WO2017187763A1 - 透明導電膜および透明導電膜の製造方法 - Google Patents

透明導電膜および透明導電膜の製造方法 Download PDF

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WO2017187763A1
WO2017187763A1 PCT/JP2017/007706 JP2017007706W WO2017187763A1 WO 2017187763 A1 WO2017187763 A1 WO 2017187763A1 JP 2017007706 W JP2017007706 W JP 2017007706W WO 2017187763 A1 WO2017187763 A1 WO 2017187763A1
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transparent conductive
conductive film
vanadium
value
atomic
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PCT/JP2017/007706
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English (en)
French (fr)
Japanese (ja)
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務 原
公市 永元
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リンテック株式会社
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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • the present invention relates to a transparent conductive film and a method for producing the transparent conductive film.
  • the present invention relates to an indium-free transparent conductive film capable of widely adjusting the work function value and a method for manufacturing the same.
  • an organic EL device generally has a structure in which a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are formed on a transparent anode formed on a glass substrate.
  • the holes injected from the transparent anode and the electrons injected from the cathode enter the light emitting layer through the hole transport layer and the electron transport layer, respectively, and recombine to obtain light emission.
  • Patent Document 1 discloses an anode (anode) including a first layer in which a first metal oxide is doped with a second metal oxide different from the first metal oxide, and a cathode (cathode) facing the anode. And an organic layer having a light emitting layer provided between an anode and a cathode.
  • the first metal oxide include indium oxide, indium tin oxide, zinc oxide, indium zinc oxide, tin oxide, antimony tin oxide, antimony zinc oxide, and aluminum oxide.
  • the second metal oxide include oxidation. Ytterbium, lanthanum oxide, yttrium oxide, beryllium oxide, titanium oxide, silicon oxide, gallium oxide, palladium oxide and samarium oxide are described.
  • Patent Document 2 a transparent conductive film capable of effectively controlling the etching rate in etching using an alkaline solution is disclosed.
  • Patent Document 2 the chemical characteristics of zinc oxide are controlled without significantly impairing visible light transmittance and electrical resistivity by adding cobalt or vanadium simultaneously with at least one or more donor impurities to zinc oxide.
  • An impurity-codoped zinc oxide transparent conductive film is disclosed.
  • donor impurities aluminum, gallium, boron, indium, scandium, yttrium, silicon, titanium, germanium, zirconium and hafnium are described.
  • JP 2012-43815 A (Claims etc.)
  • JP 2002-75062 A (claims, etc.)
  • the anode in the organic light-emitting device described in Patent Document 1 is premised on using indium which is a rare metal from the viewpoint of the number of Clarkes, there is a problem that sustainability is not sufficiently considered. It was observed. Further, the anode described in Patent Document 1 has a problem that it is difficult to achieve both work function controllability and transparency. For this reason, the anode in Patent Document 1 is not limited to the first layer, which is an essential component, and it is preferable that the anode is preferably formed by further laminating a second layer or a third layer having a different composition. . Furthermore, the anode described in Patent Document 1 has insufficient wet heat characteristics, and there is a problem that the conductivity is likely to decrease with time.
  • the transparent conductive film described in Patent Document 2 is indium-free, the sustainability requirement is satisfied, but there is a problem that work function controllability is not considered at all. Furthermore, the transparent conductive film described in Patent Document 2 has insufficient wet heat characteristics, and there is also a problem that the conductivity is likely to decrease with time.
  • an object of the present invention is to provide an indium-free transparent conductive film capable of widely adjusting the work function value and a method for manufacturing the same.
  • a transparent conductive film mainly composed of zinc oxide formed on a substrate comprising gallium as a first dopant and vanadium as a second dopant.
  • the content of gallium as the first dopant is set to a value within the range of 7 to 9 atomic%
  • vanadium as the second dopant Provided is a transparent conductive film characterized in that the content is a value in the range of 1 to 9 atomic% and the work function of the transparent conductive film is a value in the range of 4.5 to 5.5 eV
  • the transparent conductive film of the present invention gallium and vanadium as dopants are contained in a predetermined range with respect to zinc oxide as a main component, so that the work function can be widely adjusted.
  • the transparent conductive film of the present invention can be easily adjusted to an optimal work function corresponding to the type of organic layer such as a hole transport layer, the options for the organic layer can be effectively expanded. As a result, it can contribute to quality improvement of an organic EL element.
  • the transparent conductive film of the present invention has an indium-free configuration that does not use indium, which is a rare metal, it can sufficiently satisfy the demand for sustainability that has recently been recognized as an important issue. .
  • Ra (hereinafter, simply referred to as Ra) as an arithmetic average roughness measured in accordance with JIS B 0601: 2001 is 1.5 nm or less. It is preferable to set the value of. By comprising in this way, the surface of a transparent conductive film becomes smooth, it effectively prevents that a water molecule physically adsorbs in a transparent conductive film in a humid heat environment, and deterioration of a transparent conductive film is effective. Can be suppressed.
  • vanadium as the second dopant contains divalent vanadium and trivalent vanadium, and the total number of moles of vanadium atoms (100 atomic%).
  • V 2+ atomic%
  • V 3+ / V 2+ is 0.5 to 1
  • a value within the range of .5 is preferable.
  • the initial surface resistivity is ⁇ 0 ( ⁇ / ⁇ ), and the surface resistivity after being left for 1100 hours at 60 ° C. and 95% RH is ⁇ 1.
  • ⁇ 1 / ⁇ 0 it is preferable to set ⁇ 1 / ⁇ 0 to a value less than 2.5.
  • the thickness is preferably set to a value in the range of 20 to 300 nm.
  • Another embodiment of the present invention includes zinc oxide as a main component, gallium as the first dopant, and vanadium as the second dopant, and the total number of moles of zinc, gallium, and vanadium is 100.
  • the content of gallium as the first dopant is a value within the range of 7 to 9 atomic%
  • the content of vanadium as the second dopant is within the range of 1 to 9 atomic%.
  • Step of preparing material materials for the base material and the transparent conductive film, respectively A transparent conductive film derived from the material material is formed on the base material by a sputtering method or a vapor deposition method (including at least an ion plating method). Step of Forming Film That is, according to the method for producing a transparent conductive film of the present invention, a predetermined transparent conductive film capable of widely adjusting a work function can be efficiently produced.
  • step (1) a zinc oxide-gallium oxide binary sintered body and a vanadium chip are used as the material for the transparent conductive film, or It is preferable to use a ternary sintered body of zinc oxide-gallium oxide-vanadium oxide.
  • the surface temperature of the substrate it is preferable to control the surface temperature of the substrate to a value within the range of 10 to 300 ° C. in the step (2).
  • a predetermined transparent conductive film can be manufactured more efficiently and stably.
  • FIG. 1 is a diagram provided for explaining the relationship between the vanadium content and the work function.
  • FIG. 2 is a diagram for explaining how to obtain the optical band gap.
  • FIGS. 3 (a) to 3 (b) are views for explaining a transparent conductive laminate provided with the transparent conductive film of the present invention.
  • FIG. 4 is a diagram provided to explain the relationship between the vanadium content and V 3+ / V 2+ .
  • FIGS. 5A to 5B show the X-ray diffraction charts of the transparent conductive films of Examples 1, 2, 5, and Comparative Example 1 (based on the In plane method and based on the Out of plane method).
  • FIGS. 6A to 6B are diagrams for explaining the relationship between the vanadium content and the lattice constants (Ia, Ic).
  • FIGS. 7A to 7B show the wet heat test time for the transparent conductive films of Examples 1, 2, 5 and Comparative Example 1, and the conductivity ( ⁇ 1 , ⁇ 1 / ⁇ 0 ) of the transparent conductive film. It is a figure provided in order to demonstrate the relationship of.
  • FIGS. 8A and 8B are views for explaining the relationship between the depth from the surface and the hydrogen ion secondary ion intensity in the transparent conductive films of Example 1 and Comparative Example 1.
  • FIG. FIGS. 9A to 9B are diagrams provided to show optical characteristics (light transmittance and reflectance) of the transparent conductive films of Examples 1, 2, and 5 and Comparative Example 1.
  • the first embodiment is a transparent conductive film mainly composed of zinc oxide formed on a base material, and includes gallium as a first dopant and vanadium as a second dopant.
  • the content of gallium as the first dopant when the total number of moles of zinc, gallium and vanadium is 100 atomic%. Is in the range of 7-9 atomic%, the content of vanadium as the second dopant is in the range of 1-9 atomic%, and the work function of the transparent conductive film is 4.5-5.
  • It is a transparent conductive film characterized by having a value in the range of .5 eV.
  • the transparent conductive film of the first embodiment will be specifically described with reference to the drawings as appropriate.
  • Blending composition Zinc oxide
  • the transparent conductive film of the present invention is characterized by containing zinc oxide as a main component of the blending composition. This is because, when zinc oxide is the main component, when a transparent conductive film is formed, excellent conductivity and transparency can be obtained at low cost.
  • the transparent conductive film of the present invention includes gallium as the first dopant and vanadium as the second dopant. This is because by including vanadium as appropriate, the carrier concentration can be adjusted to change the Fermi level, and as a result, the work function can be adjusted. Further, when a relatively large amount of vanadium is contained, it is estimated that vanadium is segregated on the film surface. In this case, the segregated vanadium may exist as vanadium oxide. However, the work function of vanadium oxide is about 7.0 eV, and it exists on the film surface separately from the change in the carrier concentration of the entire film. It is inferred that vanadium oxide contributes significantly to the work function. Further, the inclusion of gallium can effectively improve the initial conductivity, and the inclusion of vanadium can effectively improve the wet heat characteristics while maintaining good initial conductivity.
  • the transparent conductive film of the present invention may contain other dopants other than gallium and vanadium.
  • examples of such other dopants include boron, magnesium, aluminum, titanium, manganese, iron, nickel, copper, germanium, yttrium, zirconium, niobium, molybdenum, tin, lanthanoids (excluding promethium), hafnium, tantalum, Examples include tungsten.
  • the content of gallium as the first dopant is set to a value in the range of 7 to 9 atomic% with respect to the total number of moles of zinc, gallium and vanadium (100 atomic%). It is characterized by. This is because the initial conductivity may be insufficient when the gallium content is less than 7 atomic% or more than 9 atomic%. Therefore, the lower limit value of the gallium content is more preferably 7.2 atomic% or more, and further preferably 7.4 atomic% or more. Further, the upper limit value of the gallium content is more preferably 8.8 atomic% or less, and further preferably 8.6 atomic% or less.
  • the content of vanadium as the second dopant is set to a value in the range of 1 to 9 atomic% with respect to the total mole number (100 atomic%) of zinc, gallium, and vanadium.
  • the reason for this is that when the vanadium content is less than 1 atomic%, the work function can be adjusted to a lower value, but the moist heat characteristic is lowered, and the conductivity is changed over time. It is because it may become easy to fall.
  • the vanadium content exceeds 9 atomic% the work function can be adjusted to a higher value, but both initial conductivity and wet heat characteristics are likely to decrease. Because there is.
  • the lower limit of the vanadium content is more preferably 1.5 atomic% or more, and further preferably 2.0 atomic% or more.
  • the upper limit value of the vanadium content is more preferably 7.0 atomic% or less, and further preferably 5.5 atomic% or less.
  • vanadium as the second dopant contains divalent vanadium and trivalent vanadium, and the content of divalent vanadium is V 2+ (to the total mole number of these vanadium (100 atomic%).
  • V 3+ / V 2+ is preferably set to a value within the range of 0.5 to 1.5. The reason for this is that when V 3+ / V 2+ becomes a value less than 0.5, the work function can be adjusted to a smaller value, but the wet heat characteristic is lowered and the conductivity becomes low. This is because there is a case where it tends to decrease with time.
  • V 3+ / V 2+ exceeds 1.5, the work function can be adjusted to a larger value, but the crystal structure tends to be disturbed and the initial conductivity is increased. This is because both the wet heat characteristics are likely to deteriorate. Therefore, the lower limit value of V 3+ / V 2+ is more preferably 0.8 or more, and further preferably 1.0 or more. Further, the upper limit value of V 3+ / V 2+ is more preferably 1.4 or less, and further preferably 1.3 or less. It has been confirmed that the value of V 3+ / V 2+ can be adjusted, for example, by changing the vanadium atom content (atomic%).
  • the value is preferably in the range of 0.1 to 10 atomic% with respect to the total number of moles of zinc atoms and dopant atoms (100 atomic%).
  • a value in the range of ⁇ 8 atomic% is more preferable, and a value in the range of 0.3 to 6 atomic% is more preferable.
  • the transparent conductive film of this invention is indium free, it is fundamentally preferable that it does not contain indium at all, ie, it is 0 atomic%.
  • the value is preferably less than 5 atomic%, preferably less than 3 atomic%, based on the total number of moles of zinc atoms and dopant atoms (100 atomic%). More preferably, the value is more preferably less than 1 atomic%, and most preferably less than 0.1 atomic%.
  • the transparent conductive film of the present invention is characterized in that the work function is set to a value in the range of 4.5 to 5.5 eV.
  • the reason for this is that the work function can be adjusted widely so that the work function can be easily adjusted to the optimum work function corresponding to the type of the organic layer such as the hole transport layer. Therefore, it is because the choice of an organic layer can be expanded effectively and by extension, it can contribute to quality improvement of the device using an organic EL element. More specifically, as shown in FIG. 1, when the work function is less than 4.5 eV, it is necessary to excessively reduce the vanadium atom content, and as a result, a desired initial conductivity can be obtained.
  • the lower limit value of the work function is more preferably 4.7 eV or more, and even more preferably 4.8 eV or more.
  • the upper limit value of the work function is more preferably a value of 5.2 eV or less, and further preferably a value of 5.0 eV or less.
  • the work function here means the energy difference between the vacuum level and the Fermi level.
  • 1 is a vanadium content-work function chart in which the horizontal axis represents the vanadium content (atomic%) and the vertical axis represents the work function (eV). 2 and 5 and the results of Comparative Example 1.
  • Ra Arithmetic surface roughness
  • the upper limit value of Ra is more preferably 1.2 nm or less, and further preferably 1.0 nm or less.
  • the lower limit of Ra is preferably set to a value of 0.01 nm or more, more preferably set to 0.05 nm or more, and further preferably set to a value of 0.1 nm or more.
  • the initial surface resistivity ⁇ 0 is preferably set to a value in the range of 10 to 1,000,000 ⁇ / ⁇ . This is because when ⁇ 0 is less than 10 ⁇ / ⁇ , the film forming conditions may become excessively complicated. On the other hand, when ⁇ 0 is a value exceeding 1,000,000 ⁇ / ⁇ , it is difficult to obtain sufficient initial conductivity. Therefore, the lower limit value of ⁇ 0 is more preferably 20 ⁇ / ⁇ or more, and further preferably 50 ⁇ / ⁇ or more. The upper limit value of ⁇ 0 is more preferably 100,000 ⁇ / ⁇ or less, and even more preferably 10,000 ⁇ / ⁇ or less.
  • the surface resistivity ⁇ 1 after leaving the transparent conductive film of the present invention for 1100 hours at 60 ° C. and 95% RH is set to a value within the range of 10 to 2,000,000 ⁇ / ⁇ . Is preferred. This is because when ⁇ 1 is less than 10 ⁇ / ⁇ , the film forming conditions may become excessively complicated. On the other hand, when ⁇ 1 exceeds 2,000,000 ⁇ / ⁇ , although it depends on ⁇ 0 , it becomes difficult to obtain sufficient wet heat characteristics, and the function as a conductive film may not be achieved. Because. Therefore, the lower limit value of ⁇ 1 is more preferably 20 ⁇ / ⁇ or more, and further preferably 50 ⁇ / ⁇ or more. Further, the upper limit value of ⁇ 1 is more preferably 100,000 ⁇ / ⁇ or less, and even more preferably 10,000 ⁇ / ⁇ or less.
  • ⁇ 1 / ⁇ 0 is preferably set to a value of 0.5 to 2.5. This is because the balance between excellent initial conductivity and wet heat characteristics can be more clearly controlled by setting ⁇ 1 / ⁇ 0 to a value within a predetermined range. That is, when ⁇ 1 / ⁇ 0 is less than 0.5, the initial surface resistivity ⁇ 0 becomes excessively high, or even if not, the film forming conditions become excessively complicated. This is because there are cases. On the other hand, when ⁇ 1 / ⁇ 0 exceeds 2.5, it may be difficult to obtain sufficient wet heat characteristics.
  • the lower limit value of ⁇ 1 / ⁇ 0 is more preferably 0.7 or more, and further preferably 0.9 or more.
  • the upper limit value of ⁇ 1 / ⁇ 0 is more preferably 2.0 or less, and further preferably 1.5 or less.
  • Carrier concentration n in the transparent conductive film of the present invention is preferably set to a value in the range of 1 ⁇ 10 18 cm ⁇ 3 to 5 ⁇ 10 21 cm ⁇ 3 . This is because when the carrier concentration n is less than 1 ⁇ 10 18 cm ⁇ 3 , the conductivity may be significantly impaired. On the other hand, when the carrier concentration n exceeds 5 ⁇ 10 21 cm ⁇ 3 , the absorption region by the carrier is applied to the visible light region, and the optical characteristics may be significantly impaired. Therefore, the lower limit value of the carrier concentration n is more preferably 1 ⁇ 10 19 cm ⁇ 3 or more, and further preferably 1 ⁇ 10 20 cm ⁇ 3 or more. The upper limit value of the carrier concentration n is more preferably 2 ⁇ 10 21 cm ⁇ 3 or less, and further preferably 5 ⁇ 10 20 cm ⁇ 3 or less.
  • the band gap E of the transparent conductive film of the present invention is preferably set to a value within the range of 3.3 to 4.0 eV. This is because when the band gap is less than 3.3 eV, the crystal structure as zinc oxide may not be maintained. On the other hand, when the band gap exceeds 4.0 eV, the carrier concentration becomes excessively large and the transparency may be excessively impaired. Therefore, the lower limit value of the band gap is preferably set to a value of 3.35 eV or more, and more preferably set to a value of 3.4 eV or more. Further, the upper limit value of the band gap is more preferably 3.9 eV or less, and further preferably 3.8 eV or less.
  • the band gap E means an optical band gap, and the relationship between the absorption coefficient ⁇ calculated from the light transmittance, reflectance, and thickness of the transparent conductive film and the following formula (1): Holds.
  • ⁇ is an absorption coefficient
  • A is a proportionality coefficient
  • h ⁇ is light energy
  • E is a band gap.
  • an approximate curve represented by the dotted line B is obtained from the curve based on the actually measured value of ⁇ 2 represented by the solid line A within the range in which the above-described equation (1) is established.
  • the band gap (E) can be obtained by obtaining the intersection with the horizontal axis indicating the energy of light.
  • the band gap is a value unique to the substance, but it is known that the value changes due to Burstein-Moss shift depending on the carrier concentration.
  • Lattice constant lc in the transparent conductive film of the present invention is preferably set to a value in the range of 5.2 to 5.5 mm. This is because the transparent conductive film of the present invention has a hexagonal wurtzite type crystal structure derived from zinc oxide as a main component, and the c-axis lattice constant lc is set to a value within a predetermined range. This is because the disorder of crystallinity can be controlled, and the initial conductivity and wet heat characteristics can be effectively improved. That is, when the lattice constant lc is less than 5.2, the disorder of crystallinity can be suppressed, but sufficient initial conductivity may not be obtained.
  • the lower limit value of the lattice constant lc is more preferably 5.22 cm or more, and further preferably 5.24 mm or more.
  • the upper limit value of the lattice constant lc is more preferably 5.45 ⁇ or less, and further preferably 5.4 ⁇ or less.
  • the thickness of the transparent conductive film of the present invention is preferably set to a value in the range of 20 to 300 nm. This is because work function adjustability, wet heat characteristics, defects in the transparent conductive film, and the like may occur. That is, when the thickness is less than 20 nm, the work function value may not be stably obtained or the wet heat characteristics may be deteriorated. On the other hand, if the thickness exceeds 300 nm, the internal stress of the film may increase or defects such as cracks may occur. Accordingly, the lower limit value of the thickness is more preferably 30 nm or more, and further preferably 50 nm or more. In addition, the upper limit value of the thickness is more preferably 250 nm or less, and further preferably 200 nm or less.
  • Predetermined pattern when using the transparent conductive film of this invention for an electrode, a transistor, etc., it is preferable to give an etching process etc. and to set it as a predetermined pattern. That is, for example, various patterns such as a line shape, a lattice shape, a dot shape, a circular shape, and an irregular shape with a line width of 0.1 ⁇ m to 1 cm are preferable.
  • a substrate as a base on which a transparent conductive film is formed will be described in detail in the second embodiment.
  • the transparent conductive film formed into a film on this base material turns into a transparent conductive film laminated body including a base material, even if it is such an aspect, it may only call a transparent conductive film for convenience. It shall be.
  • the second embodiment contains zinc oxide as a main component, includes gallium as the first dopant, and vanadium as the second dopant, and the total number of moles of zinc, gallium, and vanadium is 100 atomic%.
  • the content of gallium as the first dopant is within a range of 7 to 9 atomic%
  • the content of vanadium as the second dopant is within a range of 1 to 9 atomic%.
  • Step of preparing a material material for the base material and the transparent conductive film, respectively Step of forming a transparent conductive film derived from the material material by sputtering or vapor deposition on the base material
  • Step of forming a transparent conductive film derived from the material material by sputtering or vapor deposition on the base material The manufacturing method of the transparent conductive film of embodiment is demonstrated concretely.
  • Step (1) Step of preparing a base material and a sintered body (material material)
  • material material The type of material material of the transparent conductive film used in the present invention is not particularly limited, for example, In the case of forming a transparent conductive film by sputtering or vapor deposition (including at least ion plating), gallium and vanadium as dopants with respect to zinc oxide powder as the main component of the transparent conductive film
  • a sintered body obtained by adding a powder of a metal simple substance, a metal oxide, or a mixture of a metal simple substance and a metal oxide and sintering the powder can be used as a material substance.
  • a material substance having a predetermined composition can be obtained. Further, a material substance having a predetermined composition can be obtained by using a ternary sintered body of zinc oxide-gallium oxide-vanadium oxide.
  • the zinc oxide content is in the range of 70 to 99.98% by weight and the gallium oxide content is in the range of 0.01 to 15% by weight with respect to the total amount of the sintered body.
  • the amount of vanadium oxide is preferably in the range of 0.01 to 15% by weight.
  • a zinc oxide-gallium oxide binary sintered body with controlled blending amount + vanadium chip is used, or a zinc oxide-gallium oxide-vanadium oxide ternary with similarly controlled blending amount.
  • a transparent conductive film containing gallium and vanadium as dopants in a predetermined range with respect to zinc oxide as the main component can be formed efficiently and stably by using a system sintered body. This is because it can be done.
  • the blending amount of zinc oxide is set to a value within the range of 76 to 99% by weight
  • the blending amount of gallium oxide is set to a value within the range of 0.5 to 12% by weight.
  • the amount of vanadium oxide is set to a value within the range of 0.5 to 12% by weight.
  • the amount of zinc oxide is set to a value within the range of 80 to 98% by weight
  • the amount of gallium oxide is set to a value within the range of 1 to 10% by weight
  • More preferably, the amount of vanadium oxide is set to a value within the range of 1 to 10% by weight.
  • what is necessary is just to prepare the sintered compact containing the said metal suitably, when a transparent conductive film contains another dopant.
  • the base material is not particularly limited as long as it has excellent transparency, and examples thereof include glass, ceramics, and resin films.
  • the material of the resin film polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic type
  • polyester since they are excellent in transparency and versatile, at least one material selected from the group consisting of polyester, polyimide, polyamide, and cycloolefin-based polymer is used. It is preferable that it is a base material. More specifically, suitable polyester includes polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate and the like. Examples of the polyamide include wholly aromatic polyamide, nylon 6, nylon 66, nylon copolymer, and the like. Suitable cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof.
  • cycloolefin polymers include, for example, Apel (ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals), Arton (norbornene polymer manufactured by JIR), Zeonore (Nippon Zeon). And norbornene-based polymers).
  • the thickness of the substrate is preferably a value in the range of 1 to 1000 ⁇ m, more preferably a value in the range of 10 to 500 ⁇ m, and a value in the range of 50 to 200 ⁇ m. Is more preferable.
  • a gas barrier layer, a metal layer, an electrical insulating layer, or the like may be provided on the base material, but these layers are usually provided even when these layers are provided.
  • the total thickness of the base material is preferably set to a value within the range of 1 to 1000 ⁇ m.
  • Step (2) Step of forming transparent conductive film
  • the method of forming the transparent conductive film may be dry coating or wet coating.
  • sputtering method or vapor deposition method may be used as the dry coating.
  • a sputtering method or a vapor deposition method is preferable because a transparent conductive film can be easily formed. This is because the composition of the transparent conductive film to be formed can be easily controlled by forming the film by sputtering or vapor deposition, so that a predetermined transparent conductive film can be efficiently formed. It is.
  • Examples of the sputtering method include DC sputtering method, DC magnetron sputtering method, RF sputtering method, RF magnetron sputtering method, DC + RF superposition sputtering method, DC + RF superposition magnetron sputtering method, counter target sputtering method, ECR sputtering method, dual magnetron sputtering method and the like. It is done.
  • Examples of the vapor deposition method include a resistance heating method, an electron beam heating method, a laser heating method, an ion plating method, and an induction heating method.
  • the sputtering conditions or the deposition is not particularly limited, as the back pressure, preferably in the following values 1 ⁇ 10 -2 Pa, and more preferably the following value 1 ⁇ 10 -3 Pa .
  • argon (Ar) or a mixed gas of argon (Ar) and oxygen (O 2 ) is preferably used in terms of production cost, but rare gas other than Ar or nitrogen (N 2) ) Etc. may be used.
  • the mixing ratio (O 2 / (Ar + O 2 )) is preferably set to a value within the range of 0.01 to 20, and a value within the range of 0.1 to 10 More preferably. This is because the composition of the transparent conductive film to be formed can be easily controlled as long as the mixing ratio of argon and oxygen is within such a range, so that the predetermined transparent conductive film is efficiently formed. Because it can.
  • the film forming pressure is not particularly limited, but is preferably a value within the range of 0.1 to 1 Pa. This is because a predetermined transparent conductive film can be manufactured more efficiently and stably by setting the film forming pressure to a value within this range. That is, when the film forming pressure is less than 0.1 Pa, the ionization of the gas species introduced into the system is not continuously performed, and the plasma state in the system may not be maintained. On the other hand, when the film formation pressure exceeds 1 Pa, the mean free path of particles contributing to film formation in the system decreases, and the collision frequency between particles increases near the base material.
  • the lower limit value of the film forming pressure is more preferably set to a value of 0.12 Pa or more, and further preferably set to a value of 0.15 Pa or more.
  • the upper limit value of the film formation pressure is more preferably 0.95 Pa or less, and even more preferably 0.9 Pa or less.
  • the temperature of the substrate when forming the transparent conductive film on the substrate is preferably set to a value within the range of 10 to 300 ° C. This is because a predetermined transparent conductive film can be manufactured more efficiently and stably by setting the temperature of the substrate to a value within such a range. That is, when the temperature of the substrate is less than 10 ° C., productivity may be greatly impaired. On the other hand, when the temperature of the substrate exceeds 300 ° C., the substrate shrinks due to heat and a desired arithmetic average roughness may not be obtained. Therefore, the lower limit value of the temperature of the base material is more preferably set to a value of 12 ° C. or higher, and further preferably set to a value of 15 ° C. or higher. Moreover, it is more preferable to make the upper limit of the temperature of a base material into the value of 250 degrees C or less, and it is more preferable to set it as a value of 200 degrees C or less.
  • the transparent conductive film 10 of the present invention forms a transparent conductive laminate 50 by being formed on one side or both sides of a substrate 12. To do.
  • a functional layer such as a barrier layer (gas barrier layer), an undercoat layer, and an auxiliary electrode may be inserted between the transparent conductive film 10 and the substrate 12 as a single layer or a plurality of layers.
  • an average light transmittance for light (visible light) having a wavelength of 380 to 780 nm of a transparent conductive laminate formed by forming the transparent conductive film of the present invention (hereinafter sometimes simply referred to as light transmittance). ) Is preferably set to a value of 60% or more. The reason for this is that when the light transmittance is less than 60%, the light transmittance may be excessively lowered. On the other hand, when the light transmittance exceeds 99%, the structure of the laminate and the film formation conditions may become excessively complicated. Therefore, the lower limit of the light transmittance is more preferably set to 65% or more, and further preferably set to 70% or more. In addition, the upper limit value of the light transmittance is preferably 98% or less, and more preferably 97% or less.
  • the average reflectance (hereinafter sometimes simply referred to as reflectance) of light (visible light) with a wavelength of 380 to 780 nm of the transparent conductive laminate formed by forming the transparent conductive film of the present invention is 30%.
  • the following values are preferable.
  • the reason for this is that when the reflectance exceeds 30%, the light transmittance may be excessively reduced or reflection may occur easily.
  • the reflectance is less than 1%, the configuration of the laminate and the film formation conditions may become excessively complicated. Therefore, the lower limit of the reflectance is preferably 2% or more, and more preferably 3% or more.
  • the upper limit value of the reflectance is more preferably 25% or less, and further preferably 20% or less.
  • an average light transmittance for light (near infrared light) having a wavelength of 1500 to 2500 nm (hereinafter simply referred to as light transmittance) of a transparent conductive laminate formed by forming the transparent conductive film of the present invention may be referred to.
  • the lower limit value of the light transmittance of the transparent conductive laminate is preferably 55% or more, and more preferably 60% or more.
  • the upper limit value of the light transmittance of the transparent conductive laminate is more preferably 85% or less, and further preferably 75% or less.
  • examples of the use of the transparent conductive laminate including the above-described transparent conductive film include an aspect of using as a transparent electrode of an electronic device. Specifically, it is preferably applied to electronic devices such as liquid crystal displays, organic EL displays, inorganic EL displays, electronic paper, solar cells, organic transistors, organic EL lighting, inorganic EL lighting, thermoelectric conversion devices, and gas sensors.
  • electronic devices such as liquid crystal displays, organic EL displays, inorganic EL displays, electronic paper, solar cells, organic transistors, organic EL lighting, inorganic EL lighting, thermoelectric conversion devices, and gas sensors.
  • the thickness of the transparent conductive film was measured using a spectroscopic ellipsometer (M-2000U, manufactured by JA Woollam Japan Co., Ltd.). Substrate temperature: 130 ° C DC output: 50W Carrier gas: Argon (Ar) Deposition pressure: 0.5 Pa
  • the ratio (molar ratio) of bivalent vanadium and trivalent vanadium in the transparent conductive film was measured using an XPS (X-ray photoelectron spectroscopy) measurement analyzer (Quantum 2000 manufactured by ULVAC-PHI Co., Ltd.). The obtained results are shown in Table 1 and FIG. In FIG. 4, the horizontal axis represents the vanadium content (atomic%), and the vertical axis represents the trivalent vanadium / divalent vanadium molar ratio ( ⁇ ). Vanadium content ⁇ V 3+ / V 2+ It is a chart and was created from the results of Examples 1, 2, 5 and Comparative Example 1.
  • FIG. 5A is an X-ray diffraction chart by the In plane method when the vanadium content is changed, and the characteristic curves A, B, C, and D are the vanadium content, respectively.
  • FIG. 5B is an X-ray diffraction chart by the out of plane method when the vanadium content is changed, and the characteristic curves A, B, C, and D have vanadium contents of 3. It is a characteristic curve in the transparent conductive film of 1 atomic% (Example 1), 4.1 atomic% (Example 2), 8.2 atomic% (Example 5), and 0 atomic% (Comparative Example 1).
  • FIG. 6A shows a vanadium content-la chart in which the horizontal axis represents the vanadium content (atomic%) and the vertical axis represents the lattice constant la ( ⁇ ), and FIG.
  • FIG. 6A shows that the lattice constant la is constant regardless of the vanadium content.
  • FIG. 6 (b) shows that the lattice constant lc tends to increase as the vanadium content increases.
  • the lattice constant was confirmed similarly, but it was the same as the result shown to Fig.6 (a) and FIG.6 (b). Therefore, it is considered that the crystal structure before the wet heat test affects the wet heat characteristics.
  • n is an integer
  • ⁇ is the incident wavelength of X-rays
  • d is the lattice spacing
  • ⁇ is the X-ray diffraction angle
  • d is the lattice spacing
  • h, k and l are Miller indices
  • la is the a-axis lattice constant
  • lc is the c-axis lattice constant.
  • FIG. 1 is a vanadium content-work function chart in which the horizontal axis represents the vanadium content (atomic%) and the vertical axis represents the work function (eV). Prepared from the results of Example 1.
  • FIG. 1 shows that the work function greatly increases as the vanadium content increases.
  • the characteristic curves A, B, C, and D have a vanadium content of 3.1 atomic% (Example 1), 4.1 atomic% (Example 2), and 8. It is a characteristic curve corresponding to a transparent conductive film of 2 atomic% (Example 5) and 0 atomic% (Comparative Example 1).
  • ⁇ 1 / ⁇ 0 ( ⁇ ) was calculated from the obtained ⁇ 0 and ⁇ 1 .
  • the obtained results are shown in Table 1 and FIG.
  • the horizontal axis represents the wet heat test time (hour)
  • the vertical axis represents ⁇ 1 / ⁇ 0 ( ⁇ )
  • the wet heat test time ⁇ 1 / It is a ⁇ 0 chart.
  • the characteristic curves A, B, C, and D in FIG. 7B have vanadium contents of 3.1 atomic% (Example 1), 4.1 atomic% (Example 2), and 8. It is a characteristic curve corresponding to a transparent conductive film of 2 atomic% (Example 5) and 0 atomic% (Comparative Example 1).
  • the hydrogen atom secondary ion intensity in the thickness direction from the surface was measured by SIMS (secondary ion mass spectrometry). That is, the initial hydrogen atom secondary ionic strength (cps) of the obtained transparent conductive film was placed in a humid heat environment of 60 ° C. and 95% RH for 1100 hours, and then one day in an environment of 23 ° C. and 50% RH. The hydrogen ion secondary ionic strength (cps) after the wet heat test after temperature adjustment and humidity control was measured under the following conditions. The obtained result is shown in FIG. In FIG.
  • the horizontal axis represents the distance (depth) (nm) from the surface in the thickness direction
  • the vertical axis represents the hydrogen atom secondary ion intensity (cps) -depth-hydrogen atom. It is a secondary ionic strength chart.
  • a characteristic curve A is a characteristic curve for the initial transparent conductive film
  • a characteristic curve B is a characteristic curve for the transparent conductive film after the wet heat test.
  • FIG. 8B is a depth-hydrogen atom secondary ion intensity chart obtained for the transparent conductive film of Comparative Example 1 in which the vanadium content is 0 atomic%.
  • 8 (a) shows that the increase in the secondary ion intensity of hydrogen atoms remains about 30 nm from the film surface, based on the curve shape before and after the wet heat test. Since 8 (b) shows an increase from the film surface to about 50 nm, the transparent conductive film containing vanadium is less likely to infiltrate water molecules in the film depth direction and suppresses the decrease in conductivity. Is understood.
  • Measuring device PHI ADEPT 1010 (manufactured by ULVAC-PHI) Measurement mode: Dynamic mode Primary ion species: Cs + Primary acceleration voltage: 3.0 kV Detection area: 120 ⁇ m ⁇ 120 ⁇ m
  • the average transmittance (%) and average reflectance (%) of the obtained transparent conductive film with respect to light (visible light) having a wavelength of 380 to 780 nm and light having a wavelength of 1500 to 2500 nm was measured using an ultraviolet-visible-near infrared spectrophotometer (manufactured by Shimadzu Corporation, UV-3600). The obtained results are shown in Table 1. Further, the wavelength-transmittance chart obtained at this time is shown in FIG. 9A, and the wavelength-reflectance chart is shown in FIG. 9B.
  • Characteristic curves A, B, C, and D have a vanadium content of 3.1 atomic% (Example 1), 4.1 atomic% (Example 2), and 8.2 atomic% (Example 5), respectively. It is a characteristic curve in the transparent conductive film of 0 atomic% (Comparative Example 1). From FIG. 9A, it is understood that the visible light transmittance is constant regardless of the vanadium content. Moreover, regarding the transmittance of near infrared rays, it is understood that the transmittance can be reduced by appropriately adjusting the vanadium content. From FIG. 9B, the reflectance of near-infrared rays is constant regardless of the vanadium content.
  • Example 2 In Example 2, a transparent conductive film was formed in the same manner as in Example 1 except that sputtering was performed with the vanadium chip placed at a position 21 to 26 mm from the center of the binary sintered body. A film was formed and evaluated. The obtained results are shown in Table 1, FIG. 1, FIGS. 4 to 7 and FIG.
  • Example 3 In Example 3, a transparent conductive film was formed and evaluated in the same manner as in Example 1 except that sputtering was performed until the thickness of the transparent conductive film reached 200 nm. The obtained results are shown in Table 1.
  • Example 4 In Example 4, a transparent conductive film was formed and evaluated in the same manner as in Example 2 except that sputtering was performed until the thickness of the transparent conductive film reached 200 nm. The obtained results are shown in Table 1.
  • Example 5 In Example 5, a transparent conductive film was formed in the same manner as in Example 1 except that the vanadium chip was placed at a position 19 to 24 mm from the center of the binary sintered body. ,evaluated. The obtained results are shown in Table 1, FIG. 1, FIGS. 4 to 7 and FIG.
  • the film thickness and evaluation method were the same as in Example 1 except that a transparent conductive film was formed under the following sputtering conditions using a target of diameter: 5 inches and thickness: 5 mm.
  • the obtained results are shown in Table 1.
  • DC output 500W
  • Carrier gas Argon (Ar)
  • Deposition pressure 0.6Pa
  • Comparative Example 1 In Comparative Example 1, a transparent conductive film was formed and evaluated in the same manner as in Example 1 except that the vanadium chip was not placed and only the binary sintered body was used as a target. The obtained results are shown in Table 1, FIG. 1, and FIGS.
  • indium-free is realized by containing gallium and vanadium as dopants in a predetermined range with respect to zinc oxide as a main component.
  • the work function can be adjusted widely. Therefore, since the transparent conductive film of the present invention can be easily adjusted to an optimal work function corresponding to the type of organic layer such as a hole transport layer, the choice of the organic layer can be effectively expanded. As a result, it is expected to significantly contribute to the improvement of the quality of the organic EL element.
  • the transparent conductive film of the present invention has an indium-free configuration that does not use indium, which is a rare metal, it can meet the demand for sustainability that has recently been recognized as an important issue.
  • the transparent conductive film of the present invention can further improve the wet heat characteristics by further limiting the contents of gallium and vanadium as dopants, and can stably maintain excellent initial conductivity. it can. Therefore, the transparent conductive film of the present invention is effectively used as a transparent electrode in various applications such as liquid crystal displays, inorganic EL displays, electronic paper, solar cells as well as organic EL displays and organic EL lighting. It is expected.

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WO2011010603A1 (ja) * 2009-07-21 2011-01-27 日立金属株式会社 ＺｎＯ系透明導電膜用ターゲットおよびその製造方法
JP2013189331A (ja) * 2012-03-13 2013-09-26 Sumitomo Chemical Co Ltd 酸化亜鉛系焼結体およびその製造方法
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WO2011010603A1 (ja) * 2009-07-21 2011-01-27 日立金属株式会社 ＺｎＯ系透明導電膜用ターゲットおよびその製造方法
JP2013189331A (ja) * 2012-03-13 2013-09-26 Sumitomo Chemical Co Ltd 酸化亜鉛系焼結体およびその製造方法
JP2014172807A (ja) * 2013-03-12 2014-09-22 Sekisui Chem Co Ltd 金属複合酸化物粒子の製造方法

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