WO2005040455A1 - Nanofil et nanoreseau constitues de tungstene, de molybdene et de leur oxyde, presentant une grande surface, procede de preparation et application de ces derniers - Google Patents

Nanofil et nanoreseau constitues de tungstene, de molybdene et de leur oxyde, presentant une grande surface, procede de preparation et application de ces derniers Download PDF

Info

Publication number
WO2005040455A1
WO2005040455A1 PCT/CN2004/000992 CN2004000992W WO2005040455A1 WO 2005040455 A1 WO2005040455 A1 WO 2005040455A1 CN 2004000992 W CN2004000992 W CN 2004000992W WO 2005040455 A1 WO2005040455 A1 WO 2005040455A1
Authority
WO
WIPO (PCT)
Prior art keywords
molybdenum
tungsten
nanowires
substrate
dioxide
Prior art date
Application number
PCT/CN2004/000992
Other languages
English (en)
Chinese (zh)
Inventor
Ningsheng Xu
Juncong She
Shaozhi Deng
Jun Chen
Jun Zhou
Original Assignee
Zhongshan University
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 Zhongshan University filed Critical Zhongshan University
Publication of WO2005040455A1 publication Critical patent/WO2005040455A1/fr

Links

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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising

Definitions

  • the present invention relates to a large area of nanowires of tungsten, molybdenum, and oxides thereof, an array thereof, a preparation method thereof, and applications thereof.
  • Tungsten and molybdenum have relatively low work functions in metals, good mechanical properties, especially high temperature performance, and low evaporation rate. They were first used as field emission materials. As field electron emission materials, they also have the most significant advantage of being able to output a large emission current density, which is very important for applications in field electron emission devices.
  • Tungsten dioxide and molybdenum dioxide are both metal conductive oxides. They are also widely used as memory materials, catalysts and sensors.
  • Tungsten trioxide and molybdenum trioxide are both n-type wide bandgap semiconductor materials. They are widely used in displays, sensors, solar cells, and as catalysts.
  • Another object of the present invention is to provide application of a nanowire of tungsten, molybdenum, and its oxide, and an array thereof.
  • Technical solution adopted by the present invention is to provide a nanowire of tungsten, molybdenum, and its oxide, and an array thereof.
  • nanowires or arrays of tungsten dioxide and molybdenum dioxide we first prepare a large area of nanowires or arrays of tungsten dioxide and molybdenum dioxide, and then obtain tungsten and molybdenum simple nanowires or arrays by reduction, respectively, and use the oxidation method Nanowires or arrays of tungsten trioxide and molybdenum trioxide are obtained.
  • the present invention adopts the following process steps: 1. Preparation of nanowires or arrays of tungsten dioxide and molybdenum dioxide:
  • tungsten (molybdenum) source and substrate separately.
  • the tungsten source is heated to 1000 ⁇ 2000 ° C, and the substrate is heated to 900 ⁇ 1400 ° C ;
  • the molybdenum source is heated to 1000 ⁇ 2000 ° C, and the substrate is heated to 80 (10O ° C. Holding time is 1 minute to 120 minutes.
  • thorium uses tungsten powder, tungsten flakes, or tungsten boats as the tungsten source (molybdenum powder, molybdenum flakes, or molybdenum boats as the molybdenum source).
  • the substrates used are single crystal silicon wafers, silicon pinpoint arrays, metal wafers, glass, ceramics, and other high-temperature resistant materials, and the geometry is not limited.
  • the temperature of the sample is raised to 500-1000 ° C, and the temperature is maintained for 2-60 minutes; when preparing the molybdenum trioxide, the temperature of the sample is raised to 300-600 ° C, and the temperature is maintained for 2-60 minutes.
  • the invention provides a method for preparing nanowires of tungsten, molybdenum, and their oxides, and arrays thereof, by using large flours.
  • the preparation method is simple and straightforward, does not require high equipment, and has low cost.
  • it has been proved through experiments that they have excellent field electron emission properties and have great application prospects as cold cathode electron sources, especially in field electron emission flat panel displays, cold cathode light emitting tubes, and cold light sources.
  • Figure la is the XRD spectrum of the MoO2 nanowire film.
  • Figure lb is a SEM photograph of a MoO nanowire film.
  • Figure lc is a high-resolution TEM and corresponding electron diffraction pattern of a Mo 2 nanowire film.
  • Figure 2a is an XRD spectrum of a simple molybdenum nanowire film.
  • Figure 2b is a morphology of a simple molybdenum nanowire film.
  • Fig. 2c is a high-resolution TEM and corresponding electron diffraction pattern of a simple molybdenum nanowire film.
  • Fig. 3a is an XRD spectrum of a molybdenum trioxide nanowire film.
  • Figure 3b is a morphology of a MoO3 nanowire film.
  • Figure 3c is a high-resolution TEM and corresponding electron diffraction pattern of a MoO3 nanowire film.
  • Figure 4a is the XRD spectrum of the tungsten dioxide nanowire film.
  • Figure 4b is a SEM photograph of a tungsten dioxide nanowire film.
  • Figure 4c is a high-resolution TEM and corresponding electron diffraction pattern of a tungsten dioxide nanowire film.
  • Figure 5a is the IXRD spectrum of a simple tungsten nanowire film.
  • Figure 5b is an SEM image of a simple tungsten nanowire film.
  • Figure 5c is a high-resolution TEM and corresponding electron diffraction pattern of a simple tungsten nanowire film.
  • Figure 6a is an XRD spectrum of a tungsten trioxide nanowire film.
  • Figure 6b is a SEM image of a tungsten trioxide nanowire film.
  • Figure 6c is a high-resolution TEM and corresponding electron diffraction pattern of a tungsten trioxide nanowire film.
  • Figure 7a is a field emission image of a molybdenum dioxide nanowire film.
  • Figure 8a is a field emission image of a simple molybdenum nanowire film.
  • Figure 9a is a field emission image of a molybdenum trioxide nanowire film.
  • Figure 7b shows the field emission J-E and F-N characteristics of the MoO2 nanowire film.
  • Figure 8b shows the field emission J-E and F-N characteristics of the elemental molybdenum nanowire film.
  • Figure 9b shows the field emission J-E and F-N characteristics of the MoO3 nanowire film.
  • Figure 7c is the field emission stability curve of the MoO2 nanowire film.
  • Figure 8c is the field emission stability curve of the elemental molybdenum nanowire film.
  • Fig. 9c is the field emission stability curve of the molybdenum trioxide nanowire film.
  • Fig. 10 is a graph of field emission J-E and F-N characteristics of a tungsten dioxide nanowire film.
  • Figure 11a is a field emission image of a tungsten dioxide nanowire film.
  • Figure lib is a graph of field emission J-E and F-N characteristics of elemental tungsten nanowire films.
  • Fig. 11c is a graph of field emission stability of a thin film of tungsten dioxide nanowires.
  • Figure 12a is a field emission image of a tungsten trioxide nanowire film.
  • Figure 12b is a graph of field emission JE and FN characteristics of a tungsten trioxide nanowire film.
  • FIG. 12c is a field emission stability graph of a tungsten trioxide nanowire film.
  • FIG. 13a shows a case where a molybdenum oxide nanowire film is applied to a cold cathode light emitting tube, and the light emitting tube is working.
  • FIG. 13b is an IV characteristic curve of a molybdenum oxide nanowire film applied to a cold cathode light-emitting tube when the anode voltage is 7 kV, and the anode voltage is 7 kV.
  • XRD X-ray diffraction
  • SEM scanning electron microscopy
  • TEM transmission electron microscopy
  • EDS energy spectroscopy
  • RAMAN Raman spectroscopy
  • Figure 1 (a) is the XRD spectrum of the molybdenum dioxide sodium noodle film.
  • Figure 1 (b) is the SEM photos of typical samples.
  • Figure 1 (c) shows that the nanowires are grown perpendicular to the substrate.
  • the diameter of the nanowires is about 150 nanometers and the length is about 3 micrometers.
  • Figure 2 (a) is the XRD spectrum of the elemental molybdenum nanowire film.
  • the nanowire film is a very pure molybdenum nanowire with a body-centered cubic structure.
  • the morphology of molybdenum nanowires is similar to that of molybdenum dioxide nanowires.
  • the diameter is slightly smaller, about 100 nm [Fig. 2 (b)].
  • Figure 3 (a) is the XRD spectrum of the trioxide nanowire film.
  • the nanowire film is a very pure molybdenum trioxide nanowire with an orthogonal structure.
  • Molybdenum trioxide nanowires are also grown on a vertical substrate, and their morphology is basically similar to that of molybdenum dioxide nanowires, with a diameter of about 200 nm [Fig. 3 (b)].
  • Figure 3 (c) By high-resolution TEM [ Figure 3 (c)] and corresponding electron diffraction analysis (inset in the upper right corner of Figure 3 (c)), we can know that the nanowire has a crystal structure.
  • Figure 4 (a) is the XRD spectrum of the tungsten dioxide nanowire film.
  • the nanowire film is a tungsten dioxide nanowire with a monoclinic structure. From the SEM photos of typical samples ( Figure 4 (b)), it can be seen that the diameter of the nanowires is about 100 nanometers and the length is about 2 micrometers. Through high-resolution TEM ( Figure 4 (c)) and corresponding electron diffraction (inset in the upper right corner of Figure 1 (c)) analysis, we can also confirm that the nanowire has a crystal structure, but there are many defects.
  • Figure 5 (a) is the XRD spectrum of the elemental tungsten nanowire film. By analyzing the spectrum, we can confirm that the nanowire film is a very pure tungsten nanowire with a body-centered cubic structure. FIG.
  • FIG. 5 (b) is an SEM image of tungsten nanowires.
  • Fig. 5 (c) ytterbium-resolved TEM
  • Fig. 2 (c) corresponding electron diffraction
  • Figure 6 (a) is the XRD spectrum of the tungsten trioxide nanowire film.
  • FIG. 6 (b) is a SEM image of a tungsten trioxide nanowire film. From high-resolution TEM [ Figure 6 (c)] and the corresponding electron line analysis (inset in the upper right corner of Figure 6 (c)), we can know that the nanowire has a single crystal structure.
  • Figures 7 (a), 8 (a), and 9 (a) are the field emission images of molybdenum dioxide, elemental molybdenum, and molybdenum trioxide nanowire thin films. We can find that these nanowire thin films have very uniform field emission and emit light.
  • the morphology of the area is basically the same as the morphology of the film (insets in the upper left corner of Figures 7 (a), 8 (a), and 9 (a)).
  • Figures 7 (b), 8 (b), and 9Cb) and the upper left illustration are the field emission JE and FN characteristic curves of molybdenum dioxide, elemental molybdenum, and molybdenum trioxide nanowire films, respectively.
  • molybdenum dioxide, open field and threshold field elemental molybdenum and molybdenum trioxide nanowire film are 2MV / m, 2.2MV / m, 3.5MV / m and 4.75MV / m, 6.24MV / m and 7.65MV / m.
  • Their threshold electric field can be comparable to that of carbon nanotubes.
  • Their FN curves are linear, indicating that their field emission meets the classical field emission theory.
  • Figures ⁇ (c), 8 (c) and 9 (c) are dioxide
  • the field emission stability curves of molybdenum, elemental molybdenum, and molybdenum trioxide nanowire films have only fluctuations, respectively.
  • Figure 11 (a) and Figure 12 (a) are the field emission images of tungsten dioxide and tungsten trioxide nanowire films, respectively. We can find that the nanowire films have very uniform field emission, and the morphology of the light-emitting area and the film morphology ( Figure 11 (a) and Figure 12 (a)) are basically the same.
  • Figure 10, Figure 11 (b) and Figure 12 (b), and the upper left illustration are the field emission JE and FN characteristic curves of tungsten dioxide, elemental tungsten, and tungsten trioxide nanowire films, respectively.
  • Figure 11 (c) and Figure 12 (c) are the field emission stability curves of tungsten dioxide and tungsten trioxide nanowire films, respectively, and their fluctuations are only ⁇ 4% and ⁇ 2%, respectively. This shows that they have excellent field emission stability, which is of great significance to them in practical applications.
  • Table 1 shows the field emission characteristics of various nanowire films: (see Table 1)
  • FIG. 13 shows the application of molybdenum dioxide nanowire thin film to a cold cathode light emitting tube.
  • Fig. 13 (a) shows the situation that the arc tube is working. It can be seen that the arc tube emits light very uniformly.
  • 13 (b) shows the IV characteristic curve when the anode voltage is 7 kV. From the curve, we can see that the arc tube At below 500 volts there is an emission current.
  • nanowire thin films of tungsten, molybdenum and their oxides have very good field emission characteristics. Their opening electric fields and threshold electric fields are low, and their stability is relatively good. This shows that they can fully meet the requirements for field electron emission display materials and can be applied to field emission Flat panel display, cold cathode light emitting tube, cold light source, etc.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cold Cathode And The Manufacture (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)

Abstract

La présente invention concerne un nanofil et un nanoréseau qui sont constitués de tungstène, de molybdène et de leur oxyde et qui présentent une grande surface. Cette invention se rapporte également au procédé de préparation du nanofil et du nanoréseau, ainsi que l'application de ces derniers. Le procédé selon l'invention est simple et direct, le besoin en matériel et le coût sont faibles. Le nanofil et le nanoréseau qui présentent une grande surface possèdent également une excellente propriété d'émission électronique de champ et une application future extensive, notamment dans le domaine des FDP à émission électronique, des tubes fluorescents à cathode froide, des illuminateurs à lumière froide et autres.
PCT/CN2004/000992 2003-08-29 2004-08-27 Nanofil et nanoreseau constitues de tungstene, de molybdene et de leur oxyde, presentant une grande surface, procede de preparation et application de ces derniers WO2005040455A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN 03140333 CN1283835C (zh) 2003-08-29 2003-08-29 钨、钼及其氧化物纳米线薄膜与纳米线阵列以及其制备与应用
CN03140333.6 2003-08-29

Publications (1)

Publication Number Publication Date
WO2005040455A1 true WO2005040455A1 (fr) 2005-05-06

Family

ID=34240290

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2004/000992 WO2005040455A1 (fr) 2003-08-29 2004-08-27 Nanofil et nanoreseau constitues de tungstene, de molybdene et de leur oxyde, presentant une grande surface, procede de preparation et application de ces derniers

Country Status (2)

Country Link
CN (1) CN1283835C (fr)
WO (1) WO2005040455A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101046976B1 (ko) 2004-10-19 2011-07-07 삼성에스디아이 주식회사 전자 방출원 형성용 조성물, 이를 이용한 전자 방출원제조 방법 및 전자 방출원
CN100402695C (zh) * 2005-03-22 2008-07-16 中山大学 物理气相沉积法直接生长成份单一的金属纳米线
WO2006099776A1 (fr) * 2005-03-25 2006-09-28 Zhongshan University Fabrication d’un nanofil métallique à simple composant directement par procédé physique en phase gaseuze
CN102358938B (zh) * 2011-07-14 2014-04-09 中山大学 一种低温大面积可控合成具有优良场发射特性的单晶wo2和wo3纳米线阵列的方法
CN103117199A (zh) * 2011-11-17 2013-05-22 浙江海洋学院 一种松树状纳米阵列场发射阴极制备方法
CN103515180B (zh) * 2013-05-16 2016-08-03 中山大学 一种提高氧化钨纳米材料薄膜场发射特性的原位等离子体辉光处理方法
CN104928642B (zh) * 2015-07-14 2018-02-16 合肥工业大学 一种二氧化钼纳米线阵列的制备方法
CN105543972B (zh) * 2016-02-24 2018-03-27 中国地质大学（北京） 高纯度高密度MoO2层片状纳米结构的制备方法
CN105859151B (zh) * 2016-03-31 2018-10-02 东华大学 一种喷涂法制备大面积多孔电致变色薄膜的方法
CN107626300B (zh) * 2017-09-30 2021-01-26 五邑大学 一种热驱动催化剂及其应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1061555A1 (fr) * 1999-06-18 2000-12-20 Iljin Nanotech Co., Ltd. Source de lumière blanche à nanotubes de carbone et procédé de fabrication
US6190634B1 (en) * 1995-06-07 2001-02-20 President And Fellows Of Harvard College Carbide nanomaterials
US6210800B1 (en) * 1996-12-18 2001-04-03 Eidg. Technische Hochschule Zurich Use and production of nanotubes containing a mixed valence venadium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6190634B1 (en) * 1995-06-07 2001-02-20 President And Fellows Of Harvard College Carbide nanomaterials
US6210800B1 (en) * 1996-12-18 2001-04-03 Eidg. Technische Hochschule Zurich Use and production of nanotubes containing a mixed valence venadium
EP1061555A1 (fr) * 1999-06-18 2000-12-20 Iljin Nanotech Co., Ltd. Source de lumière blanche à nanotubes de carbone et procédé de fabrication

Also Published As

Publication number Publication date
CN1283835C (zh) 2006-11-08
CN1492076A (zh) 2004-04-28

Similar Documents

Publication Publication Date Title
Zhou et al. Synthesis and field-emission properties of aligned MoO 3 nanowires
Singh et al. Formation of aligned ZnO nanorods on self-grown ZnO template and its enhanced field emission characteristics
Xiang et al. Field-emission properties of TiO2 nanowire arrays
Liao et al. Field emission property improvement of ZnO nanowires coated with amorphous carbon and carbon nitride films
Shen et al. Fabrication, characterization and field emission properties of large-scale uniform ZnO nanotube arrays
CN100402432C (zh) 一种氧化铜纳米线阵列定域生长方法
Liao et al. Self-assembly of aligned ZnO nanoscrews: Growth, configuration, and field emission
KR101071906B1 (ko) 단결정 게르마늄코발트 나노와이어, 게르마늄코발트 나노와이어 구조체, 및 이들의 제조방법
Chen et al. Field emission performance of SiC nanowires directly grown on graphite substrate
Nabi et al. Synthesis, photoluminescence and field emission properties of well aligned/well patterned conical shape GaN nanorods
CN111620325B (zh) 一种制备石墨烯纳米带阵列的方法
WO2005040455A1 (fr) Nanofil et nanoreseau constitues de tungstene, de molybdene et de leur oxyde, presentant une grande surface, procede de preparation et application de ces derniers
Xing et al. Solid–liquid–solid (SLS) growth of coaxial nanocables: silicon carbide sheathed with silicon oxide
Lu et al. Silicon quantum-wires arrays synthesized by chemical vapor deposition and its micro-structural properties
Singh et al. Morphological evolution and its correlation with optical and field emission properties in pulsed laser deposited ZnO nanostructures
Chen et al. Zinc sulfide nanowire arrays on silicon wafers for field emitters
Hsueh et al. CuO-nanowire field emitter prepared on glass substrate
Chen et al. Processing, property modulation and application of one-dimensional SiC nanostructure field emitters
Yanming et al. Field emission from single-crystalline CeB6 nanowires
Wu et al. Growth of aligned Cu 2 S nanowire arrays with AAO template and their field-emission properties
CN101525767B (zh) 一维纳米单晶管状碳化硅及其制备方法
Ulisse et al. Hybrid thermal-field emission of ZnO nanowires
CN104528668B (zh) 一种AlxGa1-xN纳米线阵列及其制备方法与应用
Wei et al. Field emission from hydrothermally grown ZnO nanoinjectors
Algarni et al. Enhanced field emission properties of aligned ZnO nanowires

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase