US3483110A - Preparation of thin films of vanadium dioxide - Google Patents

Preparation of thin films of vanadium dioxide Download PDF

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Publication number
US3483110A
US3483110A US639902A US3483110DA US3483110A US 3483110 A US3483110 A US 3483110A US 639902 A US639902 A US 639902A US 3483110D A US3483110D A US 3483110DA US 3483110 A US3483110 A US 3483110A
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film
thin films
vanadium
cathode
films
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US639902A
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George A Rozgonyi
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AT&T Corp
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Bell Telephone Laboratories Inc
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    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • 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
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5853—Oxidation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/021—Formation of switching materials, e.g. deposition of layers
    • H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/041—Modification of switching materials after formation, e.g. doping
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors
    • H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
    • H10N70/235—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect between different crystalline phases, e.g. cubic and hexagonal
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/883—Oxides or nitrides
    • H10N70/8833—Binary metal oxides, e.g. TaOx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S148/00—Metal treatment
    • Y10S148/118—Oxide films
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S148/00—Metal treatment
    • Y10S148/158—Sputtering

Definitions

  • This invention relates to a process for making thin films of various vanadium oxides and to the products produced in accordance with the process.
  • vanadium oxides for example, vanadium dioxide (V0 and vanadium sesquioxide (V 0
  • V0 and V 0 vanadium dioxide
  • V 0 vanadium sesquioxide
  • these vanadium compounds are provided only as single crystals and not in the form of thin films for planar devices.
  • a fracture phenomenon often occurs causing a breakdown of the material, thus possibly imposing limits on the useful life of any device incorporating them.
  • the process involves the steps of sputtering a V 0 cathode in an inert atmosphere in the presence of a desired substrate to produce an amorphous film of a composition VO where x is greater than 1.5 but less than 2, and then either weakly oxidizing the film to end-product V0 or strongly oxidizing the film to V 0 and then reducing the V 0 so produced as a V 0 endproduct.
  • a vanadium cathode can be sputtered in an inert atmosphere in a similar manner to provide a r' evacuating the reaction chamber to 10* to l0 3,483,110 Patented Dec. 9, 1969 ice polycrystalline vanadium film which then is oxidized to V 0 and then reduced to V 0
  • the initial VO film is amorphous
  • the V0 V 0 and V 0 films produced in accordance with the inventive method are made polycrystalline during the 0xidative and/or reductive steps utilized.
  • the process of the invention can provide the vanadium oxides noted, VO V0 V 0 and V 0
  • thin films of V0 and V 03 are especially of interest because of their phase transition characteristic and resistance to recycling fracture.
  • the cylindrical cathode of either V 0 or V was 3 cm. in diameter and 3 cm. long.
  • the vacuum system used was an all metal, sputter-ion pumped station with a watercooled cylindrical reaction chamber 10 cm. in diameter and 15 cm. long.
  • the cathode-to-anode spacing was 2 to 3 cm., although other spacings would be acceptable.
  • the pressures used were of the order of 10a to 300 although these can be extended to 1000p. with satisfactory results.
  • Typical voltages to meet this requirement are from several hundred to a few thousand volts.
  • Substrate temperatures may vary from C. to 500 C. with the quality of the deposited film improving somewhat at the higher temperatures. Preferably, greater temperatures are not used in order to avoid damage to the film or substrate.
  • the cathode material that is sputtered can form a thin film on a variety of substrates; by way of example, films of -VO and V have been successfully deposited on single crystal sapphire, amorphous glass, Si N and Ta O The thicknesses of the films produced ranged from 200 to 6000 A.
  • Substrate tempertatures are not critical, and temperatures within 100 to 500 C. are convenient.
  • a cathode of V 0 a thin film of amorphous vanadium oxide is produced which has a composition VO where x is greater than 1.5 but less than 2. It is theorized that the V 0 results in V O +O and that an amount of oxygen associates with the V 0 to provide a stoichiometric composition for the film between V 0 and V0
  • the VO film can be converted either to V0 or V 0 or V 0 by suitable post-deposition treatment involving oxidation and/ or reduction in open tube furnaces.
  • the VO film is contacted with an oxidizing atmosphere of water vapor which is found not to strongly oxidize the film to an oxidation state higher than V0 Optimum results are obtained at a furnace temperature of 400-500 C. with contact maintained for about 4 hours. Other weak oxidants could also be employed to achieve a V0 composition.
  • V 0 is obtained with stronger oxidants, for instance by an oxygen-rich atmosphere.
  • a or greater O mixture proves excellent, at a furnace temperature optimally at 450550 C. for about 4 hours.
  • the amount of oxygen is not critical to obtaining the desired end product, but secondary factors such as the rate of reaction depend on the oxygen concentration. The greater the oxygen content the more rapid the oxidation.
  • the V 0 film produced is characteristically yellowish and polycrystalline.
  • V 0 is produced by sputtering a vanadium cathode to obtain a polycrystalline vanadium film that is typically black.
  • the same sputtering conditions as described for V 0 are applicable.
  • the same postdeposition treatment just described for producing V 0 from V0 is also operable on the vanadium film to It was not found possible to obtain V 0 films by direct treatment of VO or V films with oxidants alone. Apparently the tendency is for these lower states to reach a vanadium pentoxide equilibrium rather than an intermediate V O state.
  • V 0 is obtainable from a V 0 film, regardless of whether it is produced by sputtering with a cathode of V 0 or V, by contacting it with a reducing atmosphere, such as wet hydrogen that has been saturated with water vapor (room temperature), while in a furnace at about 500-600 C. for about 1 hour.
  • a reducing atmosphere such as wet hydrogen that has been saturated with water vapor (room temperature)
  • This reductive step takes considerably less time than the oxidative steps above described, indicating the relative ease with which the reduction step takes place (less active reductants would take longer).
  • FIG. 2 shows the resistivity vs. reciprocal temperature characteristics for the thin films of interest. The arrows indicate the direction of change.
  • V 0 Thin films of V 0 exhibit only the properties of a semiconductive material over the temperature range studied.
  • the V0 and V 0 films clearly show the phase transition from the semiconductor to the metal state which accompanies change in temperature through the transition temperature.
  • the V0 shows a narrow hysteresis at about 65 C., which compares very favorably with the transition temperature for single crystal V0 Films of V 0 exhibited an abrupt transition to the metal state at about 110 C., with a transition back to the semiconductor state at about 145 C.
  • the resistance of these films to fracture was checked by cycling the V0 samples from room temperature to about 100 C., and by dipping the V 0 samples in and out of liquid nitrogen.
  • the samples underwent repeated resistance changes of 10 ohms for V0 and 10 ohms for V 0 A point-by-point measurement after cycling did not reveal any change in performance.
  • a process for making a thin film vanadium oxide comprising the steps of sputtering with a cathode of a composition consisting essentially of V 0 onto a substrate heated to a temperature in the range from to 500 C., in an atmosphere consisting essentially of inert gas and up to 50 percent by volume oxygen at 10 to 1000 thus forming an amorphous film, and contacting said amorphous film with a weakly oxidizing atmosphere for a time sufiicient to form a polycrystalline V0 film.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Physical Vapour Deposition (AREA)
US639902A 1967-05-19 1967-05-19 Preparation of thin films of vanadium dioxide Expired - Lifetime US3483110A (en)

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Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3620715A (en) * 1969-07-24 1971-11-16 Us Interior Steel scrap oxidation acceleration by surface impregnation techniques
US3648124A (en) * 1970-06-10 1972-03-07 Ibm Gated metal-semiconductor transition device
US3660155A (en) * 1970-04-15 1972-05-02 Us Navy Method for preparing solid films
US3688160A (en) * 1971-03-25 1972-08-29 Matsushita Electric Ind Co Ltd Thin film non-rectifying negative resistance device
US3886578A (en) * 1973-02-26 1975-05-27 Multi State Devices Ltd Low ohmic resistance platinum contacts for vanadium oxide thin film devices
US3899407A (en) * 1973-08-01 1975-08-12 Multi State Devices Ltd Method of producing thin film devices of doped vanadium oxide material
US3916432A (en) * 1974-05-17 1975-10-28 Us Energy Superconductive microstrip exhibiting negative differential resistivity
US4315905A (en) * 1980-06-30 1982-02-16 The United States Of America As Represented By The Secretary Of The Navy Process for producing an electronically conductive oxidizer material
US4393095A (en) * 1982-02-01 1983-07-12 Ppg Industries, Inc. Chemical vapor deposition of vanadium oxide coatings
FR2520727A1 (fr) * 1982-02-01 1983-08-05 Ppg Industries Inc Procede de formation de revetements d'oxyde de vanadium sur des supports en verre et produits obtenus
US4400412A (en) * 1982-02-01 1983-08-23 Ppg Industries, Inc. Thermochromic vanadium oxide coated glass
US4401690A (en) * 1982-02-01 1983-08-30 Ppg Industries, Inc. Thermochromic vanadium oxide with depressed switching temperature
WO1992016959A1 (en) * 1991-03-25 1992-10-01 Commonwealth Scientific And Industrial Research Organisation Arc source macroparticle filter
US5330855A (en) * 1991-09-23 1994-07-19 The United States Of America, As Represented By The Secretary Of Commerce Planar epitaxial films of SnO2
US5387481A (en) * 1990-07-19 1995-02-07 Westinghouse Electric Corporation Method of preparing a switchable shield
US5419890A (en) * 1994-01-19 1995-05-30 Valence Technology, Inc. Use of organic solvents in the synthesis of V6 O13+x [0<x≦2]
US5482697A (en) * 1994-01-19 1996-01-09 Valence Technology, Inc. Method of making V6 O13+x [0<X≦2.0]
US5825046A (en) * 1996-10-28 1998-10-20 Energy Conversion Devices, Inc. Composite memory material comprising a mixture of phase-change memory material and dielectric material
WO1999004441A1 (en) * 1997-07-21 1999-01-28 Nanogram Corporation Vanadium oxide particles and batteries with electroactive nanoparticles
US5952125A (en) * 1997-07-21 1999-09-14 Nanogram Corporation Batteries with electroactive nanoparticles
US5989514A (en) * 1997-07-21 1999-11-23 Nanogram Corporation Processing of vanadium oxide particles with heat
US6106798A (en) * 1997-07-21 2000-08-22 Nanogram Corporation Vanadium oxide nanoparticles
US6225007B1 (en) 1999-02-05 2001-05-01 Nanogram Corporation Medal vanadium oxide particles
US6391494B2 (en) 1999-05-13 2002-05-21 Nanogram Corporation Metal vanadium oxide particles
US6503646B1 (en) 2000-08-28 2003-01-07 Nanogram Corporation High rate batteries
US20040005472A1 (en) * 2000-05-23 2004-01-08 Saint-Gobain Glass France Glazing coated with at least one layer having thermochromic properties
US20040121195A1 (en) * 2002-07-22 2004-06-24 Ghantous Dania I. High capacity and high rate batteries
WO2005028390A1 (de) * 2003-09-13 2005-03-31 Schott Ag Verfahren zur herstellung von substraten mit temperaturbeständigen schutzschichten
EP1560008A1 (en) * 2004-01-29 2005-08-03 Korea Institute of Science and Technology Oxide thin film for bolometer and infrared detector using the oxide thin film
JP2005239516A (ja) * 2004-02-27 2005-09-08 Japan Science & Technology Agency バナジウム酸化物及びこれを用いた記録材料
US7214446B1 (en) 1997-07-21 2007-05-08 Nanogram Corporation Batteries with electroactive nanoparticles
US20090253369A1 (en) * 2006-09-08 2009-10-08 Mpb Communications Inc. Variable emittance thermochromic material and satellite system
US9952096B2 (en) 2012-06-05 2018-04-24 President And Fellows Of Harvard College Ultra-thin optical coatings and devices and methods of using ultra-thin optical coatings
US20180212145A1 (en) * 2017-01-26 2018-07-26 Hrl Laboratories, Llc Low-voltage threshold switch devices with current-controlled negative differential resistance based on electroformed vanadium oxide layer
US10541274B2 (en) 2017-01-26 2020-01-21 Hrl Laboratories, Llc Scalable, stackable, and BEOL-process compatible integrated neuron circuit
US10600961B2 (en) * 2017-07-27 2020-03-24 Hrl Laboratories, Llc Scalable and low-voltage electroforming-free nanoscale vanadium dioxide threshold switch devices and relaxation oscillators with current controlled negative differential resistance
US11861488B1 (en) 2017-06-09 2024-01-02 Hrl Laboratories, Llc Scalable excitatory and inhibitory neuron circuitry based on vanadium dioxide relaxation oscillators

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2917442A (en) * 1955-12-30 1959-12-15 Electronique & Automatisme Sa Method of making electroluminescent layers
US3294669A (en) * 1963-07-22 1966-12-27 Bell Telephone Labor Inc Apparatus for sputtering in a highly purified gas atmosphere

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2917442A (en) * 1955-12-30 1959-12-15 Electronique & Automatisme Sa Method of making electroluminescent layers
US3294669A (en) * 1963-07-22 1966-12-27 Bell Telephone Labor Inc Apparatus for sputtering in a highly purified gas atmosphere

Cited By (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3620715A (en) * 1969-07-24 1971-11-16 Us Interior Steel scrap oxidation acceleration by surface impregnation techniques
US3660155A (en) * 1970-04-15 1972-05-02 Us Navy Method for preparing solid films
US3648124A (en) * 1970-06-10 1972-03-07 Ibm Gated metal-semiconductor transition device
US3688160A (en) * 1971-03-25 1972-08-29 Matsushita Electric Ind Co Ltd Thin film non-rectifying negative resistance device
US3886578A (en) * 1973-02-26 1975-05-27 Multi State Devices Ltd Low ohmic resistance platinum contacts for vanadium oxide thin film devices
US3899407A (en) * 1973-08-01 1975-08-12 Multi State Devices Ltd Method of producing thin film devices of doped vanadium oxide material
US3916432A (en) * 1974-05-17 1975-10-28 Us Energy Superconductive microstrip exhibiting negative differential resistivity
US4315905A (en) * 1980-06-30 1982-02-16 The United States Of America As Represented By The Secretary Of The Navy Process for producing an electronically conductive oxidizer material
US4400412A (en) * 1982-02-01 1983-08-23 Ppg Industries, Inc. Thermochromic vanadium oxide coated glass
JPS62256743A (ja) * 1982-02-01 1987-11-09 ピ−ピ−ジ−・インダストリ−ズ・インコ−ポレ−テツド サ−モクロミツクウインドガラスの製法
JPS58135154A (ja) * 1982-02-01 1983-08-11 ピ−ピ−ジ−・インダストリ−ズ・インコ−ポレ−テツド 酸化バナジウムコ−ティング製品
DE3303154A1 (de) 1982-02-01 1983-08-11 PPG Industries, Inc., 15222 Pittsburgh, Pa. Verfahren zur chemischen abscheidung von vanadinoxidfilmen aus der dampfphase und mit vanadinoxidfilmen ueberzogene gegenstaende
US4393095A (en) * 1982-02-01 1983-07-12 Ppg Industries, Inc. Chemical vapor deposition of vanadium oxide coatings
US4401690A (en) * 1982-02-01 1983-08-30 Ppg Industries, Inc. Thermochromic vanadium oxide with depressed switching temperature
DE3347918A1 (en:Method) * 1982-02-01 1985-05-15 Ppg Industries Inc
FR2520727A1 (fr) * 1982-02-01 1983-08-05 Ppg Industries Inc Procede de formation de revetements d'oxyde de vanadium sur des supports en verre et produits obtenus
JPS62256742A (ja) * 1982-02-01 1987-11-09 ピ−ピ−ジ−・インダストリ−ズ・インコ−ポレ−テツド 酸化バナジウムフイルムの化学蒸着法
US5387481A (en) * 1990-07-19 1995-02-07 Westinghouse Electric Corporation Method of preparing a switchable shield
WO1992016959A1 (en) * 1991-03-25 1992-10-01 Commonwealth Scientific And Industrial Research Organisation Arc source macroparticle filter
US5433836A (en) * 1991-03-25 1995-07-18 Commonwealth Scientific And Industrial Research Organization Arc source macroparticle filter
US5330855A (en) * 1991-09-23 1994-07-19 The United States Of America, As Represented By The Secretary Of Commerce Planar epitaxial films of SnO2
US5419890A (en) * 1994-01-19 1995-05-30 Valence Technology, Inc. Use of organic solvents in the synthesis of V6 O13+x [0<x≦2]
US5482697A (en) * 1994-01-19 1996-01-09 Valence Technology, Inc. Method of making V6 O13+x [0<X≦2.0]
US5825046A (en) * 1996-10-28 1998-10-20 Energy Conversion Devices, Inc. Composite memory material comprising a mixture of phase-change memory material and dielectric material
US5989514A (en) * 1997-07-21 1999-11-23 Nanogram Corporation Processing of vanadium oxide particles with heat
WO1999004441A1 (en) * 1997-07-21 1999-01-28 Nanogram Corporation Vanadium oxide particles and batteries with electroactive nanoparticles
US6106798A (en) * 1997-07-21 2000-08-22 Nanogram Corporation Vanadium oxide nanoparticles
US7214446B1 (en) 1997-07-21 2007-05-08 Nanogram Corporation Batteries with electroactive nanoparticles
US5952125A (en) * 1997-07-21 1999-09-14 Nanogram Corporation Batteries with electroactive nanoparticles
US7722787B2 (en) 1999-02-05 2010-05-25 Greatbatch Ltd. Metal vanadium oxide particles
US6225007B1 (en) 1999-02-05 2001-05-01 Nanogram Corporation Medal vanadium oxide particles
US6749966B2 (en) 1999-05-13 2004-06-15 Nanogram Devices Corporation Metal vanadium oxide particles
US6391494B2 (en) 1999-05-13 2002-05-21 Nanogram Corporation Metal vanadium oxide particles
US20040005472A1 (en) * 2000-05-23 2004-01-08 Saint-Gobain Glass France Glazing coated with at least one layer having thermochromic properties
US6872453B2 (en) * 2000-05-23 2005-03-29 Saint-Gobain Glass France Glazing coated with at least one layer having thermochromic properties
US20050147825A1 (en) * 2000-05-23 2005-07-07 Saint-Gobain Glass France Glazing coated with at least one layer having thermochromic properties
US7311976B2 (en) 2000-05-23 2007-12-25 Saint-Gobain Glass France Glazing coated with at least one layer having thermochromic properties
US20030077513A1 (en) * 2000-08-28 2003-04-24 Nanogram Corporation High rate batteries
US6503646B1 (en) 2000-08-28 2003-01-07 Nanogram Corporation High rate batteries
US20040121195A1 (en) * 2002-07-22 2004-06-24 Ghantous Dania I. High capacity and high rate batteries
US7198869B2 (en) 2002-07-22 2007-04-03 Greatbatch, Inc. High capacity and high rate batteries
WO2005028390A1 (de) * 2003-09-13 2005-03-31 Schott Ag Verfahren zur herstellung von substraten mit temperaturbeständigen schutzschichten
EP1560008A1 (en) * 2004-01-29 2005-08-03 Korea Institute of Science and Technology Oxide thin film for bolometer and infrared detector using the oxide thin film
JP2005239516A (ja) * 2004-02-27 2005-09-08 Japan Science & Technology Agency バナジウム酸化物及びこれを用いた記録材料
US20090253369A1 (en) * 2006-09-08 2009-10-08 Mpb Communications Inc. Variable emittance thermochromic material and satellite system
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US9952096B2 (en) 2012-06-05 2018-04-24 President And Fellows Of Harvard College Ultra-thin optical coatings and devices and methods of using ultra-thin optical coatings
US20180212145A1 (en) * 2017-01-26 2018-07-26 Hrl Laboratories, Llc Low-voltage threshold switch devices with current-controlled negative differential resistance based on electroformed vanadium oxide layer
US10297751B2 (en) * 2017-01-26 2019-05-21 Hrl Laboratories, Llc Low-voltage threshold switch devices with current-controlled negative differential resistance based on electroformed vanadium oxide layer
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US10903277B2 (en) 2017-01-26 2021-01-26 Hrl Laboratories, Llc Scalable, stackable, and BEOL-process compatible integrated neuron circuit
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FR1565917A (en:Method) 1969-05-02
BE715161A (en:Method) 1968-09-30

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