsten by Potassium Ion Implantatio", pages 1886-1888. *
APPL. PHYS. LETT., 21 April 1986, Vol. 48, No. 16, TOMPA et al., "Cesium Coverage of Molybdenum Due to Cesium Ion Bombardment", pages 1048-1050. *
See also references of EP0904159A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999045560A1 (fr) * 1998-03-04 1999-09-10 Koninklijke Philips Electronics N.V. Tube electronique comprenant une source de cesium
US8058159B2 (en) 2008-08-27 2011-11-15 General Electric Company Method of making low work function component
JP2009152645A (ja) * 2009-04-06 2009-07-09 Canon Inc 電子ビーム照明装置、および該照明装置を用いた電子ビーム露光装置
RU2399114C1 (ru) * 2009-07-20 2010-09-10 Федеральное государственное образовательное учреждение высшего профессионального образования Санкт-Петербургский государственный университет (СПбГУ) Способ изготовления многослойного полевого эмиттера

Also Published As

Publication number Publication date
TW400553B (en) 2000-08-01
JP2000508110A (ja) 2000-06-27
EP0904159A1 (fr) 1999-03-31
EP0904159A4 (fr) 2002-02-27

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