EP0618984A1 - Verre reflechissant exothermique, verre transparent exothermique et leur procede de fabrication - Google Patents

Verre reflechissant exothermique, verre transparent exothermique et leur procede de fabrication

Info

Publication number
EP0618984A1
EP0618984A1 EP93901531A EP93901531A EP0618984A1 EP 0618984 A1 EP0618984 A1 EP 0618984A1 EP 93901531 A EP93901531 A EP 93901531A EP 93901531 A EP93901531 A EP 93901531A EP 0618984 A1 EP0618984 A1 EP 0618984A1
Authority
EP
European Patent Office
Prior art keywords
glass
exothermic
sputtering
reflexible
manufacturing
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP93901531A
Other languages
German (de)
English (en)
Inventor
Chull Woo Han
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HIGHER VACUUM IND CO Ltd
Original Assignee
HIGHER VACUUM IND CO Ltd
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 HIGHER VACUUM IND CO Ltd filed Critical HIGHER VACUUM IND CO Ltd
Publication of EP0618984A1 publication Critical patent/EP0618984A1/fr
Withdrawn legal-status Critical Current

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
    • 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
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C03C17/09—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the vapour phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2453—Coating containing SnO2
    • 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
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C03C2217/231—In2O3/SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/251—Al, Cu, Mg or noble metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/257—Refractory metals
    • C03C2217/26—Cr, Mo, W
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/261—Iron-group metals, i.e. Fe, Co or Ni
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering

Definitions

  • This invention relates to the exothermic reflexible glass and exothermic transparent glass as well as to a process for the manufacture of them, whose surface temperature can be adjusted at will by means of coating non-conductive glass either with reflexibility-conductive material or transparency-conductive material by use of the sputtering technique generally used for plasma.
  • the technique of vacuum evaporation by sputtering is performed by a direct evaporation of the material to be evaporated in vacuum through colliding ionized inert gas into the surface of the target, that is, ionization of the inert gas takes place in the area of abnormal glow discharge and the thus ionized gas, under the influence of the electric field, is made to beat the surface of a cathode.
  • the target is
  • the cathode and the vacuum container or the matrix, as the anode are used as the cathode and the vacuum container or the matrix, as the anode.
  • FIG. 1 A simplest diode planar sputtering technique is shown in Fig. 1, wherein a low
  • the electric pressure applicable to the cathode can be varied from hundreds of volts to thousands of volts, while the distance between the cathode and the matrixCvacuum container), the anode, is so near as about 5cm.
  • the velocity of vacuum evaporation being about lOOA/min, it is decided according to the energy and quantity of the ion being shot out. That is, the velocity of vacuum evaporation can be increased by raising the electric pressure and restricted by the decrease of the ionized cross section.
  • the velocity of vacuum evaporation can rather be decreased in an effect of dispersion of the gas.
  • the optimum condition as to the velocity of the vacuum evaporation will have to be determined only through
  • plasma(4) is given rise to around the target and the positive ions existing in the area of the electric discharge come to beat the surface of the target by virtue of electric forces.
  • the kinetic energy of the positive ions is transferred to the atoms which exist on the surface of target, and if this energy is stronger than the bonding energy of the atom which are beaten, the atoms of the target are emitted.
  • the triode system has been invented, which, has a third electrode for control of both the source of thermion emission, and the flow of the emitted thermion is added to the diode system, where a tungsten filament is used as the source of emission for the thermions.
  • vhen a triode system is adopted the velocity of vacuum evaporation can be increased, because it is possible to increase the concentration of plasma by the emission of thermions.
  • the concentration of the electrons in plasma is increased by emission of thermions, the probability of ionization is heightened by brisk action of electrons, the number of ions that beat the target is increased, and thus the velocity of vacuum evaporation is accelerated.
  • Fig. 2(A)(B) show the structure of the target, wherein the highest probability of ionization is to be seen at the point at which a line of magnetic force intersects another perpendicularly, showing a regional sputtering taking place forming a belt of high plasma concentration.
  • the present invention is intended to provide both the process of manufacturing exothermic reflexible glass by coating any such metals as Cr, Ni, Au, Ag, Al, Cu over the surface of glass by the technique of magnetic sputtering as given above, and the process of manufacturing exothermic transparent glass by creating a layer of oxidized coating with InOOZ)-Sn(lOX) alloy in a vacuum container.
  • DESCRIPTION OF THE DRAWINGS Fig. 1 is a sketch of the diode planar sputtering apparatus of the present invention.
  • Fig. 2CA) and (B) are sketches to show the structure of a target for the sputtering.
  • Fig. 3 is a graph showing the different transparencies of the respective 110 and Au thin coating test pieces on glass of different times spent on vacuum evaporation.
  • Fig. 4 is a graph showing the different resistivilities of the respective ITO and Au thin coating test pieces of different times spent on vacuum evaporation.
  • Figs. 5CA) and (B) are graphs showing the surface temperatures of ITO and Au thin coatings of 6,000A and 400A thicknesses, respectively.
  • Fig.6 shows results of the XRD analysis of ITO test piece whose FU2/FAr value is 0.43.
  • magnetron was attached to the back of the target to raise the velocity of vacuum evaporation up to l,000 ⁇ /min.
  • the glass used as the matrix was 2mm thick, of 130mm respectively in length and breadth. It was placed under a process of cleansing with alcohol, distilled
  • Exothermic transparent glass is, unlike exothermic reflexible glass, made by coating glass with transparent oxide instead of using any single metal, and in the present invention a target of In(90%)-Sn(10%) was used for production of exothermic transparent glass, and indium-tin oxideCITO) was synthesized under the mixture of Ar and O2 for formation of the oxide.
  • the specific feature of this material is that even when its thickness is 1,000A it can allow penetration of light by more than 80% so that it can be made wide use of in production of the liquid crystal for TV or other liquid crystal display systems. Hence the extensive study of this material has been made recently.
  • indium-tin oxide(110) in the present invention is made through the reactional process of DC magnetron, and what is important at this time is the
  • the ratio of Ar and O2 gas in the mixture If the ratio of O2 is lower than the preferable ratio, the desired oxide is not produced, while if it ' is higher than that, the transparency decreases and the transparent conductive coating is not
  • the density of the electric power can be 1.5 - 8.0W/cm 3 and if it is higher, it takes short time for the vacuum evaporation and if it is lower, it takes long time for it. It is more desirable to set the density of the power at 2.26W/cm 3 and the time at 6.5 minutes.
  • the experimental conditions for said indium-tin oxide(ITO) are given in Table 1 below:
  • coating layers is Au with the best conductivity, and in the present invention Au
  • Fig. 3 is a graph to show the different transparencies of the ITO and Au thin coating layers obtained by varied times of vacuum evaporation.
  • the penetration of light was about 80% when the thin coating layer's thickness was 0.8 /im.vacuum evaporation by sputtering for 6.5 minutes), and the transparency gradually decreased as the layer's thickness
  • the resistive features were measured by calculating the current, as 10V electric pressure was applied, after placing a Cu electrode each on both ends of
  • Fig. 4(A) carries a graph showing the resistive features of an ITO experimental piece, different as the time for vacuum evaporation by the
  • the value of resistance was 400 ⁇ when the time for vacuum evaporation by the sputtering was two minutes, but it declined rapidly as the time was protracted to fall, for instance, as low as about 20 ⁇ when the time was
  • Fig. 4(B) carries a graph of the resistive features in the case of an Au coating layer, and in this, too, as in the case of the ITO coating layer, the resistance rapidly declined with rapidity as the time for vacuum ' evaporation by the sputtering increased.
  • the object of the present invention is to develop a material as well as the software for the manufacture of conductive and transparent glass for use in automobiles, and since the change of temperatures of the experimental piece makes, as well as its transparency, a most important part of the present invention, the temperatures should be measured acculately.
  • a K-type thermo-electric band was attached by means of silver paste and it was connected to a X-Y recorder in order to measure continuously the temperatures of the surface of the experimental piece varying at the change of the electric pressure and the electric current.
  • Fig. 5(A) is a graph showing the measured surface temperatures of the ITO thin
  • the 110 thin coating of 6,000A having, as shown in Fig. 3, a transparency of 80%, it can be adopted as a very important material in production of the conductive glass for automobiles.
  • Fig. 5(B) shows the curve indicating the surface temperatures of the Au thin
  • coating layers of 400A in thickness the electric current being 0.114A when it was supplied at 13.8V, the surface temperature showing about 45 * C 600 seconds later.
  • Fig. 6 shows the results of XRD analysis of the ITO experimental piece with its FO ⁇ /EAr value at 0.43, wherein in the case of an experimental piece of good transparency and conductivity its In ⁇ SnOs coating exceedingly well develops at 2 ⁇ - 45.36, and it was found that the above ITO coating contributed to
  • Such exothermic reflexible glass coated over the surface of the glass in automobiles, can be used very preferably to remove the moisture inside, and is extensively made use of for liquid crystal display systems also.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

Procédé de fabrication de verre réfléchissant exothermique pouvant émettre de la chaleur à une température supérieure à 50 °C. Il consiste à utiliser la technique de pulvérisation au plasma pour enduire le verre matrice d'une couche mince de métaux tels que Cr, Ni, Au, Ag, Al, Cu. On a également prévu un procédé de fabrication de verre transparent exothermique dont on peut porter la température superficielle à un degré voulu grâce à un raccordement à une source de courant, après avoir enduit le verre matrice d'une couche mince d'un matériau transparent en oxyde d'indium-étain au moyen de la technique de pulvérisation réactive. On décrit également les verres produits à l'aide de ces procédés.
EP93901531A 1991-12-28 1992-12-28 Verre reflechissant exothermique, verre transparent exothermique et leur procede de fabrication Withdrawn EP0618984A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
KR2485691 1991-12-28
KR910024856 1991-12-28
KR2342391 1992-12-05
KR920023423 1992-12-05
PCT/KR1992/000081 WO1993013239A1 (fr) 1991-12-28 1992-12-28 Verre reflechissant exothermique, verre transparent exothermique et leur procede de fabrication

Publications (1)

Publication Number Publication Date
EP0618984A1 true EP0618984A1 (fr) 1994-10-12

Family

ID=26628884

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93901531A Withdrawn EP0618984A1 (fr) 1991-12-28 1992-12-28 Verre reflechissant exothermique, verre transparent exothermique et leur procede de fabrication

Country Status (4)

Country Link
EP (1) EP0618984A1 (fr)
JP (1) JPH07509534A (fr)
CA (1) CA2126674A1 (fr)
WO (1) WO1993013239A1 (fr)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4842705A (en) * 1987-06-04 1989-06-27 Siemens Aktiengesellschaft Method for manufacturing transparent conductive indium-tin oxide layers
US4964962A (en) * 1988-10-08 1990-10-23 Matsushita Electric Works, Ltd. Method for forming conducting metal layer on inorganic substrate
JP2936276B2 (ja) * 1990-02-27 1999-08-23 日本真空技術株式会社 透明導電膜の製造方法およびその製造装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9313239A1 *

Also Published As

Publication number Publication date
CA2126674A1 (fr) 1993-07-08
WO1993013239A1 (fr) 1993-07-08
JPH07509534A (ja) 1995-10-19

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