WO2011019040A1 - Substrat à couche mince transparente fixée audit substrat, et substrat pour écran plasma - Google Patents

Substrat à couche mince transparente fixée audit substrat, et substrat pour écran plasma Download PDF

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Publication number
WO2011019040A1
WO2011019040A1 PCT/JP2010/063576 JP2010063576W WO2011019040A1 WO 2011019040 A1 WO2011019040 A1 WO 2011019040A1 JP 2010063576 W JP2010063576 W JP 2010063576W WO 2011019040 A1 WO2011019040 A1 WO 2011019040A1
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conductive film
transparent conductive
substrate
film
barrier layer
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PCT/JP2010/063576
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English (en)
Japanese (ja)
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健 岡東
秀文 小高
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旭硝子株式会社
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Priority to CN2010800361033A priority Critical patent/CN102471147A/zh
Priority to JP2011526770A priority patent/JPWO2011019040A1/ja
Publication of WO2011019040A1 publication Critical patent/WO2011019040A1/fr

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    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • C03C2217/948—Layers comprising indium tin oxide [ITO]

Definitions

  • the present invention relates to a substrate with a transparent conductive film and a substrate for a plasma display panel (PDP) using the substrate with a transparent conductive film.
  • PDP plasma display panel
  • a transparent conductive film and a bus electrode are formed in this order on a glass substrate.
  • indium oxide, zinc oxide, and tin oxide are known.
  • ITO tin-doped indium oxide
  • the reason why ITO is widely used is its low resistance and good patterning property.
  • indium has few reserve resources, and the development of alternative materials is desired.
  • a tin oxide (SnO 2 ) film is a material that is expected as an alternative material, but in order to impart conductivity to tin oxide, it is necessary to use antimony as a dopant, which may cause environmental concerns in the future. was there.
  • tin oxide is the main component, and at least one element selected from the A dopant group consisting of niobium, tungsten, tantalum, bismuth and molybdenum, and copper element are used as dopants.
  • Including transparent conductive films have been proposed.
  • copper element is a component contained as a sintering aid for the sputtering target, and it is the element of the A dopant group that imparts conductivity to tin oxide.
  • Patent Document 2 in order to solve the above problem, at least one element selected from an A dopant group composed mainly of tin oxide and made of zinc, niobium, titanium, magnesium, aluminum, and zirconium, tungsten, There has been proposed a transparent conductive film containing, as a dopant, at least one element selected from a B dopant group made of tantalum and molybdenum.
  • a silver paste containing glass frit is applied on the transparent conductive film and then fired at 500 to 600 ° C. (see Patent Document 3).
  • a glass frit to be contained in the silver paste a lead glass frit has been mainly used in the past.
  • a bismuth oxide containing bismuth oxide (Bi 2 O 3 ) as a main component is required in view of the requirement for lead-free. It is thought to move to glass frit.
  • the present invention has a contact resistance when forming a bus electrode using a silver paste containing bismuth glass frit on a transparent conductive film mainly composed of tin oxide. It is an object of the present invention to provide a substrate with a transparent conductive film in which the rise is prevented, and a substrate for PDP using the substrate with a transparent conductive film.
  • Bi 2 O 3 bismuth oxide
  • SnO 2 tin oxide
  • the barrier layer is selected from the group consisting of TiO 2 , Nb 2 O 5 , ITO (tin-doped indium oxide), TZO (tin-zinc oxide), and GZO (gallium-doped zinc oxide). It is preferable to consist of any of the above metal oxides.
  • the barrier layer preferably has a thickness of 1 to 50 nm.
  • the transparent conductive film containing tin oxide (SnO 2 ) as a main component preferably contains 0.1 to 10 atomic percent of tantalum (Ta) as a dopant in terms of element.
  • the thickness of the transparent conductive film is preferably 50 nm or more and 1 ⁇ m or less.
  • a bus electrode is formed by applying a silver paste containing bismuth-based glass frit on the barrier layer of the substrate with a transparent conductive film of the present invention and baking at a temperature of 500 to 600 ° C.
  • a substrate for a plasma display panel (PDP) is provided.
  • a barrier layer is formed on a transparent conductive film containing tin oxide as a main component. Therefore, when forming a bus electrode using a silver paste containing a bismuth-based glass frit, The contact resistance between the transparent conductive film and the bus electrode is prevented from increasing.
  • substrate with a transparent conductive film of this invention does not impair the characteristics, such as the electroconductivity of a transparent conductive film, transparency, by forming a barrier layer on a transparent conductive film. Since the substrate for PDP of the present invention has a low contact resistance between the transparent conductive film and the bus electrode, a PDP manufactured using the substrate as a front panel of the PDP is expected to have excellent display quality.
  • FIG. 1 is a schematic view showing a basic configuration of a substrate with a transparent conductive film of the present invention.
  • FIG. 2 is a schematic view showing a state in which bus electrodes are formed on a barrier layer of a substrate with a transparent conductive film in Examples.
  • FIG. 3 is a SEM photograph of the state of the surface after dissolving and removing the bus electrode in Example 1.
  • FIG. 4 is a SEM photograph of the surface state after dissolving and removing the bus electrode in Example 4.
  • FIG. 5 is an SEM photograph of the surface state after dissolving and removing the bus electrode in Comparative Example 1.
  • FIG. 1 is a schematic view showing a basic configuration of a substrate with a transparent conductive film of the present invention.
  • a transparent conductive film 2 and a barrier layer 3 are laminated on a glass transparent substrate 1 in this order.
  • a transparent conductive film 2 and a barrier layer 3 are laminated on a glass transparent substrate 1 in this order.
  • the constituent material of the glass transparent substrate can be widely selected from those used as a glass substrate for PDP, and various glass materials such as soda lime glass, high strain point glass and non-alkali glass can be used. Among these, the glass substrate composition described in Japanese Patent No. 2738036 and Japanese Patent No. 3669022 is particularly preferable.
  • the glass transparent substrate preferably has a spectral transmittance of 80% or more in the range of 425 to 475 nm, 510 to 560 nm, and 600 to 650 nm.
  • the size and thickness of the glass transparent substrate are not particularly limited, for example, those having a length and width of about 400 to 3000 mm can be preferably used.
  • the thickness is preferably 0.7 to 3.0 mm, more preferably 1.5 to 3.0 mm.
  • a transparent conductive film containing tin oxide (SnO 2 ) as a main component is used.
  • the transparent conductive film containing tin oxide as a main component means that the content of tin oxide is 80 atomic% or more in terms of tin element.
  • the transparent conductive film may be a film formed only of tin oxide, but it is usually preferable to add a dopant for the purpose of imparting conductivity to the tin oxide. Examples of the dopant added for this purpose include tantalum (Ta), tungsten (W), bismuth (Bi), and molybdenum (Mo).
  • Indium and antimony have been conventionally used as dopants added for the purpose of imparting conductivity to tin oxide, but the former is an expensive element, and the latter is environmentally concerned in the future. Therefore, it is preferably not used for the transparent conductive film in the present invention. For this reason, it is preferable that the transparent conductive film in this invention does not contain indium and antimony substantially, and these content is 0.1 atomic% or less in element conversion.
  • the dopant content in the transparent conductive film is 0.1 to 10 atomic% in terms of element. It is preferable that it is 0.5 to 5 atomic%.
  • the sputtering target used for forming a transparent conductive film mainly composed of tin oxide includes a sintering aid. Agents are usually added. Therefore, the transparent conductive film containing tin oxide as a main component usually contains a component of such a sintering aid.
  • the sintering aid added to the sputtering target include copper (Cu), zinc (Zn), niobium (Nb), titanium (Ti), magnesium (Mg), aluminum (Al), and zirconium (Zr). It is done.
  • the content of the sintering aid component in the transparent conductive film containing tin oxide as a main component is preferably 10 atomic% or less in terms of element.
  • the transparent conductive film mainly composed of tin oxide is composed of tin oxide, a dopant added for the purpose of imparting conductivity to the above-described tin oxide, and components other than the components of the sintering aid (hereinafter referred to as “others”
  • the content of the other component is preferably 10 atomic% or less in terms of element.
  • the transparent conductive film containing tin oxide as a main component preferably has a specific resistance of 5 ⁇ 10 ⁇ 2 ⁇ cm or less, more preferably 1 ⁇ 10 ⁇ 2 ⁇ cm or less, and more preferably 0.5 ⁇ 10 ⁇ 2 ⁇ cm. Or less, more preferably 9 ⁇ 10 ⁇ 3 ⁇ cm or less.
  • the transparent conductive film mainly composed of tin oxide preferably has a thickness of 1 ⁇ m or less. If a film thickness is 1 micrometer or less, there is no possibility that a transparent conductive film may have optical defects, such as a haze.
  • the film thickness of the transparent conductive film is more preferably 0.4 ⁇ m or less, and further preferably 0.25 ⁇ m or less. Moreover, it is preferable that the film thickness of a transparent conductive film is 50 nm or more.
  • the transparent conductive film mainly composed of tin oxide is preferably excellent in transparency, and specifically, the visible light transmittance is preferably 80% or more.
  • sputtering is performed using a sputtering target having a desired composition, specifically, a sputtering target having the same composition as the transparent conductive film to be formed.
  • the sputtering method to be used is not particularly limited, but a DC sputtering method using a DC power source, a DC pulse sputtering method, an AC sputtering method using a DC power source by switching, or an MF sputtering method using a medium wave power source, It is preferable because it is easy to operate and advantageous in terms of film thickness control.
  • the transparent conductive film mainly composed of tin oxide may be formed by using another sputtering method such as an RF sputtering method using a high frequency power source, or a sputtering method such as a CVD method, a sol-gel method, or a PLD method. You may form using the film-forming method other than the method.
  • another sputtering method such as an RF sputtering method using a high frequency power source, or a sputtering method such as a CVD method, a sol-gel method, or a PLD method.
  • the oxidizing atmosphere is an atmosphere containing an oxidizing gas, and is usually a mixed gas atmosphere of an oxidizing gas and an inert gas.
  • the oxidizing gas, O 2, H 2 O, CO, CO 2 , etc. means an oxygen atom-containing gas.
  • a mixed gas atmosphere of O 2 or CO 2 and argon (Ar) is preferable because the gas composition is easy to control and it is convenient for obtaining a transparent and low resistance film, and CO 2 and Ar A mixed gas atmosphere is particularly preferable.
  • the O 2 concentration in the mixed gas atmosphere of O 2 and Ar is preferably 1 to 10% by volume because a transparent and low resistance film can be obtained.
  • the CO 2 concentration in the mixed gas atmosphere of CO 2 and Ar is preferably 10 to 50% by volume because a transparent and low resistance film can be obtained.
  • Sputtering conditions vary depending on the sputtering method used, but in the case of magnetron DC sputtering, it is preferable to carry out under the following conditions.
  • Power density during sputtering 1 to 15 W / cm 2
  • Sputtering pressure 10 ⁇ 2 to 10 Pa
  • barrier layer an oxide of at least one metal selected from the group consisting of indium (In), tin (Sn), gallium (Ga), zinc (Zn), titanium (Ti), and niobium (Nb) is used. Use what is included.
  • a barrier layer on a transparent conductive film mainly composed of tin oxide, an increase in contact resistance between the bus electrode and the transparent conductive film during the formation of the bus electrode, specifically, a bismuth-based glass frit is formed.
  • the silver paste contained is applied on the barrier layer and then baked at 500 to 600 ° C., the contact resistance between the bus electrode and the transparent conductive film is prevented from increasing.
  • barrier layer having the above composition examples include a TiO 2 film, an Nb 2 O 5 film, an ITO (tin doped indium oxide) film, a TZO (tin zinc oxide) film, and a GZO (gallium doped zinc oxide) film.
  • the increase in contact resistance between the bus electrode and the transparent conductive film during the formation of the bus electrode is caused by bismuth oxide (Bi 2 O 3 ), which is the main component of the bismuth-based glass frit, and the main component of the transparent conductive film.
  • bismuth oxide Ba 2 O 3
  • certain tin oxide SnO 2
  • the action of preventing an increase in contact resistance between the bus electrode and the transparent conductive film when forming the bus electrode varies depending on the material constituting the barrier layer as described below.
  • the barrier layer is a TiO 2 film or an Nb 2 O 5 film
  • Bi 2 O 3 in which the crystalline TiO 2 film or Nb 2 O 5 film is the main component of the bismuth-based glass frit and the main component of the transparent conductive film
  • the reaction with tin oxide (SnO 2 ) is suppressed.
  • formation of Bi 2 Sn 2 O 7 is suppressed, and an increase in contact resistance between the bus electrode and the transparent conductive film is prevented.
  • the TiO 2 film or the Nb 2 O 5 film is an insulator, but since the thickness of the barrier layer is small as will be described later, the presence of the barrier layer between the bus electrode and the transparent conductive film The contact resistance between the bus electrode and the transparent conductive film does not increase.
  • the barrier layer is an ITO film, a TZO film or a GZO film
  • the effect of suppressing the reaction between Bi 2 O 3 and SnO 2 is less than that of the TiO 2 film or the Nb 2 O 5 film. Since the film itself is excellent in conductivity, the resistance of the entire film configuration of the barrier layer and the transparent conductive film is lowered (hereinafter, this action is referred to as “bypass effect by the barrier layer”). As a result, an increase in contact resistance between the bus electrode and the transparent conductive film is prevented.
  • an ITO film is preferable because of excellent conductivity of the film itself and good film patternability.
  • the conductivity of the film itself is inferior to that of the ITO film, but the influence of the film thickness on the resistance value is relatively small, the film formation cost is lower than that of the ITO film, and it is chemically stable.
  • a TZO film is also preferable because it does not dissolve even in alkaline cleaning where the GZO film dissolves.
  • the thickness of the barrier layer is preferably 1 to 50 nm.
  • the thickness of the barrier layer is in the above range, the effect of preventing an increase in contact resistance between the bus electrode and the transparent conductive film when forming the bus electrode is excellent.
  • the thickness of the barrier layer is less than 1 nm, it is impossible to prevent an increase in contact resistance between the bus electrode and the transparent conductive film when the bus electrode is formed. More specifically, when the barrier layer is a TiO 2 film or an Nb 2 O 5 film, if the thickness of the barrier layer is less than 1 nm, the effect of suppressing the reaction between Bi 2 O 3 and SnO 2 is ineffective. This is sufficient, and an increase in contact resistance between the bus electrode and the transparent conductive film during the formation of the bus electrode cannot be prevented.
  • the barrier layer is an ITO film, a TZO film, or a GZO film
  • the thickness of the barrier layer is less than 1 nm, the increase in contact resistance due to the formation of Bi 2 Sn 2 O 7 cannot be offset by the bypass effect. An increase in contact resistance between the bus electrode and the transparent conductive film during electrode formation cannot be prevented.
  • the thickness of the barrier layer exceeds 50 nm, the effect of preventing the increase in contact resistance between the bus electrode and the transparent conductive film during the formation of the bus electrode is not increased, increasing the tact time, increasing the material cost, This is not preferable because problems due to an increase in the thickness of the barrier layer such as an influence on patternability of a subsequent process occur.
  • the barrier layer is a TiO 2 film or an Nb 2 O 5 film
  • the thickness of the barrier layer exceeds 50 nm, an increase in resistance due to the barrier layer itself becomes a problem.
  • the thickness of the barrier layer is more preferably 1 to 30 nm.
  • the total thickness of the laminate of the transparent conductive film and the barrier layer is preferably 50 to 1000 nm, considering the balance of conductivity, barrier properties, film transparency and productivity, and preferably 50 to 500 nm. It is more preferable that the thickness is 50 to 200 nm.
  • the barrier layer formed on the transparent conductive film is required to have the same optical characteristics as the transparent conductive film. That is, the barrier layer is required to have excellent transparency, and the visible light transmittance is preferably 80% or more.
  • sputtering may be performed using a sputtering target having a desired composition.
  • the sputtering method to be used is not particularly limited, but a DC sputtering method using a DC power source, a DC pulse sputtering method, an AC sputtering method using a DC power source by switching, or an MF sputtering method using a medium wave power source, It is preferable because it is easy to operate and advantageous in terms of film thickness control.
  • the barrier layer may be formed by using another sputtering method such as an RF sputtering method using a high-frequency power source, or by using a film forming method other than the sputtering method such as a CVD method, a sol-gel method, or a PLD method. May be formed.
  • another sputtering method such as an RF sputtering method using a high-frequency power source
  • a film forming method other than the sputtering method such as a CVD method, a sol-gel method, or a PLD method. May be formed.
  • the oxidizing atmosphere is an atmosphere containing an oxidizing gas, and is usually a mixed gas atmosphere of an oxidizing gas and an inert gas.
  • the oxidizing gas, O 2, H 2 O, CO, CO 2 , etc. means an oxygen atom-containing gas.
  • a mixed gas atmosphere of O 2 or CO 2 and argon (Ar) is preferable because the gas composition is easy to control and it is convenient for obtaining a transparent and low resistance film, and CO 2 and Ar A mixed gas atmosphere is particularly preferable.
  • the O 2 concentration in the mixed gas atmosphere of O 2 and Ar is preferably 1 to 10% by volume because a transparent film can be obtained.
  • the CO 2 concentration in the mixed gas atmosphere of CO 2 and Ar is preferably 10 to 50% by volume because a transparent film can be obtained.
  • the sputtering conditions vary depending on the sputtering method used, but in the case of the magnetron DC sputtering method, the sputtering can be performed under the same conditions as the sputtering conditions for forming the transparent conductive film.
  • the substrate for PDP of the present invention is such that a bus electrode is formed on the barrier layer of the substrate with a transparent conductive film of the present invention as described below.
  • a silver paste containing bismuth-based glass frit is applied to a portion where a bus electrode is formed on a transparent conductive film.
  • the silver paste used for this purpose is usually prepared by mixing 60% by mass or more of silver powder, 1 to 20% by mass of a bismuth glass frit, and 10 to 30% by mass of an organic binder. A typical composition of the bismuth glass frit used for this purpose is shown below.
  • the coating method of the silver paste is not particularly limited, and for example, a coating method such as screen printing, a spray method, a blade coater method, or a die coating method can be used.
  • the thickness to which the silver paste is applied is not particularly limited, and can be appropriately selected according to the thickness of the silver electrode to be formed.
  • the thickness of the formed silver electrode is usually in the range of several ⁇ m to several tens of ⁇ m.
  • a bus electrode is formed by baking at a temperature of 500 to 600 ° C. for a predetermined time (for example, 5 minutes to 1 hour), and the PDP substrate of the present invention is obtained.
  • the barrier layer is formed on the transparent conductive film mainly composed of tin oxide, the contact between the bus electrode and the transparent conductive film when forming the bus electrode. Resistance rise is prevented.
  • the PDP substrate of the present invention has a low contact resistance between the transparent conductive film and the bus electrode, and a PDP produced using the substrate as a front panel of the PDP is expected to have excellent luminous efficiency.
  • Example 1 to 5 a Ta-doped SnO 2 film was formed as a transparent conductive film on a glass transparent substrate by the following procedure, and a TiO 2 film and Nb 2 were formed as a barrier layer on the Ta-doped SnO 2 film.
  • a bus electrode is formed on the barrier layer, and a contact resistance between the bus electrode and the barrier layer using a TLM (Transmission Line Model) method, And sheet resistance was calculated
  • the sheet resistance referred to here is the sheet resistance of the laminate including the transparent conductive film and the barrier layer.
  • Glass transparent substrate As the glass transparent substrate, a high strain point glass substrate for PDP (PD200 manufactured by Asahi Glass Co., Ltd.) was used.
  • Transparent conductive film On the top surface of the substrate, a film (Ta-doped SnO 2 film) containing tin oxide as a main component and tantalum as a dopant as a transparent conductive film was formed under the following conditions.
  • the composition of the Ta-doped SnO 2 film is 2.1 atomic% in terms of tantalum atomic weight, and the film thickness is 100 nm.
  • Sputtering method magnetron DC sputtering sputtering target: Ta-doped SnO 2 target (Ta 2 O 3 doping amount 6 mass%)
  • Sputtering gas Mixed gas of Ar and O 2 (O 2 1% by volume)
  • Power density during sputtering 5 W / cm 2
  • Sputtering pressure 0.5 Pa
  • TiO 2 film, Nb 2 O 5 film, ITO film (SnO 2 doping amount 10 mass%), TZO film (Sn 2 ZnO 3 ) or GZO film (Ga 2 O 3 doping amount 5) .7 mass%) was formed under the following conditions.
  • [Bus electrode] A mixture of vehicle, terpineol, bismuth glass frit and silver powder mixed so as to be 10% by mass of bismuth glass frit and 90% by mass of silver powder was screen-printed on the barrier layer.
  • the composition of the bismuth glass frit is as follows. SiO 2 1-5% by mass B 2 O 3 5-15% by mass Al 2 O 3 3-8 mass% Bi 2 O 3 70-90 mass% Then, it baked at 600 degreeC for 1 hour, and formed the bus electrode. As shown in FIG. 2, a plurality of bus electrodes 4 and 5 were formed on the barrier layer 3 at intervals.
  • [TLM method] Contact resistance and sheet resistance were determined according to the following formula.
  • R T 2 ⁇ R C + (R SH ⁇ l) / W
  • RT is a resistance between bus electrodes
  • RC is a contact resistance between the barrier layer and the bus electrode
  • R SH is a sheet resistance
  • l is a distance between the bus electrodes
  • W is a width of the bus electrode.
  • Examples 1 to 5 in which a TiO 2 film, Nb 2 O 5 film, ITO film, TZO film or GZO film was formed as a barrier layer on a transparent conductive film containing tin oxide as a main component are as follows: It was confirmed that the contact resistance was lower than that of Comparative Example 1 in which no barrier layer was formed, and an increase in the contact resistance between the bus electrode and the transparent conductive film during the formation of the bus electrode was prevented.
  • Example 1 carrier layer: TiO 2 film
  • Example 4 carrier layer: TZO film
  • Comparative Example 1 no barrier layer
  • Example 4 in Example 4 in which the TZO film was formed as the barrier layer on the transparent conductive film, the formation of crystals was observed, but the TZO film itself has high conductivity, so the barrier layer By virtue of the bypass effect, the increase in contact resistance between the bus electrode and the transparent conductive film is prevented.
  • a barrier layer is formed on a transparent conductive film containing tin oxide as a main component. Therefore, when forming a bus electrode using a silver paste containing a bismuth-based glass frit, The contact resistance between the transparent conductive film and the bus electrode is prevented from increasing. Moreover, the board
  • Transparent glass substrate 2 Transparent conductive film 3: Barrier layer 4, 5: Bus electrode

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  • Manufacturing Of Electric Cables (AREA)

Abstract

L'invention concerne un substrat à couche mince conductrice transparente fixée audit substrat, comprenant un substrat en verre transparent, une couche mince conductrice transparente composée essentiellement d'oxyde d'étain (SnO2), et une couche barrière comprenant un oxyde d'au moins un métal sélectionné dans le groupe constitué par indium (In), étain (Sn), gallium (Ga), zinc (Zn), titane (Ti) et niobium (Nb), la couche mince conductrice transparente et la couche barrière étant stratifiées dans l'ordre précité sur le substrat en verre transparent.
PCT/JP2010/063576 2009-08-14 2010-08-10 Substrat à couche mince transparente fixée audit substrat, et substrat pour écran plasma WO2011019040A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2010800361033A CN102471147A (zh) 2009-08-14 2010-08-10 带透明导电膜的基板及等离子体显示器面板用基板
JP2011526770A JPWO2011019040A1 (ja) 2009-08-14 2010-08-10 透明導電膜付基板およびプラズマディスプレイパネル用基板

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JP2009187969 2009-08-14
JP2009-187969 2009-08-14

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WO2011019040A1 true WO2011019040A1 (fr) 2011-02-17

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PCT/JP2010/063576 WO2011019040A1 (fr) 2009-08-14 2010-08-10 Substrat à couche mince transparente fixée audit substrat, et substrat pour écran plasma

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JP (1) JPWO2011019040A1 (fr)
KR (1) KR20120055558A (fr)
CN (1) CN102471147A (fr)
WO (1) WO2011019040A1 (fr)

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CN102584034A (zh) * 2012-03-19 2012-07-18 山东力诺新材料有限公司 一种用于太阳能高温集热管的低辐射膜及其成型工艺
JP2014150061A (ja) * 2013-02-01 2014-08-21 Heraeus Precious Metals North America Conshohocken Llc 低焼成銀導体
WO2014188822A1 (fr) * 2013-05-23 2014-11-27 リンテック株式会社 Pellicule conductrice et dispositif électronique comprenant la pellicule conductrice

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CN104766546A (zh) * 2015-04-15 2015-07-08 京东方科技集团股份有限公司 显示面板及其制备方法、显示装置
CN104822188A (zh) * 2015-04-17 2015-08-05 扬州明晟新能源科技有限公司 一种多功能玻璃及其生产方法

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JPH05294673A (ja) * 1992-04-17 1993-11-09 Asahi Glass Co Ltd 透明導電膜被覆ガラスの製造方法
JP2003162962A (ja) * 1999-12-21 2003-06-06 Matsushita Electric Ind Co Ltd プラズマディスプレイパネルおよびその製造方法
JP2005199275A (ja) * 1995-09-15 2005-07-28 Saint-Gobain Glass France 光触媒コーティングを備えた基材
WO2007142330A1 (fr) * 2006-06-08 2007-12-13 Asahi Glass Company, Limited Film conducteur transparent, son procédé de production et cible de pulvérisation cathodique destinée à la production dudit film
WO2008111324A1 (fr) * 2007-03-14 2008-09-18 Asahi Glass Co., Ltd. Film conducteur transparent et procédé de fabrication du film conducteur transparent, et cible de pulvérisation cathodique utilisée dans le procédé

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JPH05294673A (ja) * 1992-04-17 1993-11-09 Asahi Glass Co Ltd 透明導電膜被覆ガラスの製造方法
JP2005199275A (ja) * 1995-09-15 2005-07-28 Saint-Gobain Glass France 光触媒コーティングを備えた基材
JP2003162962A (ja) * 1999-12-21 2003-06-06 Matsushita Electric Ind Co Ltd プラズマディスプレイパネルおよびその製造方法
WO2007142330A1 (fr) * 2006-06-08 2007-12-13 Asahi Glass Company, Limited Film conducteur transparent, son procédé de production et cible de pulvérisation cathodique destinée à la production dudit film
WO2008111324A1 (fr) * 2007-03-14 2008-09-18 Asahi Glass Co., Ltd. Film conducteur transparent et procédé de fabrication du film conducteur transparent, et cible de pulvérisation cathodique utilisée dans le procédé

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102584034A (zh) * 2012-03-19 2012-07-18 山东力诺新材料有限公司 一种用于太阳能高温集热管的低辐射膜及其成型工艺
JP2014150061A (ja) * 2013-02-01 2014-08-21 Heraeus Precious Metals North America Conshohocken Llc 低焼成銀導体
WO2014188822A1 (fr) * 2013-05-23 2014-11-27 リンテック株式会社 Pellicule conductrice et dispositif électronique comprenant la pellicule conductrice
KR20160014577A (ko) * 2013-05-23 2016-02-11 린텍 가부시키가이샤 도전 필름 및 도전 필름을 갖는 전자 디바이스
JPWO2014188822A1 (ja) * 2013-05-23 2017-02-23 リンテック株式会社 導電フィルムおよび導電フィルムを有する電子デバイス
US9859033B2 (en) 2013-05-23 2018-01-02 Lintec Corporation Conductive film and electronic device having conductive film
KR102194500B1 (ko) 2013-05-23 2020-12-23 린텍 가부시키가이샤 도전 필름 및 도전 필름을 갖는 전자 디바이스

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CN102471147A (zh) 2012-05-23
KR20120055558A (ko) 2012-05-31

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