WO2015133007A1 - Procédé de fabrication de conducteur transparent - Google Patents

Procédé de fabrication de conducteur transparent Download PDF

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Publication number
WO2015133007A1
WO2015133007A1 PCT/JP2014/079789 JP2014079789W WO2015133007A1 WO 2015133007 A1 WO2015133007 A1 WO 2015133007A1 JP 2014079789 W JP2014079789 W JP 2014079789W WO 2015133007 A1 WO2015133007 A1 WO 2015133007A1
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Prior art keywords
layer
transparent
refractive index
metal layer
high refractive
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PCT/JP2014/079789
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English (en)
Japanese (ja)
Inventor
節夫 徳弘
一成 多田
仁一 粕谷
健一郎 平田
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コニカミノルタ株式会社
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Priority to JP2016506078A priority Critical patent/JPWO2015133007A1/ja
Publication of WO2015133007A1 publication Critical patent/WO2015133007A1/fr

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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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
    • 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
    • C23C14/3464—Sputtering using more than one target
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to a method for producing a transparent conductor. More specifically, the present invention relates to a method for manufacturing a transparent conductor that suppresses a decrease in light transmittance due to sulfidation of a transparent metal layer material.
  • metals such as Au, Ag, Pt, Cu, Rh, Pd, Al, and Cr, In 2 O 3 , CdO, CdIn 2 O 4 , Cd 2 SnO 4 , and TiO 2 are used.
  • SnO 2 , ZnO, ITO (indium tin oxide) and other oxide semiconductors are known.
  • a wiring made of a transparent conductive film or the like is disposed on the image display surface of the display element. Therefore, the transparent conductive film is required to have high light transmittance.
  • a transparent conductive film made of ITO having high light transmittance is often used.
  • a capacitive touch panel display device has been developed, and the surface electrical resistance of the transparent conductive film is further reduced, and specifically, a resistance value of 50 ⁇ / ⁇ or less is strongly demanded.
  • the ITO film that has been widely used conventionally has a resistance value of only about 150 ⁇ / ⁇ , which is insufficient for the above demand.
  • development of next-generation transparent conductive films to replace ITO has been actively conducted.
  • Japanese Patent Application Laid-Open No. 2011-138628 discloses a method for manufacturing a conductive element to which a silver mesh is applied.
  • the mesh diameter is about 20 ⁇ m, it can be visually recognized by human eyes, and it is difficult to apply to a touch panel display device or the like.
  • silver nanowires that are commercially available from some manufacturers have a minute size that is invisible to the naked eye and expresses electrical conductivity in the film, but the sheet resistance is about 60 ⁇ / ⁇ , The quality required for current touch panel display devices was insufficient.
  • the film thickness of the conductive film needs to be laminated to about 200 nm, and it was formed in the manufacturing process.
  • stress is applied to the conductive film, cracks and the like are likely to occur in the film, resulting in a decrease in yield and a problem in terms of production efficiency.
  • Patent Document 1 a method of applying a silver vapor-deposited film as a transparent conductive film has been actively studied (for example, see Patent Document 1). Further, in order to increase the light transmittance of the transparent conductor, a silver thin film is formed by sputtering, a metal film having a high refractive index (for example, niobium oxide (Nb 2 O 5 ), IZO (indium zinc oxide), ICO A transparent conductive film having a structure sandwiched between (indium cerium oxide) and a-GIO (a film of an amorphous oxide made of gallium, indium and oxygen) is also proposed (for example, Patent Documents 2 to 4, Non-Patent Documents (See Patent Document 1). Furthermore, a method of sandwiching a silver thin film with a zinc sulfide film has also been proposed (see, for example, Non-Patent Documents 2 and 3).
  • a metal film having a high refractive index for example, niobium oxide (Nb 2 O 5
  • the moisture resistance of the transparent conductor is sufficiently high, but when forming a silver thin film layer or a zinc sulfide layer During the formation of silver, silver is easily sulfided to form silver sulfide. As a result, there are problems such as a decrease in light transmittance of the transparent conductor and an increase in unnecessary absorption due to sulfurization.
  • a sulfidation prevention layer made of a metal oxide or the like between the transparent metal layer and the zinc sulfide layer for the purpose of preventing sulfidation of silver which is a transparent metal layer material.
  • the zinc sulfide layer is formed before the sulfidation prevention layer is formed on the transparent substrate. This sulfur component sulfides the silver of the transparent metal layer material, making it difficult to obtain a transparent conductor having sufficient light transmittance.
  • a transparent conductive film on a long substrate such as a film by a vacuum film forming method in order to efficiently form a film with high productivity.
  • a to-roll film forming method is known.
  • a partition wall and a differential pressure chamber are provided so as not to affect the film formation in the adjacent film formation chambers (for example, patents).
  • the target is divided in order to prevent the target size from becoming large and cracking due to a difference in thermal expansion between the backing plate (support for fixing the target) and the target (metal material).
  • the technology is known (for example, refer to Patent Document 6), no consideration has been given to film formation using, for example, a metal oxide as a split target material.
  • the present invention has been made in view of the above-mentioned problems and situations, and a solution to that problem is to provide a method for producing a transparent conductor that suppresses a decrease in light transmittance due to sulfidation of a transparent metal layer material.
  • the present inventor has a plurality of film forming steps for forming a thin film layer on a transparent substrate by a plurality of evaporation sources in the process of examining the cause of the above problems. It has been found that the reduction of the light transmittance due to the sulfidation of the transparent metal layer material can be suppressed by the method for producing a transparent conductor, which is a split target composed of different materials, of the targets possessed by the two evaporation sources.
  • a first high-refractive index layer, a transparent metal layer, and a second high-refractive index layer are sequentially laminated on a transparent substrate that is continuously transported, and further, the first high-refractive index layer and the second high-refractive index layer.
  • the at least two divided targets include a divided target that is a material of the anti-sulfurization layer and a divided target that is a material of the transparent metal layer.
  • splitting target which is a material of the antisulfurization layer, is Zn, a metal oxide containing Zn, or a metal oxide containing Ga.
  • the above-mentioned means of the present invention can provide a method for producing a transparent conductor that suppresses a decrease in light transmittance due to sulfidation of a transparent metal layer material.
  • the deposition distance between the sulfidation prevention layer and the transparent metal layer is reduced, that is, the target constituting the sulfidation prevention layer and the target constituting the transparent metal layer are used as one evaporation source.
  • the target constituting the sulfidation prevention layer and the target constituting the transparent metal layer are used as one evaporation source.
  • Schematic sectional view showing an example of a layer structure of a transparent conductor according to the present invention Schematic sectional view showing an example of a layer structure of a transparent conductor according to the present invention
  • Graph showing the deposition rate of each target with respect to the electric power supplied to the evaporation source Schematic diagram showing an example of transparent conductor manufacturing equipment
  • Schematic diagram of split targets in transparent conductor manufacturing equipment Schematic diagram of split targets in transparent conductor manufacturing equipment
  • Schematic diagram of split targets in transparent conductor manufacturing equipment Schematic diagram showing an example of transparent conductor manufacturing equipment
  • Schematic diagram showing an example of transparent conductor manufacturing equipment Schematic diagram showing a conventional transparent conductor manufacturing device
  • a first high refractive index layer, a transparent metal layer, and a second high refractive index layer are sequentially laminated on a transparent substrate that is continuously conveyed
  • a method of manufacturing a transparent conductor in which a sulfidation prevention layer is laminated between at least one of a high refractive index layer and a second high refractive index layer and a transparent metal layer, and a plurality of evaporation sources on a transparent substrate It has a plurality of film forming steps for forming a thin film layer, and the target of at least one evaporation source is composed of at least two divided targets made of different materials.
  • At least two division targets are a division target that is a material for an antisulfation layer and a division target that is a material for a transparent metal layer. are preferably included.
  • the divided target that is the material of the transparent metal layer is silver or an alloy containing silver.
  • the split target that is the material of the sulfidation prevention layer is a metal oxide containing Zn or Zn, or a metal oxide containing Ga.
  • ⁇ representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • ⁇ Layer structure of transparent conductor ⁇ 1A to 1C are schematic cross-sectional views showing an example of a layer structure of a transparent conductor according to the present invention.
  • a transparent conductor 1 according to the present invention is formed on a transparent substrate 2 from the transparent substrate 2 side, a first high refractive index layer 3a, an antisulfurization layer 4a (also referred to as a first antisulfurization layer). ), A transparent metal layer 5 and a second high refractive index layer 3b are sequentially laminated.
  • the first high refractive index layer 3a or the second high refractive index layer 3b contains at least zinc sulfide (ZnS).
  • an antisulfurization layer 3 b (also referred to as a second antisulfurization layer) is provided between the second high refractive index layer 3 b and the transparent metal layer 5. It is good also as a formed structure, and as shown to FIG. 1C, between the 1st high refractive index layer 3a and the transparent metal layer 5, the 1st antisulfurization layer 4a, the 2nd high refractive index layer 3b, and a transparent metal
  • the second sulfidation preventing layer 4b may be formed between the layer 5 and the layer 5.
  • the antisulfurization layer 4a or 4b between at least the first high refractive index layer 3a or the second high refractive index layer 3b and the transparent metal layer 5, the first high refractive index layer 3a or the first high refractive index layer 3a or 2 It is possible to prevent movement and mixing of sulfur atoms constituting the zinc sulfide contained in the high refractive index layer 3b to the transparent metal layer 5, which is a preferable mode.
  • the transparent metal layer 5 for example, silver layer
  • the first high refractive index layer 3a or the second high refractive index layer 3b containing at least a metal sulfide such as ZnS are formed adjacent to each other, the metal sulfide
  • an object for example, silver sulfide
  • the light transmittance of the transparent conductor 1 is likely to be lowered.
  • the metal sulfide is presumed to be generated under the following conditions.
  • the transparent metal layer 5 When the transparent metal layer 5 is formed on the first high refractive index layer 3a containing at least zinc sulfide, the unreacted sulfur component in the first high refractive index layer 3a containing zinc sulfide is converted into the transparent metal layer 5
  • the material for example, silver
  • the ejected sulfur component reacts with a metal, for example, silver, and metal sulfide (silver sulfide) is deposited on the first high refractive index layer 3a containing zinc sulfide.
  • the transparent metal layer 5 on the 1st high refractive index layer 3a containing zinc sulfide when forming the transparent metal layer 5 on the 1st high refractive index layer 3a containing zinc sulfide by the continuous film-forming process, it is contained in the formation atmosphere of the 1st high refractive index layer 3a containing zinc sulfide.
  • the sulfur component remains in the atmosphere of the transparent metal layer 5.
  • metal sulfide silver sulfide
  • there are some Zn and unbonded sulfur on the outermost surface of the first high refractive index layer 3a and then when the transparent metal layer 5 is laminated, the unbonded active sulfur component becomes transparent metal. Bonds with constituent atoms of layer 5, for example silver.
  • the metal in the transparent metal layer 5 is a material of the second high refractive index layer 3b containing zinc sulfide. Is played in the forming atmosphere. The ejected metal reacts with the sulfur component, and metal sulfide is deposited on the surface of the transparent metal layer 5. Furthermore, a metal sulfide is also generated on the surface of the transparent metal layer 5 when the surface of the transparent metal layer 5 comes into contact with the sulfur component in the forming atmosphere.
  • the zinc and sulfur are partly present in the atmosphere in a free state, and the free sulfur is present in the transparent metal layer 5 Bonds to a constituent atom, such as silver.
  • an antisulfurization layer 4a is formed on the first high refractive index layer 3a.
  • the first high refractive index layer 3a is protected by the sulfidation preventing layer 4a, so that the sulfur component in the first high refractive index layer 3a is not easily ejected when the transparent metal layer 5 is formed.
  • the sulfur component contained in the atmosphere in which the first high refractive index layer 3a is formed reacts with the constituent components of the sulfurization preventing layer 4a.
  • the atmosphere in which the transparent metal layer 5 is formed is less likely to contain sulfur, and the formation of metal sulfide is suppressed.
  • the sulfidation preventing layer 4b is laminated on the transparent metal layer 5.
  • the metal in the transparent metal layer 5 is not easily ejected when the second high refractive index layer 3b is formed.
  • the sulfur component in the atmosphere in which the second high refractive index layer 3 b is formed is less likely to come into contact with the surface of the transparent metal layer 5. As a result, metal sulfides are hardly generated on the surface of the transparent metal layer 5.
  • the transparent conductor 1 includes a known functional layer as necessary. It may be provided.
  • an underlayer that can be a growth nucleus when the transparent metal layer 5 is formed may be formed between the transparent metal layer 5 and the first high refractive index layer 3a.
  • a first high refractive index layer, a transparent metal layer, and a second high refractive index layer are sequentially laminated on a transparent substrate that is continuously conveyed
  • a method of manufacturing a transparent conductor in which a sulfidation prevention layer is laminated between at least one of a high refractive index layer and a second high refractive index layer and a transparent metal layer, and a plurality of evaporation sources on a transparent substrate It has a plurality of film forming steps for forming a thin film layer, and the target of at least one evaporation source is composed of at least two divided targets made of different materials.
  • the “divided target” means each target obtained by dividing one target into at least two parts having different chemical compositions (see FIGS. 4A to 4C).
  • a sputtering method may be mentioned as a method for forming the high refractive index layer, the sulfurization preventing layer and the transparent metal layer.
  • the type of the sputtering method is not particularly limited, and ion beam sputtering, magnetron sputtering, reactive sputtering, bipolar sputtering, bias sputtering, RF sputtering, counter sputtering, and the like can be used.
  • the transparent metal layer is preferably a layer formed by an RF sputtering method or a counter sputtering method, and more preferably a layer formed by a counter sputtering method.
  • the transparent metal layer is a layer formed by an RF sputtering method or a counter sputtering method
  • the transparent metal layer becomes dense and surface smoothness is likely to increase.
  • the surface electrical resistance of the transparent metal layer can be further reduced, and the light transmittance can be improved.
  • At least two split targets include a split target that is a material for an antisulfurization layer and a split target that is a material for a transparent metal layer.
  • the sulfide prevention layer material (for example, metal oxide) target is a divided target that is disposed adjacent to the metal (for example, silver) target, so that the input power to the evaporation source is not reduced. Since the same effect as reducing the input power to the metal oxide target can be obtained, the antisulfurization layer can be stably formed.
  • the transparent metal layer material and the antisulfurization layer material which are ultrathin films, are provided as a split target on one evaporation source, the number of targets of the high refractive index layer can be increased. Therefore, even if the conveyance speed is increased, a high refractive index layer having a sufficient layer thickness can be formed with an input power of 10 W / cm 2 .
  • the metal oxide target (ITO, IZO, GZO, ZnO, IGZO), which is an antisulfurization layer material, is stable at an input power of 4 W / cm 2 or more. Sputtering failed.
  • the anti-sulfurization layer material target is a split target, the same effect as reducing the input power to the split target can be obtained, and stable sputtering can be achieved.
  • FIG. 3 is a schematic view showing an example of a transparent conductor manufacturing apparatus according to the present invention.
  • the manufacturing apparatus 100 mainly includes a feed roller 180 that sends out the transparent substrate 2 before forming various functional layers into the vacuum chamber 110, guide rollers 181 and 183 that guide the transparent substrate 2, and a transparent substrate. 2, a main roller 182 that transports 2, a winding roller 184 that winds up the transparent substrate 2 on which various functional layers are formed, an evaporation source 131 that forms a first high refractive index layer, an evaporation that forms a sulfidation prevention layer and a transparent metal layer. It comprises a source 151, an evaporation source 171 that forms the second high refractive index layer, and partition walls 190 to 195 that partition the space in the vacuum chamber 110.
  • the inside of the vacuum chamber 110 is partitioned by a main roller 182 and partition walls 190 to 195.
  • a main roller 182 Around the main roller 182, there are an unwind chamber 120, a first film formation chamber 130, a first differential pressure chamber 140, a second formation chamber.
  • a film chamber 150, a second differential pressure chamber 160, and a third film formation chamber 170 are formed.
  • the unwinding chamber 120 includes an inner wall surface of the vacuum chamber 110, a peripheral surface of the main roller 182 and partition walls 190 and 195 extending from the inner wall surface of the vacuum chamber 110 to the vicinity of the peripheral surface of the main roller 182. Yes.
  • the ends of the partition walls 190 and 195 extend to a position where they do not contact the transparent substrate 2 stretched around the main roller 182, close to the peripheral surface of the main roller 182, and the unwind chamber 120 and the first
  • the film formation chamber 130 and the third film formation chamber 170 are separated in a substantially airtight manner.
  • the other partition walls 191 to 194 are similarly configured, and the first film formation chamber 130 and the first differential pressure chamber 140 are partitioned by the partition wall 191, and the first differential pressure chamber 140 and the second film formation chamber 150 are formed by the partition wall 192.
  • the second film forming chamber 150 and the second differential pressure chamber 160 are partitioned by a partition wall 193, and the second differential pressure chamber 160 and the third film forming chamber 170 are partitioned by a partition wall 194. Since each chamber is partitioned by the partition walls 190 to 195, it is possible to suppress the target of each film formation chamber from entering another film formation chamber. In particular, for example, the sulfur component contained in the material of the first high refractive index layer or the second high refractive index layer is prevented from entering the second film forming chamber 150, and corrosion of the transparent metal layer containing silver is prevented. Can be suppressed.
  • the unwinding chamber 120, the first film forming chamber 130, the first differential pressure chamber 140, the second film forming chamber 150, the second differential pressure chamber 160, and the third film forming chamber 170 are respectively evacuated (not shown). And an inert gas supply means (not shown) and the like are provided, and the degree of vacuum in each chamber can be adjusted.
  • the vacuum exhaust means is not particularly limited.
  • a vacuum pump such as a turbo pump, a mechanical booster pump, a rotary pump, or a dry pump, an auxiliary means such as a cryocoil, an ultimate vacuum degree or exhaust amount adjusting means, etc.
  • a known (vacuum) evacuation means or the like used in a vacuum film forming apparatus can be used.
  • the partition walls 190 to 195 are provided between the chambers and are separated from each other in a substantially hermetic manner.
  • the first differential pressure chamber 140 is provided between the first film formation chamber 130 and the second film formation chamber 150
  • the second differential pressure chamber 160 is provided between the second film formation chamber 150 and the third film formation chamber 170.
  • the degree of vacuum in the first differential pressure chamber 140 and the second differential pressure chamber 160 is lower than that in the first to third film formation chambers 130, 150, and 170, that is, the pressure is high. By doing so, it is possible to suppress the target in each film formation chamber from entering another film formation chamber. In particular, for example, the sulfur component contained in the first high-refractive index layer or the second high-refractive index layer is prevented from entering the second film forming chamber 150 and the corrosion of the transparent metal layer containing silver is suppressed. Can do.
  • the degree of vacuum of the second film formation chamber 150 is lower than that of the first film formation chamber 130 and the third film formation chamber 170, that is, the pressure is high. It is preferable that Thereby, it can suppress that the sulfur component in the 1st film-forming chamber 130 and the 3rd film-forming chamber 170 penetrate
  • the transparent substrate 2 used in the manufacturing apparatus 100 is formed in a long length, is unwound from the feed roller 180 in the unwind chamber 120, and is taken up by the take-up roller 184.
  • the transparent substrate 2 unwound from the delivery roller 180 is conveyed to the main roller 182 via the guide roller 181, and sequentially in the first film formation chamber 130, the second film formation chamber 150, and the third film formation chamber 170.
  • a thin film layer is formed, and is further wound around a winding roller 184 via a guide roller 183.
  • the composition of each layer formed by sputtering changes, so the moisture is removed from the transparent substrate 2 before forming the layer. It is preferable. Specifically, it is preferable to perform preliminary heating, evacuation by a cryopump, or the like on the transparent substrate 2, and the manufacturing apparatus 100 may have a configuration for performing them.
  • the manufacturing apparatus 100 may be equipped with the structure for performing them.
  • the feed roller 180 supplies the long transparent substrate 2 and sends it to the downstream side in the transport direction X. Further, the winding roller 184 winds the layer-formed transparent substrate 2.
  • the feed roller 180 and the take-up roller 184 are provided in the unwind chamber 120.
  • the control unit (not shown) of the manufacturing apparatus 100 synchronizes the feeding of the transparent substrate 2 by the feeding roller 180 and the winding of the transparent substrate 2 on which the layer has been formed by the winding roller 184, so Layers are sequentially formed in the first film formation chamber 130, the second film formation chamber 150, and the third film formation chamber 170 while the transparent substrate 2 is conveyed in the longitudinal direction along a predetermined conveyance path. Therefore, the unwinding chamber 120 is the most upstream chamber in the transport direction X of the transparent substrate 2 and the most downstream chamber in the manufacturing apparatus 100.
  • the guide rollers 181 and 183 are normal guide rollers that are provided in the unwind chamber 120 and guide the transparent substrate 2 along a predetermined transport path.
  • the main roller 182 is a cylindrical member that rotates in the direction of the arrow in FIG.
  • the main roller 182 wraps the transparent substrate 2 conveyed by the guide roller 181 in a predetermined path around a predetermined area of the peripheral surface and conveys the transparent substrate 2 in the longitudinal direction while holding it at a predetermined position.
  • the transparent substrate 2 is passed through the first differential pressure chamber 140, the second film formation chamber 150, the second differential pressure chamber 160, and the third film formation chamber 170 in this order, and is sent to the guide roller 183 in the unwind chamber 120.
  • the main roller 182 also functions as a counter electrode for the evaporation source 131 of the first film formation chamber 130, the evaporation source 151 of the second film formation chamber 150, and the evaporation source 171 of the third film formation chamber 170.
  • the main roller 182 may incorporate a cooling means for cooling the transparent substrate 2.
  • the cooling means for the main roller 182 is not particularly limited, and may be a cooling means for circulating a refrigerant or the like, or a cooling means using a piezo element or the like.
  • the cooling means is configured to cool the temperature of the transparent substrate 2 to about ⁇ 20 to 65 ° C., for example.
  • the evaporation source 131 is provided in the first film forming chamber 130, and a target 133 that is a raw material for the first high refractive index layer is attached to the sputtering cathode 132.
  • the evaporation source 131 forms a first high refractive index layer having a layer thickness corresponding to the input power amount on the transparent substrate 2 conveyed by the main roller 182 when power is input.
  • the evaporation source 151 is provided in the second film formation chamber 150, and the split targets 153 a and 153 b that are raw materials for the sulfurization prevention layer and the transparent metal layer are attached to the sputtering cathode 152.
  • the split target 153a of the sulfidation prevention layer (first sulfidation prevention layer) is upstream in the transport direction X upstream of the transparent substrate 2, and the transparent metal is downstream in the transport direction X of the transparent substrate 2.
  • a layer split target 153b is provided. As shown in FIG.
  • the split target provided on the sputtering cathode 152 is provided with a transparent metal layer split target 153 b on the upstream side in the transport direction X of the transparent substrate 2, and prevents sulfurization on the downstream side in the transport direction X of the transparent substrate 2.
  • a split target 153c for the layer may be provided, and as shown in FIG. 4C, the first anti-sulfur layer is divided from the upstream side toward the downstream side in the transport direction X of the transparent substrate 2.
  • the evaporation source 151 forms an anti-sulfurization layer and a transparent metal layer having a layer thickness corresponding to the input power amount on the transparent substrate 2 conveyed by the main roller 182 when power is input.
  • a partition plate 196 may be provided on the extended line of the boundary between the divided targets 153a and 153b so that the divided targets are not mixed.
  • the partition plate 196 is held by a holding shaft 197 extending substantially horizontally between the opposing wall surfaces of the partition walls 192 and 193. Both ends of the partition plate 196 are disposed so as not to contact the main roller 182 and the divided targets 153a and 153b, but may be provided to extend as close as possible so that the divided targets do not mix. preferable.
  • the partition plate 196 may be provided in a straight line with respect to the direction perpendicular to the divided target surface, or may be provided in a curved shape in one of the divided targets 153a and 153b. Note that the partition plate 196 is appropriately provided on the extended line of the boundary according to the number of division targets (see FIGS. 4A to 4C).
  • an opening limiting mask (not shown) may be provided between the transparent substrate 2 transported to the main roller 182 and the evaporation source 151.
  • the opening limiting mask is not provided in the first film formation chamber 130 and the third film formation chamber 170.
  • a thin layer is formed by reducing the amount of input power input to the evaporation source.
  • the transparent metal layer is formed by reducing the amount of electric power input to the evaporation source, the average light absorptance of the formed transparent metal layer increases and the average light transmittance decreases.
  • the width in the substrate transport direction of the region facing the transparent substrate 2 in the divided target 153b can be increased.
  • a transparent metal layer having a thin layer thickness can be formed without reducing the function.
  • the evaporation source 171 is provided in the third film formation chamber 170, and a target 173, which is a raw material for the second high refractive index layer, is attached to the sputtering cathode 172.
  • the evaporation source 171 forms a second high refractive index layer having a layer thickness corresponding to the input power amount on the transparent substrate 2 conveyed by the main roller 182 when power is input.
  • the sputtering cathodes 132, 152, and 172 those of the so-called magnetron cathode type in which a magnet is disposed inside and the plasma is confined by a magnetic field to increase the sputtering efficiency are preferable.
  • sputtering cathodes 132, 152 and 172 either a flat cathode or a rotary cathode may be used.
  • the rotary cathode is used. More preferably.
  • the magnetic flux density of the magnet is preferably in the range of 300 to 1000 G (3 ⁇ 10 ⁇ 2 to 10 ⁇ 10 ⁇ 2 T).
  • Examples of sputtering conditions in each of the film forming chambers 130, 150, and 170 include an inert gas flow rate of 5 to 40 sccm (Standard Cubic Centimeter per Minute), a pressure of 0.1 to 1.0 Pa, such as Ar, Kr, and Xe. And by setting to such conditions, it can suppress that the surface of each layer formed becomes rough.
  • the layer thickness of each layer formed in each of the film formation chambers 130, 150, and 170 is preferably monitored by a layer thickness monitor such as a crystal resonator or an interferometer.
  • the first differential pressure chamber 140 is provided between the first film formation chamber 130 and the second film formation chamber 150, and the second film formation chamber 150, the third film formation chamber 170,
  • the first differential pressure chamber 140 and the second differential pressure chamber 160 may not be provided.
  • the first film formation chamber 130, the second film formation chamber 150, and the third film formation chamber 170 are provided.
  • the first differential pressure chamber 140 and the second differential pressure are provided.
  • a film forming chamber for forming another functional layer constituting the transparent conductor may be provided. That is, as shown in FIG. 6, the manufacturing apparatus 200 includes a first film formation chamber 230 and a second film formation chamber 240 that form the first high refractive index layer, a third formation layer that forms the sulfidation prevention layer and the transparent metal layer.
  • the film chamber 250 and the fourth film forming chamber 260 and the fifth film forming chamber 270 for forming the second high refractive index layer may be provided.
  • the transparent conductor according to the present invention is preferably performed using the manufacturing apparatus 100.
  • the case where the said manufacturing apparatus 100 is used is demonstrated.
  • a film forming process of the first high refractive index layer is performed by the evaporation source 131 on the transparent substrate 2 that is fed from the feed roller 180 and conveyed by the main roller 182. Subsequently, a film forming step of an antisulfurization layer and a transparent metal layer is performed on the transparent substrate 2 conveyed by the main roller 182 by the evaporation source 151. Under the present circumstances, you may perform the film-forming process of a sulfide prevention layer and a transparent metal layer through the opening restriction
  • the sulfidation prevention layer and the transparent metal layer By forming the sulfidation prevention layer and the transparent metal layer through the opening limiting mask, the sulfidation prevention layer and the transparent metal layer having a thinner thickness than the first and second high refractive index layers can be formed without reducing the function. Can be formed. Subsequently, a film forming process of the second high refractive index layer is performed by the evaporation source 171 on the transparent substrate 2 conveyed by the main roller 182. Thus, the transparent substrate 2 on which the first high refractive index layer, the sulfidation preventing layer, the transparent metal layer, and the second high refractive index layer are formed is wound up by the winding roller 184. As described above, a desired transparent conductor can be manufactured.
  • the transparent substrate 2 may be a transparent substrate and may be the same as the transparent substrate of various conventionally known display devices.
  • transparent means that the light transmittance at a wavelength of 550 nm is 50% or more.
  • the transparent substrate 2 for example, a glass substrate, a cellulose ester resin (for example, triacetyl cellulose, diacetyl cellulose, acetyl propionyl cellulose, etc.), a polycarbonate resin (for example, Panlite, Multilon (both manufactured by Teijin Ltd.)), cyclo Olefin resins (for example, ZEONOR (manufactured by ZEON CORPORATION), ARTON (manufactured by JSR), APPEL (manufactured by Mitsui Chemicals)), acrylic resins (for example, polymethyl methacrylate, acrylite (manufactured by Mitsubishi Rayon), Sumipex (Sumitomo) Chemical)), polyimide, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyester resin (eg, polyethylene terephthalate (PET), polyethylene naphthalate (PEN)), polyethersulfone, ABS AS resin, MBS resin, polys
  • examples of the material of the transparent substrate 2 include a glass substrate, cellulose ester resin, polycarbonate resin, polyester resin (particularly polyethylene terephthalate), triacetyl cellulose, cycloolefin resin, phenol resin, epoxy resin, and polyphenylene.
  • a transparent resin film made of ether (PPE) resin, polyethersulfone, ABS / AS resin, MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), styrene block copolymer resin, or the like is preferable. .
  • the transparent substrate 2 preferably has high transparency to visible light, and the average transmittance of light having a wavelength of 450 to 800 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 85% or more. is there.
  • the average light transmittance of the transparent substrate 2 is 70% or more, the light transmittance of the transparent conductor 1 is likely to increase.
  • the average absorption rate of light at a wavelength of 450 to 800 nm of the transparent substrate 2 is preferably 10% or less, more preferably 5% or less, and still more preferably 3% or less.
  • the average transmittance is measured by making light incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent substrate 2.
  • the average transmittance and average reflectance are measured with a spectrophotometer.
  • the refractive index of light at a wavelength of 570 nm of the transparent substrate 2 is preferably 1.40 to 1.95 at 25 ° C., more preferably 1.45 to 1.75, still more preferably 1.45 to 1. .70.
  • the refractive index of the transparent substrate 2 is usually determined by the material of the transparent substrate 2. The refractive index of the transparent substrate 2 is measured with an ellipsometer.
  • the haze value of the transparent substrate 2 is preferably in the range of 0.01 to 2.5, more preferably in the range of 0.1 to 1.2.
  • the haze value of the transparent conductor 1 is suppressed as the haze value of the transparent substrate 2 is 2.5 or less.
  • the haze value is measured with a haze meter.
  • the thickness of the transparent substrate 2 is preferably in the range of 1 ⁇ m to 20 mm, more preferably in the range of 10 ⁇ m to 2 mm.
  • the thickness of the transparent substrate 2 is 1 ⁇ m or more, the strength of the transparent substrate 2 is increased, and it is possible to suppress cracking or tearing when the first high refractive index layer 3a is formed.
  • the thickness of the transparent substrate 2 is 20 mm or less, the flexibility of the transparent conductor 1 is sufficient.
  • the thickness of the apparatus using the transparent conductor 1 can be reduced.
  • the apparatus using the transparent conductor 1 can also be reduced in weight.
  • a glass substrate, a resin film, or the like is used as the transparent substrate 2.
  • a smooth layer (clear hard coat layer: CHC layer), a protective layer, an adhesion layer, a reflective layer is used.
  • a layer (film) for expressing various functions such as an antireflection layer may be formed.
  • the average surface roughness Ra is preferably 3 nm or less.
  • the first high refractive index layer 3 a is a layer that adjusts the light transmittance (optical admittance) of the transparent metal layer 5.
  • the first high refractive index layer 3a includes a dielectric material or an oxide semiconductor material having a refractive index higher than the refractive index of the transparent substrate 2 described above.
  • the dielectric material or the oxide semiconductor material included in the first high refractive index layer 3a may be an insulating material or a conductive material.
  • a metal oxide can be used as the dielectric material or the oxide semiconductor material.
  • the first high refractive index layer 3a may contain only one kind of the metal oxide or two or more kinds.
  • zinc sulfide can be used as the dielectric material or the oxide semiconductor material included in the first high refractive index layer 3a.
  • the first high refractive index layer 3a may contain only zinc sulfide, or may contain other materials together with zinc sulfide. Material contained together with zinc sulphide, a metal oxide or SiO 2 or the like which can be used as the dielectric material or an oxide semiconductor material, as will be described later, particularly preferably SiO 2.
  • SiO 2 is contained together with zinc sulfide, the first high refractive index layer 3a is likely to be amorphous, and the flexibility of the transparent conductor 1 is likely to be enhanced.
  • the content of zinc sulfide is 0. 0 relative to the total number of moles of all the materials constituting the first high refractive index layer 3a. It is preferably in the range of 1 to 95% by mass, more preferably in the range of 50 to 90% by mass, and still more preferably in the range of 60 to 85% by mass.
  • the content of zinc sulfide is large, the sputtering rate is increased and the formation rate of the first high refractive index layer 3a is increased.
  • the amorphousness of the first high refractive index layer 3a is increased, and cracking of the first high refractive index layer 3a is suppressed.
  • the refractive index of light at a wavelength of 570 nm of the dielectric material or oxide semiconductor material is preferably 0.1 to 1.1 larger than the refractive index of light at a wavelength of 570 nm of the transparent substrate 2, and is preferably 0.4 to 1.0. Larger is more preferable.
  • the specific refractive index of light at a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the first high refractive index layer 3a is preferably greater than 1.5 at 25 ° C. More preferably, it is within the range of .5, and even more preferably within the range of 1.8 to 2.5.
  • the optical admittance of the transparent conductor 1 is sufficiently adjusted by the first high refractive index layer 3a.
  • the refractive index of the first high refractive index layer 3a is adjusted by the refractive index of the material included in the first high refractive index layer 3a and the density of the material included in the first high refractive index layer 3a.
  • the layer thickness of the first high refractive index layer 3a is preferably in the range of 15 to 150 nm, more preferably in the range of 20 to 80 nm.
  • the optical admittance of the transparent conductor 1 is sufficiently adjusted by the first high refractive index layer 3a.
  • the thickness of the first high refractive index layer 3a is 150 nm or less, the light transmittance of the region where the first high refractive index layer 3a is formed is unlikely to decrease.
  • the layer thickness of the first high refractive index layer 3a is measured with an ellipsometer.
  • the first high refractive index layer 3a preferably contains zinc sulfide, but more preferably contains amorphous zinc sulfide. Since the amorphous zinc sulfide is contained in the first high refractive index layer 3a, the stress generated in the transparent conductor 1 can be reduced, and the occurrence of warpage in the transparent conductor 1 can be suppressed. It is possible to suppress the generation of cracks when the transparent conductor 1 is bent. Furthermore, the light transmittance of the first high refractive index layer 3a can be improved by containing amorphous zinc sulfide in the first high refractive index layer 3a.
  • the zinc sulfide can be made amorphous.
  • the content of the amorphized metal material can be appropriately changed, whereby the refractive index of light can be changed. Therefore, the light transmittance can be made desired.
  • the first high refractive index layer 3a is not amorphized by containing, for example, TiO 2 or Nb 2 O 5 which is a transparent material having a higher refractive index than zinc sulfide as an amorphized metal material. That is, the reflection band can be expanded as compared with the first high refractive index layer made of crystalline zinc sulfide alone. Thereby, adjustment of the optical characteristic of the transparent conductor 1 becomes easy.
  • the transparent metal layer 5 can be protected more reliably. Therefore, for example, by containing Si 3 N 4 or Al 2 O 3 as an amorphized metal material together with zinc sulfide in the first high refractive index layer 3a, it is possible to improve the scratch resistance of the transparent conductor 1. Become.
  • amorphized metal material for example, a metal oxide, a metal fluoride, a metal nitride, or the like can be used.
  • Examples of the metal oxide used as the amorphized metal material include TiO 2 , In 2 O 5 , ZnO, Nb 2 O 5 , ZrO 2 , CeO 2 , Ta 2 O 5 , Ti 3 O 5 , and Ti 4 O 7.
  • the metal oxide is used to include SiO 2 .
  • SiO 2 and TiO 2 are preferable.
  • SiO 2 zinc sulfide can be made amorphous even if its content is small. Therefore, by incorporating the SiO 2, after amorphization of zinc sulfide, high adhesion (peeling resistance) and high durability (e.g., moisture resistance, etc.) it can be particularly well achieved a.
  • TiO 2 exhibits a particularly high refractive index among transparent materials, by using TiO 2 , a wide reflection band can be obtained and the optical characteristics of the transparent conductor 1 can be easily adjusted.
  • Examples of the metal fluoride used as the amorphized metal material include LaF 3 , BaF 2 , Na 5 Al 3 F 14 , Na 3 AlF 6 , AlF 3 , MgF 2 , CaF 2 , CeF 3 , NdF 3 , YF 3 etc. are mentioned.
  • examples of the metal nitride used as the amorphized metal material include Si 3 N 4 and AlN. Among these, Si 3 N 4 is preferable. Since Si 3 N 4 has a high hardness, it is possible to improve the scratch resistance of the first high refractive index layer 3a by using Si 3 N 4 . In the present invention, the metal nitride is used in the meaning including Si 3 N 4 .
  • these amorphized metal materials may be used independently, and 2 or more types may be used in arbitrary ratios and combinations.
  • the amount of the amorphized metal material contained with respect to the crystalline zinc sulfide there is no particular limitation on the amount of the amorphized metal material contained with respect to the crystalline zinc sulfide.
  • SiO 2 when SiO 2 is used as the amorphized metal material, it is usually 1% by mass or more, more preferably 5% by mass with respect to crystalline zinc sulfide. % Or more and usually 99% by mass or less, and more preferably 95% by mass or less of SiO 2 can be used to make amorphous zinc sulfide.
  • the first sulfidation preventing layer 4a for example, metal oxide, metal nitride, metal fluoride, or Zn can be used. Among these, Zn, a metal oxide containing Zn, or a metal oxide containing Ga is preferable. Only 1 type may be contained in the 1st sulfurization prevention layer 4a, and 2 or more types may be contained. However, when the first high refractive index layer 3a, the first antisulfurization layer 4a, and the transparent metal layer 5 are continuously formed, the first antisulfurization layer 4a is composed of a compound capable of reacting with sulfur, It is preferable to contain a compound capable of adsorbing sulfur. When the material contained in the first sulfurization prevention layer 4a is a compound that reacts with sulfur, the reaction product with the sulfur preferably has a high visible light transmittance.
  • metal oxide examples include TiO 2 , ITO, ZnO, Nb 2 O 5 , ZrO 2 , CeO 2 , Ta 2 O 5 , Ti 3 O 5 , Ti 4 O 7 , Ti 2 O 3 , TiO, SnO 2.
  • Examples of the metal fluoride include LaF 3 , BaF 2 , Na 5 Al 3 F 14 , Na 3 AlF 6 , AlF 3 , MgF 2 , CaF 2 , CeF 3 , NdF 3 , YF 3 and the like.
  • Examples of the metal nitride include Si 3 N 4 and AlN.
  • the material constituting the first anti-sulfuration layer 4a preferably a metal oxide, in particular, ZnO, ITO, IGZO, Ga 2 O 3, Nb 2 O 5, SnO 2, Y 2 O 3 and M3 (registered Trademark) is preferred.
  • a metal oxide in particular, ZnO, ITO, IGZO, Ga 2 O 3, Nb 2 O 5, SnO 2, Y 2 O 3 and M3 (registered Trademark) is preferred.
  • adhesiveness with the zinc sulfide contained in the 1st high refractive index layer 3a or the 2nd high refractive index layer 3b can be improved, and durability can be improved more.
  • the layer thickness of the first sulfidation preventing layer 4a is preferably a layer thickness capable of protecting the surface of the first high refractive index layer 3a from an impact when forming the transparent metal layer 5 described later.
  • zinc sulfide that can be contained in the first high refractive index layer 4 a has high affinity with the metal contained in the transparent metal layer 5. Therefore, if the thickness of the first anti-sulfurization layer 4a is very thin and a part of the first high refractive index layer 3a is slightly exposed, the transparent metal layer 5 grows around the exposed part and is transparent. The metal layer 5 tends to be dense.
  • the first antisulfurization layer 4a is preferably relatively thin, preferably in the range of 0.1 to 10 nm, more preferably in the range of 0.5 to 5 nm, and still more preferably 1 to 3 nm. Is within the range.
  • the layer thickness of the first sulfidation preventing layer 4a is measured with an ellipsometer.
  • the transparent metal layer 5 is a layer for conducting electricity in the transparent conductor 1.
  • the transparent metal layer 5 preferably contains silver. From the viewpoint of obtaining high conductivity, the transparent metal layer 5 is preferably made of silver or an alloy containing 90 at% or more of silver. As a metal combined with silver, for example, zinc, gold, copper, palladium, aluminum, manganese, bismuth, neodymium, molybdenum, nickel, iron, cobalt, tungsten, tantalum, chromium, indium, titanium, or the like can be used. Among these, copper, palladium, or bismuth is preferable.
  • the transparent metal layer 5 may contain a simple substance or compound of silver and a simple substance or compound of copper, palladium, or bismuth, or is included in the form of an alloy of silver and at least one of these metals. However, it is preferably contained in the form of an alloy. Moreover, it is preferable that all of the materials constituting the transparent metal layer 5 are an alloy of silver and at least one of these metals. By including at least one of these metals in the transparent metal layer 5, it is possible to further improve the durability, peel resistance, and the like of the transparent conductor 1. Further, for example, when the transparent metal layer 5 contains an alloy of silver and zinc, the sulfidation resistance of the transparent metal layer 5 can be improved.
  • the transparent metal layer 5 contains an alloy of silver and gold
  • the salt resistance (NaCl) resistance of the transparent metal layer 5 can be improved.
  • the transparent metal layer 5 contains an alloy of silver and copper
  • the oxidation resistance of the transparent metal layer 5 can be improved.
  • the plasmon absorption rate of the transparent metal layer 5 is preferably 10% or less (over the entire range) over a wavelength range of 400 to 800 nm, more preferably 7% or less, and even more preferably 5% or less. If there is a region having a large plasmon absorption rate in a part of the wavelength of 400 to 800 nm, the transmitted light of the transparent conductor 1 is easily colored.
  • the plasmon absorption rate at a wavelength of 400 to 800 nm of the transparent metal layer 5 is measured by the following procedure.
  • Platinum palladium is formed to 0.1 nm on a glass substrate by a magnetron sputtering apparatus. The average thickness of platinum palladium is calculated from the formation rate of the manufacturer's nominal value of the sputtering apparatus. Thereafter, a film made of metal is formed with a thickness of 20 nm on the substrate to which platinum palladium is adhered by sputtering. (Ii) Then, measurement light is incident from an angle inclined by 5 ° with respect to the normal of the surface of the obtained metal film, and the light transmittance and light reflectance of the metal film are measured.
  • the light transmittance and light reflectance are measured with a spectrophotometer.
  • a transparent metal layer to be measured is formed on the same glass substrate. And about the said transparent metal layer, light transmittance and light reflectance are measured similarly.
  • the reference data is subtracted from the obtained absorption rate, and the calculated value is defined as the plasmon absorption rate.
  • the layer thickness of the transparent metal layer 5 is preferably 10 nm or less, more preferably in the range of 3 to 9 nm, and still more preferably in the range of 5 to 8 nm.
  • the layer thickness of the transparent metal layer 5 is measured with an ellipsometer.
  • the transparent metal layer 5 may be formed by any film formation method, but from the viewpoint of increasing the average transmittance of the transparent metal layer 5, it is preferably a layer formed by a sputtering method. It is preferable that the transparent metal layer 5 be a layer formed on an underlayer that can become a growth nucleus when forming the transparent metal layer 5. When the transparent metal layer 5 is a layer formed on the underlayer, the underlayer becomes a growth nucleus when the transparent metal layer 5 is formed, so that the transparent metal layer 5 tends to be a smooth layer. As a result, even if the transparent metal layer 5 is thin, plasmon absorption is less likely to occur.
  • the material collides with the deposition target at high speed, so that a dense and smooth film can be easily obtained and the light transmittance of the transparent metal layer 5 can be improved. Further, when the transparent metal layer 5 is a layer formed by sputtering, the transparent metal layer 5 is hardly corroded even in a high temperature and low humidity environment.
  • the type of the sputtering method is not particularly limited, and ion beam sputtering, magnetron sputtering, reactive sputtering, bipolar sputtering, bias sputtering, RF sputtering, counter sputtering, and the like can be used.
  • the transparent metal layer 5 is preferably a layer formed by RF sputtering or counter sputtering.
  • the transparent metal layer 5 becomes dense and the surface smoothness is likely to be increased. As a result, the surface electrical resistance of the transparent metal layer 5 can be further reduced, and the light transmittance can be improved.
  • a second antisulfurization layer 4b is provided between the transparent metal layer 5 and the second high refractive index layer 3b. Is preferred. Since the second sulfidation preventing layer 4b is configured in the same manner as the first sulfidation preventing layer 4a, description of common points is omitted, and only points different from the first sulfidation preventing layer 4a are described below. .
  • the layer thickness of the second antisulfurization layer 4b is preferably a layer thickness that can protect the surface of the transparent metal layer 5 from an impact during the formation of the second high refractive index layer 3b.
  • the metal contained in the transparent metal layer 5 and zinc sulfide that can be contained in the second high refractive index layer 3b have high affinity. Therefore, if the thickness of the second antisulfurization layer 4b is very thin and a part of the transparent metal layer 5 is slightly exposed, the transparent metal layer 5, the second antisulfurization layer 4b, and the second high refractive index layer. Adhesion with 3b tends to increase.
  • the specific layer thickness of the second antisulfurization layer 4b is preferably in the range of 0.1 to 10 nm, more preferably in the range of 0.5 to 5 nm, and still more preferably 1 to 3 nm. Is within the range.
  • the layer thickness of the second sulfurization preventing layer 4b is measured with an ellipsometer.
  • the second high refractive index layer 3b is a layer for adjusting the light transmittance (optical admittance) of the region where the transparent metal layer 5 is formed.
  • the second high-refractive index layer 3b is configured in the same manner as the first high-refractive index layer 3a. Therefore, description of common points is omitted, and only differences from the first high-refractive index layer 3a are described below. Explained.
  • the second high-refractive index layer 3b may contain zinc sulfide. If the second high-refractive index layer 3b contains zinc sulfide, the second metal layer 5b transmits moisture to the transparent metal layer 5. It is possible to suppress the corrosion of the transparent metal layer 5.
  • the average transmittance of light at a wavelength of 450 to 800 nm of the transparent conductor according to the present invention is preferably 94% or more.
  • the transparent conductor can be applied to applications requiring high transparency to visible light.
  • the average transmittance of light at a wavelength of 400 to 1000 nm of the transparent conductor is preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more.
  • the present invention also relates to applications requiring transparency with respect to light in a wide wavelength range, such as a transparent conductive film for solar cells.
  • a transparent conductor can be applied.
  • the average absorptance of light at a wavelength of 400 to 800 nm of the transparent conductor is preferably 10% or less, more preferably 8% or less, and still more preferably 7% or less.
  • the maximum value of the light absorptance at a wavelength of 450 to 800 nm of the transparent conductor is preferably 15% or less, more preferably 10% or less, and further preferably 9% or less.
  • the average reflectance of light at a wavelength of 500 to 700 nm of the transparent conductor is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. The lower the average absorptance and average reflectance of the transparent conductor, the higher the aforementioned average transmittance.
  • the average transmittance and the average reflectance are preferably the average transmittance and the average reflectance under the usage environment of the transparent conductor. Specifically, when the transparent conductor is used by being bonded to an organic resin, it is preferable to measure the average transmittance and the average reflectance by disposing a layer made of the organic resin on the transparent conductor. On the other hand, when the transparent conductor is used in the air, it is preferable to measure the average transmittance and the average reflectance in the air.
  • the average transmittance and average reflectance can be measured with a spectrophotometer by making measurement light incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent conductor. The average absorptance is calculated from a calculation formula of 100 ⁇ (average transmittance + average reflectance).
  • the luminous reflectance of the transparent conductor is preferably 5% or less, more preferably 3% or less, and still more preferably 1% or less.
  • the luminous reflectance is a Y value measured with a spectrophotometer (U4100: manufactured by Hitachi High-Technologies Corporation).
  • the a * value and b * value in the L * a * b * color system of the transparent conductor are each preferably within ⁇ 30, more preferably within ⁇ 5.0, and ⁇ 3. It is further preferably within 0, and particularly preferably within ⁇ 2.0.
  • the a * value and b * value in the L * a * b * color system are within ⁇ 30, the color is observed as colorless and transparent.
  • the a * value and b * value in the L * a * b * color system are measured with a spectrophotometer.
  • the surface electric resistance value of the transparent conductor is preferably 50 ⁇ / ⁇ or less, and more preferably 30 ⁇ / ⁇ or less.
  • a transparent conductor having a surface electrical resistance value of 50 ⁇ / ⁇ or less can be applied to a transparent conductive panel for a capacitive touch panel.
  • the surface electrical resistance value of the transparent conductor is adjusted by the thickness of the transparent metal layer and the like.
  • the surface electrical resistance value of the transparent conductor is measured in accordance with, for example, JIS K7194, ASTM D257, and the like. It is also measured by a commercially available surface electrical resistivity meter.
  • the transparent conductor according to the present invention includes various types of optoelectronics such as liquid crystal, plasma, organic electroluminescence, field emission, various types of displays, touch panels, mobile phones, electronic paper, various solar cells, various electroluminescence dimming elements, etc. It can be preferably used for a substrate of a device.
  • the first high refractive index layer and the first sulfurization prevention are produced as follows using the production apparatus 300 shown in FIG. A transparent metal layer 101, a transparent metal layer, a second anti-sulfurization layer, and a second high-refractive index layer to produce transparent conductors 101 to 104, and the manufacturing apparatus 200 shown in FIG. In this way, the first high refractive index layer, the first antisulfurization layer, the transparent metal layer, the second antisulfurization layer, and the second high refractive index layer were formed, and the transparent conductors 105 to 108 were produced.
  • the split target shown in FIG. 4C was used.
  • first sulfidation prevention layer On the first high refractive index layer, Ar 40.0 sccm, sputtering pressure 0.1 Pa, room temperature (25 ° C.), the electric power input to the evaporation source 341 is 1.2 W. ZnO was sputtered at / cm 2 to form a first sulfidation preventive layer having a layer thickness of 2.4 nm. The target length of the evaporation source 341 was 0.20 m.
  • ZnS is used as the target 333 of the evaporation source 331
  • ZnO is used as the target 343 of the evaporation source 341
  • Ag is used as the target 353 of the evaporation source 351
  • ZnO is used as the target 363 of the evaporation source 361.
  • ZnS was used as the target 373 of the evaporation source 371.
  • the conveyance speed of the transparent substrate was set to 0.36 m / min.
  • first sulfidation prevention layer On the first high refractive index layer, Ar 40.0 sccm, sputtering pressure 0.1 Pa, room temperature (25 ° C.), the amount of power supplied to the evaporation source 341 is 1.9 W. ZnO was sputtered at / cm 2 to form a first sulfidation preventing layer having a layer thickness of 2.1 nm. The target length of the evaporation source 341 was 0.20 m.
  • Transparent conductor 104 was produced in the same manner as in production of transparent conductor 103, except that the target length was changed when forming the first and second sulfidation prevention layers.
  • first anti-sulfuration layer (5.2) Formation of first anti-sulfuration layer, transparent metal layer and second anti-sulfur layer
  • evaporation source 151 is sputtered at an input power amount of 1.9 W / cm 2 to form a first antisulfurization layer having a thickness of 0.7 nm, a transparent metal layer having a thickness of 8.4 nm, and a first metal having a thickness of 0.7 nm.
  • a disulfide prevention layer was formed.
  • the division target lengths corresponding to the first sulfidation prevention layer, the transparent metal layer, and the second sulfidation prevention layer of the evaporation source 151 were 0.08 m, 0.04 m, and 0.08 m, respectively.
  • the target lengths of the first anti-sulfuration layer, the transparent metal layer, and the second anti-sulfur layer were controlled using an opening limiting mask.
  • the width of the aperture limiting mask is the target length.
  • a second high refractive index layer is formed on each second antisulfurization layer by the respective evaporation sources 171 in the same manner as the first high refractive index layer.
  • a body 105 was produced.
  • Transparent conductor 106 was produced in the same manner as in production of transparent conductor 105, except that the amount of electric power applied to evaporation source 151 was changed as shown in Table 2.
  • each layer in the transparent conductors 101 to 108 is J.P. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.
  • the static formation speed at the time of forming each layer was calculated.
  • the static deposition rate (nm / min) is the thickness of the layer actually deposited on the transparent substrate after the transparent substrate passes over the region facing the transparent substrate of the deposition source.
  • t (nm) the transport speed (constant speed) of the transparent substrate is R (m / min)
  • the width in the substrate transport direction of the region facing the transparent substrate of the film forming source is w (m)
  • the width of the opening of the film formation mask in the substrate transport direction is w (m).
  • the substrate transport direction is a direction substantially parallel to the surface of the film forming source facing the transparent substrate, and is a direction along the direction in which the transparent substrate is transported on the film forming source.
  • measurement light (light having a wavelength of 450 to 800 nm) is incident from an angle inclined by 5 ° with respect to the normal line of the surface of the alkali-free glass substrate, and the spectrophotometer U4100 manufactured by Hitachi, Ltd.
  • the transmittance (%) and the reflectance (%) were measured.
  • the average absorptance was calculated from a calculation formula of 100 ⁇ (average transmittance + average reflectance). The measurement results are shown in Table 2.
  • the average reflectance of the transparent conductor is the reflection at the interface between the non-alkali glass substrate and the atmosphere (4%), and the reflection at the interface between the transparent substrate of the transparent conductor and the atmosphere. A value obtained by subtracting (4%) was used. Further, the transmittance of the transparent conductor is 8 in the measured value of the transmittance considering the reflection at the interface between the alkali-free glass substrate and the atmosphere and the reflection at the interface between the transparent substrate and the atmosphere of the transparent conductor. % was added.
  • the transparent conductor 101 of the comparative example has a large amount of absorption loss and a low average light transmittance.
  • improvements were observed in the average light transmittance, the amount of absorption loss, and the resistance value.
  • the transparent conductor manufacturing method is useful for suppressing a decrease in light transmittance due to sulfidation of the transparent metal layer material.
  • the present invention can be particularly suitably used for providing a method for producing a transparent conductor that suppresses a decrease in light transmittance due to sulfidation of a transparent metal layer material.

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Abstract

La présente invention concerne un procédé de fabrication d'un conducteur transparent, qui supprime une diminution de la transmittance de la lumière due à la sulfuration d'un matériau de couche métallique transparente. Dans un procédé de fabrication d'un conducteur transparent (1) selon la présente invention, une première couche à indice de réfraction élevé (3a), une couche métallique transparente (5) et une seconde couche à indice de réfraction élevé (3b) sont stratifiées de façon séquentielle sur un substrat transparent (2) qui est transporté en continu ; et une couche de prévention de sulfuration est stratifiée entre la première couche à indice de réfraction élevé (3a) et la couche métallique transparente (5) et/ou entre la seconde couche à indice de réfraction élevé (3b) et la couche métallique transparente (5). Ce procédé de fabrication d'un conducteur transparent (1) est caractérisé en ce qu'il comprend une pluralité d'étapes de formation de film destinées à former des couches de film mince sur le substrat transparent (2) au moyen d'une pluralité de sources d'évaporation ; et est également caractérisé en ce qu'une cible d'au moins une source d'évaporation est constituée d'au moins deux cibles fendues qui sont formées de différents matériaux.
PCT/JP2014/079789 2014-03-07 2014-11-11 Procédé de fabrication de conducteur transparent WO2015133007A1 (fr)

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JP2016506078A JPWO2015133007A1 (ja) 2014-03-07 2014-11-11 透明導電体の製造方法

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JP2014-044818 2014-03-07
JP2014044818 2014-03-07

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WO2015133007A1 true WO2015133007A1 (fr) 2015-09-11

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JP (1) JPWO2015133007A1 (fr)
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005004899A (ja) * 2003-06-12 2005-01-06 Fuji Photo Film Co Ltd 磁気記録媒体およびその製造方法
JP2006184849A (ja) * 2004-11-30 2006-07-13 Toppan Printing Co Ltd 反射防止積層体、光学機能性フィルタ、光学表示装置および光学物品

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005004899A (ja) * 2003-06-12 2005-01-06 Fuji Photo Film Co Ltd 磁気記録媒体およびその製造方法
JP2006184849A (ja) * 2004-11-30 2006-07-13 Toppan Printing Co Ltd 反射防止積層体、光学機能性フィルタ、光学表示装置および光学物品

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