WO2015190227A1 - Procédé de fabrication de conducteur transparent - Google Patents

Procédé de fabrication de conducteur transparent Download PDF

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Publication number
WO2015190227A1
WO2015190227A1 PCT/JP2015/064154 JP2015064154W WO2015190227A1 WO 2015190227 A1 WO2015190227 A1 WO 2015190227A1 JP 2015064154 W JP2015064154 W JP 2015064154W WO 2015190227 A1 WO2015190227 A1 WO 2015190227A1
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WIPO (PCT)
Prior art keywords
layer
refractive index
transparent conductor
conductive layer
conductive
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Ceased
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PCT/JP2015/064154
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English (en)
Japanese (ja)
Inventor
健一郎 平田
仁一 粕谷
一成 多田
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; 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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances

Definitions

  • the present invention relates to a method for producing a transparent conductor excellent in light transmittance and having good electrical connection between a connection wiring and a conductive layer.
  • transparent conductors have been used in various devices such as liquid crystal displays, plasma displays, display devices such as inorganic and organic EL (electroluminescence) displays, touch panels, and solar cells.
  • a transparent conductor In a touch panel type display device or the like, wiring including a transparent conductor is disposed on the image display surface of the display element. Therefore, the transparent conductor is required to have high light transmittance.
  • a transparent conductor using ITO (indium tin oxide) having high light transmittance is often used.
  • the Ag layer is made of a film having a high refractive index (for example, niobium oxide (Nb 2 O 5 ), IZO (indium / zinc oxide), ICO (indium / cerium oxide)).
  • a-GIO film made of an amorphous oxide of gallium, indium, oxygen, etc.
  • Patent Document 2 a transparent conductor in which an Ag layer is sandwiched between dielectric layers such as niobium oxide and IZO has not been sufficiently moisture-resistant. As a result, when a transparent conductor is used in a high humidity environment, there is a problem that the Ag layer is easily corroded.
  • a technique for forming a wiring circuit by printing a conductive paste on a substrate is known (see, for example, Patent Documents 3 and 4)
  • a high refractive index layer such as a ZnS-containing layer is laminated on the conductive layer.
  • the high-refractive-index layer is often an insulator or a high-resistance material, and there is a problem that conduction cannot be obtained when forming the connection wiring.
  • the present invention has been made in view of the above problems and situations, and its solution is to provide a method for producing a transparent conductor that has excellent light transmission and good electrical connection between a connection wiring and a conductive layer. It is.
  • the present inventor applied an AC voltage between the conductive layer and the connection wiring after arranging the connection wiring at the surface end of the insulating layer in the process of examining the cause of the problem. As a result, it was found that good conductivity between the conductive layer and the connection wiring can be obtained, and the present invention has been achieved.
  • a method of manufacturing a transparent conductor having at least a conductive layer, an insulating layer, and a connection wiring that conducts to the conductive layer, wherein an AC voltage is applied to the conductive layer after forming the connection wiring on a surface end of the insulating layer.
  • connection wiring is made of at least a silver paste.
  • Schematic sectional view showing an example of the layer structure of a transparent conductor Schematic sectional view showing an example of the layer structure of a patterned transparent conductor
  • the method for producing a transparent conductor according to the present invention is a method for producing a transparent conductor having at least a conductive layer, an insulating layer, and a connection wiring that conducts to the conductive layer, wherein the connection wiring is formed on the surface end of the insulating layer.
  • the conductive layer is electrically connected to the connection wiring through a conduction step in which an alternating voltage is applied between the conductive layer and the connection wiring after the formation of the conductive layer.
  • connection wiring is preferably made of at least a silver paste.
  • the conductive layer is preferably a conductive layer containing silver because high conductivity can be obtained.
  • the conductive layer is sandwiched between two insulating layers containing zinc sulfide because an effect of improving moisture resistance can be obtained.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the method for producing a transparent conductor according to the present invention is a method for producing a transparent conductor having at least a conductive layer, an insulating layer, and a connection wiring that conducts to the conductive layer, wherein the connection wiring is formed on the surface end of the insulating layer.
  • the conductive layer is electrically connected to the connection wiring through a conduction step in which an alternating voltage is applied between the conductive layer and the connection wiring after the formation of the conductive layer.
  • FIGS. 1A to 1C An outline of a process in which the conductive layer according to the present invention conducts to a connection wiring made of a conductive paste is shown in FIGS. 1A to 1C as an example.
  • FIG. 1A is a schematic sectional view showing an example of a layer structure of a transparent conductor.
  • the transparent conductor before the connection wiring is formed on the substrate 1, for example, the first high refractive index layer 2, the conductive layer 3, and zinc sulfide containing zinc sulfide having a high refractive index.
  • the laminated body 10 in which the insulating layer 3 (second high-refractive index layer) containing is laminated is formed.
  • the 1st high refractive index layer 2 is provided in order to make light transmittance high and to improve moisture resistance as a preferable aspect.
  • the conductive layer it is preferable to use silver because high conductivity can be obtained. Further, when silver is used as the conductive layer, an anti-sulfurization layer can be provided in a layer adjacent to the conductive layer to prevent light transmission deterioration due to the formation of silver sulfide. By setting it as such a structure, the laminated body 10 which has high light transmittance can be formed.
  • FIG. 1B is a schematic cross-sectional view showing an example of a layer structure of a patterned transparent conductor.
  • the laminated body 10 may be formed with a conductive region a and an insulating region b by patterning. It is preferable to have a lead-out wiring portion (hereinafter also simply referred to as “lead-out wiring”) drawn from the conduction region a.
  • lead-out wiring hereinafter also simply referred to as “lead-out wiring” drawn from the conduction region a.
  • FIG. 1C is a schematic cross-sectional view showing an example of a transparent conductor coated with a conductive paste.
  • a conductive paste is applied to the surface end portion of the insulating layer of the patterned transparent conductor.
  • This conductive paste has a function of electrically connecting the patterned conductive layer of the transparent conductor and the circuit board as connection wiring.
  • the high refractive index layer is often an insulator or a high resistance, and conduction is formed when the connection wiring is formed. There was a problem that could not be taken.
  • connection wiring conductive paste
  • an excellent voltage can be obtained between the conductive layer and the connection wiring by applying an AC voltage between the conductive layer and the connection wiring.
  • the method for producing a transparent conductor according to the present invention includes at least a film forming process for forming a conductive layer and an insulating layer, a connection wiring forming process on the surface end of the insulating layer after film formation, and then conducting an AC voltage. It includes at least a conduction step applied between the layer and the connection wiring, and may further include other steps such as a patterning step, if necessary.
  • ⁇ Film formation process> In the film forming process, at least a conductive layer and an insulating layer are formed on one surface of the substrate.
  • the insulating layer is preferably a layer having a high refractive index (second high refractive index layer).
  • a 1st high refractive index layer can also be provided between a conductive layer and a board
  • the first high refractive index layer 2, the first antisulfurization layer 5a, the conductive layer 3, and the second antisulfurization are formed on one surface of the substrate 1.
  • a laminate in which the layer 5b and the insulating layer (second high refractive index layer) 4 are formed in this order can be given.
  • the film forming method is not particularly limited as long as it is a process for forming such a laminate.
  • the thin film can be formed by a known method such as vacuum deposition or sputtering. If necessary, the thin film can be formed by a known wet method such as a spin coating method, an ink jet method, or a printing method.
  • connection wiring formation step connection wiring is formed between the surface end portion of the insulating layer located on the surface of the deposited laminate and the circuit board.
  • the connection wiring is provided to enable electrical connection between the conductive layer of the transparent conductor and the circuit board.
  • a conductive layer and a circuit board are disposed as connection wiring on a substrate using a conductive paste or metal. At the time of disposing, it is preferable to dispose the conductive layer and the circuit board using the lead wiring of the patterned laminated body.
  • connection wiring only needs to cover the edge of the surface of the insulating layer obtained by patterning. Specifically, the surface end portion of the insulating layer only needs to be covered by at least about 300 ⁇ m from the end.
  • the end face including the conductive layer is preferably in contact with the conductive paste, but is not necessarily in contact.
  • the surface end of the insulating layer only needs to be covered with the connection wiring.
  • the width of the connection wiring can be changed as necessary, but can be within a range of 10 to 100 ⁇ m.
  • the thickness can be in the range of 5 nm to 50 ⁇ m.
  • connection wiring is provided to enable electrical connection between the conductive layer of the transparent conductor and the circuit board. Specifically, it has a function of electrically connecting the lead wiring and the conductive layer. Therefore, a conductor having a resistance of 10 ⁇ 4 ⁇ / ⁇ or less is preferable. More preferably, the resistance is 10 ⁇ 5 ⁇ / ⁇ or less.
  • connection wiring is preferably a conductive paste or a metal.
  • the connection wiring is preferably made of a conductive paste, and more preferably at least a silver paste, because it can be formed inexpensively without using a large-scale device.
  • the metal wiring When using metal for the connection wiring, the metal wiring may be formed by sputtering or vapor deposition of metal. In this case, since uniform and accurate wiring can be performed, defects can be reduced.
  • metals Cu, Ag, Au, Cr, Ni, Mg, Ti, Mn, Fe, Co, Zn, In, Sn, Ta, W, Os, Pt, Zr, Nb, Mo, Ru, Pd, Bi and these From the viewpoint of conductivity, Cu, Ag, Au, and Pt are preferable, and from the viewpoint of durability, Cr and Ni are preferable.
  • a conductive paste is used for the connection wiring
  • a known method used for a wiring substrate such as inkjet, screen printing, or gravure printing can be appropriately used as a coating method for disposing the conductive paste on the transparent substrate.
  • printing methods such as screen printing and gravure printing are preferable because they are uniformly finished.
  • the conductive paste may contain copper.
  • the silver or copper contained in the conductive paste is preferably contained as spherical particles.
  • the silver particles or the copper particles preferably have a median diameter (D50) of each particle in the range of 0.2 to 0.9 ⁇ m.
  • CA-T30 manufactured by Daiken Chemical Manufacturing and Sales Co., Ltd. TEC-PR030 (paste A) manufactured by InkTec, TEC-PA010 (paste B) manufactured by InkTec, MDot-SLP manufactured by Mitsuboshi Belting Co., Ltd., Toyo Ink ( RA FS039, RA FS045, RA FS088, Nano Dotite XA-3541, XA-9053, LS-450-5, LS-450-7H, LS, manufactured by Asahi Chemical Laboratory -462H-2, LS-453-2, LS-470L-2, LS-460H-1, Pernox K-3100, Pertron K-3107S, K-3111, Taiyo Ink Manufacturing ECM- 100 AF6100 L10, EPH-300TR67004, Asahi Glass Co., Ltd. screen printing copper pace "EPRIMA CU", NAMICS Co., Ltd. XE108-6, it is possible to use a
  • the content of silver particles or copper particles in the conductive paste is preferably in the range of 70 to 97% by mass, and more preferably in the range of 75 to 92% by mass. Within this range, connection wiring having good conductivity can be provided.
  • the conductive paste preferably contains an organic solvent or a resin together with silver particles or copper particles.
  • the organic solvent and resin contained in the conductive paste may be any one that does not have reactivity with silver particles or copper particles.
  • organic solvent contained in the conductive paste a known organic solvent for the conductive paste can be used. Specifically, diethylene glycol mono-n-butyl ether acetate can be preferably used. These may be used individually by 1 type and may use 2 or more types together.
  • the boiling point of the organic solvent is preferably in the range of 120 to 180 ° C. from the viewpoint of the drying rate.
  • a vinyl acrylic resin can be used as the resin contained in the conductive paste.
  • a polyester resin, a vinyl chloride resin, an acrylic resin, a polyester resin, a polyurethane resin, and the like can be given. These may be used singly or in combination of two or more.
  • a conductive paste suitable for printing can be obtained by containing these organic solvents or resins.
  • connection wiring After arranging with the conductive paste, it is preferable to fix the connection wiring by sintering.
  • the resin is likely to be deformed when the temperature is high, so that the sintering temperature can be in the range of 90 to 160 ° C.
  • the sintering time is preferably in the range of 3 to 30 minutes. Sintering can be performed using a known heating furnace.
  • connection wiring is provided at both ends of the conductive layer, by applying an AC voltage between the connection wirings at both ends via the conductive layer, conduction at two locations on both ends of the conductive layer is possible with a single application of AC voltage. It can also be.
  • connection wiring Sufficient conductivity can be obtained by applying an AC voltage between the conductive layer and the connection wiring.
  • conducting means that the resistance is not more than 10 times the theoretical value of the conductive layer.
  • the voltage of the AC voltage to be applied is preferably 100 V (household power source) or less, particularly preferably in the range of 1 to 5 V.
  • the frequency used is preferably in the range of 2 Hz to 20 MHz, more preferably in the range of 10 Hz to 1 MHz, and particularly preferably in the range of 20 to 200 Hz.
  • a frequency of 13.56 MHz is also widely used for industrial applications, and is highly versatile and preferable.
  • the application time depends on the voltage, but is preferably 10 minutes or less, more preferably 1 minute or less, and particularly preferably in the range of 1 to 5 seconds.
  • a commercially available apparatus can be used as appropriate to apply the AC voltage.
  • HIOKI LCR HiTester model number 3522-50 manufactured by Hioki Electric Co., Ltd. can be used.
  • the transparent conductor according to the present invention has at least a conductive layer, an insulating layer, and a connection wiring. These layers are preferably provided on a transparent substrate.
  • the insulating layer is preferably a layer having a high refractive index (second high refractive index layer).
  • a 1st high refractive index layer can also be provided between a conductive layer and a board
  • the first high refractive index layer 2 As a specific example, the first high refractive index layer 2, the first antisulfurization layer 5 a, the conductive layer 3, the second antisulfurization layer 5 b, and the insulating layer (first layer) shown on FIG.
  • Each layer of the transparent conductor according to the present invention in which (2 high refractive index layers) 4 are laminated in this order will be described in detail.
  • the first high-refractive index layer is a layer that adjusts the light transmittance of the conductive region of the transparent conductor, that is, the region where the conductive layer is formed, and is formed at least in the conductive region of the transparent conductor.
  • the first high refractive index layer may be formed in the insulating region of the transparent conductor, but is formed only in the conductive region from the viewpoint of making it difficult to visually recognize the pattern including the conductive region and the insulating region. Is preferred.
  • the first high refractive index layer includes a dielectric material or an oxide semiconductor material having a refractive index higher than that of the substrate described later.
  • the refractive index of light with a wavelength of 570 nm (measurement temperature: 25 ° C.) of the dielectric material or oxide semiconductor material is preferably 0.1 to 1.1 higher than the refractive index of light with a wavelength of 570 nm of the substrate. More preferably, it is larger by 1.0.
  • the specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the first high refractive index layer is preferably greater than 1.5, and is within a range of 1.7 to 2.5. More preferably, it is in the range of 1.8 to 2.5.
  • the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the light transmittance of the conductive region a of the transparent conductor is sufficiently adjusted by the first high refractive index layer.
  • the refractive index of the first high refractive index layer is adjusted by the refractive index of the material included in the first high refractive index layer and the density of the material included in the first high refractive index layer.
  • the dielectric material or oxide semiconductor material contained in the first high refractive index layer may be an insulating material or a conductive material.
  • the dielectric material or oxide semiconductor material can be a metal oxide. Examples of metal oxides are TiO 2 , ITO (indium tin oxide), ZnO, Nb 2 O 5 , ZrO 2 , CeO 2 , Ta 2 O 5 , Ti 3 O 5 , Ti 4 O 7 , Ti 2 O.
  • the first high refractive index layer may contain only one kind of the metal oxide or two or more kinds.
  • the dielectric material or the oxide semiconductor material included in the first high refractive index layer may be ZnS.
  • ZnS When ZnS is contained in the first high refractive index layer, it becomes difficult for moisture to permeate from the substrate side, and corrosion of the conductive layer is suppressed.
  • the first high refractive index layer may contain only ZnS, and may contain other materials together with ZnS.
  • Materials included with ZnS is a metal oxide or SiO 2 or the like, which may be the dielectric material or an oxide semiconductor material, particularly preferably SiO 2.
  • SiO 2 is contained together with ZnS, the first high refractive index layer is likely to be amorphous, and the flexibility of the transparent conductor is likely to be enhanced.
  • the amount of ZnS is in the range of 0.1 to 95 mass% with respect to the total number of moles of the material constituting the first high refractive index layer. It is preferably 50 to 90% by mass, more preferably 60 to 85% by mass.
  • the ratio of ZnS is high, the sputtering rate increases, and the formation rate of the first high refractive index layer increases.
  • the amorphousness of the first high refractive index layer is increased, and cracking of the first high refractive index layer is suppressed.
  • the thickness of the first high refractive index layer is preferably in the range of 15 to 150 nm, more preferably 20 to 80 nm.
  • the thickness of the first high refractive index layer is 15 nm or more, the light transmittance of the conductive region of the transparent conductor is sufficiently adjusted by the first high refractive index layer.
  • the thickness of the first high refractive index layer is 150 nm or less, the light transmittance of the region including the first high refractive index layer is unlikely to decrease.
  • the thickness of the first high refractive index layer is measured with an ellipsometer.
  • the first high refractive index layer may be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, and a thermal CVD method.
  • the first high refractive index layer is preferably a layer formed by electron beam evaporation or sputtering.
  • the electron beam evaporation method in order to increase the film density, it is desirable that there is an assist by an ion assist method (ION Assisted Deposition: IAD).
  • the patterning method is not particularly limited.
  • the first high refractive index layer may be, for example, a layer formed in a pattern by a vapor deposition method by arranging a mask having a desired pattern on the surface to be formed, by a known etching method. It may be a patterned layer.
  • the first antisulfurization layer is provided between the first high refractive index layer and the conductive layer. It is preferable.
  • the first anti-sulfurization layer may be formed also in the insulating region of the transparent conductor, but from the viewpoint of making it difficult to visually recognize the pattern made of the conductive region and the insulating region, it may be formed only in the conductive region. preferable.
  • the first sulfidation preventing layer may be a metal oxide, metal nitride, metal fluoride, or the like, or a layer containing Zn.
  • the first sulfidation preventing layer may contain only one kind or two or more kinds.
  • the metal oxide in the case where the first high refractive index layer, the first antisulfurization layer, and the conductive layer are continuously formed, the metal oxide must be a compound capable of reacting with sulfur or adsorbing sulfur. Is preferred.
  • the reaction product of the metal oxide and sulfur preferably has high visible light permeability.
  • metal oxides 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. , La 2 Ti 2 O 7 , IZO, AZO, GZO, ATO, ICO, Bi 2 O 3 , a-GIO, Ga 2 O 3 , GeO 2 , SiO 2 , Al 2 O 3 , HfO 2 , SiO, MgO, Y 2 O 3 , WO 3, IGZO and the like are included.
  • metal fluorides examples include LaF 3 , BaF 2 , Na 5 Al 3 F 14 , Na 3 AlF 6 , AlF 3 , MgF 2 , CaF 2 , BaF 2 , CeF 3 , NdF 3 , YF 3 and the like. .
  • metal nitride examples include Si 3 N 4 , AlN, and the like.
  • the thickness of the first antisulfurization layer is preferably a thickness capable of protecting the surface of the first high refractive index layer from impact during formation of the conductive layer.
  • ZnS that can be contained in the first high refractive index layer has high affinity with the metal contained in the conductive layer. Therefore, if the thickness of the first antisulfurization layer is very thin and a part of the first high refractive index layer is slightly exposed, the conductive layer grows around the exposed portion, and the conductive layer becomes dense.
  • the first antisulfurization layer is preferably relatively thin, preferably 0.1 to 10 nm, more preferably 0.5 to 5 nm, and further preferably 1 to 3 nm. The thickness of the first antisulfurization layer is measured with an ellipsometer.
  • the first sulfidation preventing layer may be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like.
  • a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like.
  • the first antisulfurization layer is a layer patterned into a desired shape
  • the patterning method is not particularly limited.
  • the first antisulfurization layer may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the surface to be formed, and patterned by a known etching method. It may be a layer formed.
  • the conductive layer is a layer for conducting electricity in the transparent conductor.
  • the conductive layer may be laminated on the entire surface of the substrate, and as shown in FIG. 3, it is patterned into a desired shape according to the intended device application. It may be.
  • the region where the conductive layer is laminated is a region where electricity is conducted (hereinafter also referred to as “conduction region”).
  • a region not including the conductive layer is an insulating region.
  • the pattern composed of the conductive region and the insulating region is appropriately selected according to the use of the transparent conductor.
  • a transparent conductor when applied to an electrostatic touch panel, it may be a pattern including a plurality of conductive regions and line-shaped insulating regions that divide the conductive regions.
  • the metal contained in the conductive layer is not particularly limited as long as it is a highly conductive metal, and can be, for example, silver, copper, gold, platinum, titanium, chromium, or the like.
  • the conductive layer may contain only one kind of these metals or two or more kinds. From the viewpoint of high conductivity, the conductive layer is preferably made of silver or an alloy containing 90 atomic% or more of silver.
  • the metal combined with silver can be zinc, gold, copper, palladium, aluminum, manganese, bismuth, neodymium, molybdenum or the like.
  • the sulfidation resistance of the conductive layer is increased.
  • salt resistance (NaCl) resistance increases.
  • silver and copper are combined, the oxidation resistance increases.
  • moisture resistance improves by containing palladium and copper.
  • the plasmon absorption rate of the conductive layer is preferably 10% or less over the wavelength range of 400 to 800 nm (over the entire range), 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 conductive region a of the transparent conductor is easily colored.
  • the plasmon absorption rate at a wavelength of 400 to 800 nm of the conductive layer is measured by the following procedure.
  • a platinum palladium film is formed to a thickness of 0.1 nm on a glass substrate using a magnetron sputtering apparatus.
  • the average thickness of platinum-palladium is calculated from the film formation rate of the manufacturer's nominal value of the sputtering apparatus. After that, a 20 nm thick metal film is formed by sputtering on the substrate to which platinum palladium is attached.
  • a conductive layer to be measured is formed on the same glass substrate. And about the said conductive layer, light transmittance and light reflectance are measured similarly. The reference data is subtracted from the obtained light absorption rate, and the calculated value is defined as the plasmon absorption rate.
  • the thickness of the conductive layer is preferably 10 nm or less, more preferably 3 to 9 nm, and further preferably 5 to 8 nm.
  • the transparent conductor according to the present invention when the thickness of the conductive layer is 10 nm or less, the original reflection of metal hardly occurs in the conductive layer. Furthermore, when the thickness of the conductive layer is 10 nm or less, the light transmittance of the transparent conductor is easily adjusted by the first high refractive index layer and the second high refractive index layer, and light reflection on the surface of the conductive region is prevented. It is easy to be suppressed.
  • the thickness of the conductive layer is measured with an ellipsometer.
  • the conductive layer may be a layer formed by any formation method, but in order to change the average transmittance of the conductive layer, a layer formed by a sputtering method or a layer formed on an underlayer described later is used. Preferably there is.
  • the sputtering method since a material collides with an object to be formed at a high speed during formation, a dense and smooth layer can be easily obtained, and the light transmittance of the conductive layer is likely to be increased. Further, when the conductive layer is a layer formed by sputtering, the conductive layer is unlikely to corrode even in an environment of high temperature and low humidity.
  • the type of the sputtering method is not particularly limited, and may be an ion beam sputtering method, a magnetron sputtering method, a reactive sputtering method, a bipolar sputtering method, a bias sputtering method, a counter sputtering method, or the like.
  • the conductive layer is particularly preferably a layer formed by a counter sputtering method. That is, when the conductive layer is a layer formed by a counter sputtering method, the conductive layer becomes dense and the surface smoothness is likely to increase. As a result, the surface electrical resistance of the conductive layer becomes lower and the light transmittance is likely to increase.
  • the method for forming the conductive layer is not particularly limited, and may be a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a thermal CVD method.
  • the patterning method is not particularly limited.
  • the conductive layer may be a layer formed by arranging a mask having a desired pattern, or may be a layer patterned by a known etching method.
  • the second high refractive index layer to be described later is a zinc sulfide-containing layer
  • a second antisulfurization layer is formed between the conductive layer and the second high refractive index layer.
  • the second antisulfurization layer may be formed also in the insulating region of the transparent conductor, but from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region and the insulating region, it may be formed only in the conductive region. preferable.
  • the second antisulfurization layer is a layer containing metal oxide, metal nitride, metal fluoride, or the like, or Zn. Only one of these may be included in the second antisulfurization layer, or two or more thereof may be included.
  • the metal oxide, metal nitride, and metal fluoride may be the same as the metal oxide, metal nitride, and metal fluoride contained in the first high refractive index layer.
  • the thickness of the second antisulfurization layer is preferably a thickness capable of protecting the surface of the conductive layer from an impact during the formation of the second high refractive index layer.
  • the metal contained in the conductive layer and the ZnS contained in the second high refractive index layer have high affinity. Therefore, if the thickness of the second antisulfurization layer is very thin and a part of the conductive layer is slightly exposed, the adhesion between the conductive layer or the second antisulfurization layer and the second high refractive index layer is increased. Cheap.
  • the specific thickness of the second antisulfurization layer b is preferably 0.1 to 10 nm, more preferably 0.5 to 5 nm, and further preferably 1 to 3 nm.
  • the thickness of the second antisulfurization layer is measured with an ellipsometer.
  • the second sulfidation preventing layer may be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like.
  • a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like.
  • the second antisulfurization layer is a layer patterned into a desired shape
  • the patterning method is not particularly limited.
  • the second antisulfurization layer may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the surface to be formed, and patterned by a known etching method. It may be a layer formed.
  • the gap is between the first high refractive index layer or the second high refractive index layer and the conductive layer.
  • an antisulfurization layer may be provided, but from the viewpoint of sufficiently increasing the light transmittance of the transparent conductor, each of the first high refractive index layer and the second high refractive index layer and the conductive layer, It is preferable to provide a sulfidation prevention layer.
  • first sulfidation prevention layer and the second sulfidation prevention layer are provided between the first high refractive index layer and the conductive layer and between the conductive layer and the second high refractive index layer, respectively.
  • the insulating layer is preferably a second high refractive index layer in order to increase the light transmittance.
  • the configuration in which the second high-refractive index layer such as a ZnS-containing layer is laminated on the conductive layer is often a problem that the high-refractive index layer is often an insulator or a high-resistance material, and cannot be electrically connected when forming the connection wiring. was there.
  • the present invention has an insulating high refractive index layer such as ZnS, excellent electrical conductivity between the conductive layer and the connection wiring can be obtained.
  • an insulating layer refers to a layer having a resistance value exceeding 10 times that of a conductive layer.
  • it can be preferably applied to a layer having a resistance exceeding 10 ⁇ 4 ⁇ / ⁇ .
  • the second high refractive index layer is a layer for adjusting the light transmittance of the conductive region of the transparent conductor, that is, the region where the conductive layer is formed, and is formed at least in the conductive region of the transparent conductor. Therefore, the second high refractive index layer may be formed in the insulating region of the transparent conductor, but it is formed only in the conductive region from the viewpoint of making it difficult to visually recognize the pattern including the conductive region and the insulating region. Is preferred.
  • the second high refractive index layer preferably contains a dielectric material or an oxide semiconductor material having a refractive index higher than that of the transparent substrate from the viewpoint of light transmittance.
  • the refractive index of light having 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 having a wavelength of 570 nm of the transparent substrate 1, and is preferably 0.4 to 1.0. Larger is more preferable.
  • the specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the second high refractive index layer is preferably larger than 1.5, and is preferably 1.7 to 2.5. Is more preferably 1.8 to 2.5.
  • the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the light transmittance of the conductive region of the transparent conductor is sufficiently adjusted by the second high refractive index layer.
  • the refractive index of the second high refractive index layer is adjusted by the refractive index of the material included in the second high refractive index layer and the density of the material included in the second high refractive index layer.
  • the dielectric material or oxide semiconductor material included in the second high refractive index layer is an insulating material and can be a metal oxide.
  • the metal oxide may be the same as the metal oxide included in the first high refractive index layer.
  • the second high refractive index layer may contain only one kind of the metal oxide, or two or more kinds.
  • the dielectric material or the oxide semiconductor material included in the second high refractive index layer may be ZnS.
  • ZnS When ZnS is contained in the second high refractive index layer, moisture hardly penetrates from the second high refractive index layer side, moisture resistance is improved, and corrosion of the conductive layer is suppressed.
  • both the second high refractive index layer and the first high refractive index layer contain ZnS. That is, the conductive layer is preferably sandwiched between two insulating layers containing ZnS.
  • the second high refractive index layer may contain only ZnS, and may contain other materials together with ZnS.
  • the material included together with ZnS is a metal oxide that can be the dielectric material or the oxide semiconductor material, or SiO 2 , and particularly preferably SiO 2 .
  • SiO 2 is contained together with ZnS, the second high refractive index layer is likely to be amorphous, and the flexibility of the transparent conductor is likely to be enhanced.
  • the amount of ZnS is 0.1% by mass or more and 95% by mass or less with respect to the total number of moles of components constituting the second high refractive index layer. It is preferable that it is 50 mass% or more and 90 mass% or less, More preferably, it is 60 mass% or more and 85 mass% or less.
  • the ratio of ZnS is high, the sputtering rate is increased and the formation rate of the second high refractive index layer is increased.
  • the amount of components other than ZnS increases, the amorphousness of the second high refractive index layer increases, and cracking of the second high refractive index layer is suppressed.
  • the thickness of the second high refractive index layer is preferably 15 to 150 nm, and more preferably 20 to 80 nm.
  • the thickness of the second high refractive index layer is 15 nm or more, the light transmittance of the conductive region of the transparent conductor is sufficiently adjusted by the second high refractive index layer.
  • the thickness of the second high refractive index layer is 150 nm or less, the light transmittance of the region including the second high refractive index layer is unlikely to decrease.
  • the thickness of the second high refractive index layer is measured with an ellipsometer.
  • the method for forming the second high refractive index layer is not particularly limited, and is a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a thermal CVD method. possible. From the viewpoint of lowering the moisture permeability of the second high refractive index layer, the second high refractive index layer is particularly preferably a layer formed by a sputtering method.
  • the patterning method is not particularly limited.
  • the second high refractive index layer may be, for example, a layer formed in a pattern by a vapor deposition method by arranging a mask having a desired pattern on the surface to be formed.
  • the layer patterned by the well-known etching method may be sufficient.
  • the transparent conductor may be provided with an underlayer that becomes a growth nucleus when the conductive layer is formed.
  • the underlayer is a layer formed on the substrate side of the conductive layer and adjacent to the conductive layer, that is, between the first high refractive index layer and the conductive layer, or between the first antisulfurization layer and the conductive layer. It may be a formed layer.
  • the underlayer is preferably formed at least in the conductive region of the transparent conductor, and may be formed in the insulating region of the transparent conductor.
  • the smoothness of the surface of the conductive layer increases even if the thickness of the conductive layer is thin. The reason is as follows.
  • the material of the conductive layer is deposited, for example, on the first high refractive index layer by a general vapor deposition method
  • atoms attached on the first high refractive index layer migrate (move) at the initial stage of formation. Then, atoms gather and form a lump (island structure). And a film grows clinging to this lump. Therefore, in the layer at the initial stage of formation, there is a gap between the lumps and it does not conduct. If a lump further grows from this state, a part of the lump is connected and barely conducted. However, since there is still a gap between the lumps, plasmon absorption occurs. As the formation proceeds further, the lumps are completely connected and plasmon absorption is reduced. However, on the other hand, the intrinsic reflection of the metal occurs and the light transmittance of the layer is reduced.
  • the conductive layer grows with the base layer as a growth nucleus. That is, the material of the conductive layer is difficult to migrate, and the film grows without forming the aforementioned island structure. As a result, a smooth conductive layer can be easily obtained even if the thickness is small.
  • the base layer contains palladium, molybdenum, zinc, germanium, niobium or indium, an alloy of these metals with another metal, an oxide or a sulfide of these metals (for example, ZnS). Is preferred.
  • the underlayer may contain only one kind, or two or more kinds.
  • the amount of palladium, molybdenum, zinc, germanium, niobium or indium contained in the underlayer is preferably 20% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more. If the base layer contains 20% by mass or more of the metal, the affinity between the base layer and the conductive layer increases, and the adhesion between the base layer and the conductive layer tends to increase. It is particularly preferable that the underlayer contains palladium or molybdenum.
  • the metal that forms an alloy with palladium, molybdenum, zinc, germanium, niobium, or indium is not particularly limited, but may be a platinum group other than palladium, gold, cobalt, nickel, titanium, aluminum, chromium, or the like.
  • the thickness of the underlayer is preferably 3 nm or less, more preferably 0.5 nm or less, and even more preferably a monoatomic film.
  • the underlayer can also be a film in which metal atoms are adhered to each other on the substrate.
  • the adhesion amount of the underlayer is 3 nm or less, the underlayer hardly affects the light transmittance and optical admittance of the transparent conductor.
  • the presence or absence of the underlayer is confirmed by the ICP-MS method. Further, the thickness of the underlayer is calculated from the product of the formation speed and the formation time.
  • the underlayer can be a layer formed by sputtering or vapor deposition.
  • the sputtering method include an ion beam sputtering method, a magnetron sputtering method, a reactive sputtering method, a bipolar sputtering method, and a bias sputtering method.
  • the sputtering time for forming the underlayer is appropriately selected according to the desired average thickness and formation rate of the underlayer.
  • the sputter formation rate is preferably 0.1 to 15 ⁇ / second, more preferably 0.1 to 7 ⁇ / second.
  • examples of the vapor deposition method include vacuum vapor deposition method, electron beam vapor deposition method, ion plating method, ion beam vapor deposition method and the like.
  • the deposition time is appropriately selected according to the desired thickness and formation rate of the underlayer.
  • the deposition rate is preferably 0.1 to 15 ⁇ / second, more preferably 0.1 to 7 ⁇ / second.
  • the underlayer may be, for example, a layer formed in a pattern by a vapor deposition method by placing a mask having a desired pattern on the surface to be formed, or a layer patterned by a known etching method It may be.
  • the substrate which the transparent conductor has can be the same as the transparent substrate of various display devices.
  • the substrate may be a glass substrate, a cellulose ester resin (for example, triacetyl cellulose, diacetyl cellulose, acetylpropionyl cellulose, etc.), a polycarbonate resin (for example, Panlite, Multilon (both manufactured by Teijin Limited)), a cycloolefin resin (for example, Zeonor ( Nippon Zeon Co., Ltd., Arton (manufactured by JSR), Appel (manufactured by Mitsui Chemicals), acrylic resin (eg, polymethyl methacrylate, "Acrylite (manufactured by Mitsubishi Rayon Co., Ltd.), Sumipex (manufactured by Sumitomo Chemical Co., Ltd.)), polyimide , Phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyester resin (eg, polyethylene ethylene ethylene
  • the substrate is a glass substrate, or cellulose ester resin, polycarbonate resin, polyester resin (especially polyethylene terephthalate), triacetyl cellulose, cycloolefin resin, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyether.
  • a film made of sulfone, ABS / AS resin, MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), or styrene block copolymer resin is preferable.
  • the substrate 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 85% or more. Is more preferable. When the average light transmittance of the substrate is 70% or more, the light transmittance of the transparent conductor is likely to increase. Further, the average absorptance of light having a wavelength of 450 to 800 nm of the substrate is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.
  • the average transmittance is measured by making light incident from an angle inclined by 5 ° with respect to the normal of the surface of the substrate.
  • Average transmittance and average reflectance are measured with a spectrophotometer.
  • the refractive index of light having a wavelength of 570 nm of the substrate is preferably in the range of 1.40 to 1.95, more preferably 1.45 to 1.75, and still more preferably 1.45 to 1.70. Within range.
  • the refractive index of the substrate is usually determined by the material of the substrate.
  • the refractive index of the substrate is measured with an ellipsometer.
  • the haze value of the substrate 1 is preferably 0.01 to 2.5%, more preferably 0.1 to 1.2%. When the haze value of the substrate is 2.5% or less, the haze value of the transparent conductor is suppressed. The haze value is measured with a haze meter.
  • the thickness of the substrate 1 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 substrate is 1 ⁇ m or more, the strength of the substrate is increased, and it is difficult to crack or tear the first high refractive index layer.
  • the thickness of the substrate is 20 mm or less, the flexibility of the transparent conductor is sufficient.
  • the thickness of the apparatus using a transparent conductor can be reduced.
  • the apparatus using a transparent conductor can also be reduced in weight.
  • the average transmittance of light with a wavelength of 450 to 800 nm of the transparent conductor according to the present invention is preferably 83% or more, more preferably 85% or more, and still more preferably in both the conduction region and the insulation region. It is 88% or more.
  • the transparent conductor can be applied to applications requiring high transparency to visible light.
  • the average transmittance of light with a wavelength of 400 to 1000 nm of the transparent conductor is preferably 80% or more, more preferably 83% or more, and still more preferably 85% or more in both the conductive region and the insulating region. is there.
  • the transparent conductor can also be applied to applications requiring transparency with respect to light in a wide wavelength range, for example, solar cells.
  • the average absorptance of light having a wavelength of 450 to 800 nm of the transparent conductor is preferably 10% or less, more preferably 8% or less, and even more preferably 7% in both the conductive region and the insulating region. It is as follows. Further, the maximum value of the light absorptance of the transparent conductor having a wavelength of 450 to 800 nm is preferably 15% or less, more preferably 10% or less, and even more preferably in both the conduction region and the insulation region. 9% or less.
  • the average reflectance of light with a wavelength of 500 to 700 nm of the transparent conductor is preferably 20% or less, more preferably 15% or less, and even more preferably 10% in both the conductive region and the insulating region. % Or less.
  • the average transmittance, average absorptance, and average reflectance are preferably the average transmittance, average absorptance, and average reflectance under the usage environment of the transparent conductor.
  • the transparent conductor when the transparent conductor is used by being bonded to an organic resin, it is preferable to prepare a layer made of the organic resin on the transparent conductor and measure the average transmittance and the average reflectance.
  • the transparent conductor 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 transmittance and reflectance can be measured with a spectrophotometer by allowing measurement light to enter from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent conductor.
  • the absorptance is calculated from a calculation formula of 100 ⁇ (transmittance + reflectance).
  • the transparent conductor has a conduction region and an insulation region
  • the reflectance of the conduction region and the reflectance of the insulation region approximate.
  • the difference ⁇ R between the luminous reflectance of the conductive region and the luminous reflectance of the insulating region is preferably 5% or less, more preferably 3% or less, and still more preferably 0.8. It is 5% or less, and particularly preferably 0.3% or less.
  • the luminous reflectance of the conductive region and the insulating region is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less.
  • the luminous reflectance is a Y value measured by a spectrocolorimeter (CM-5; manufactured by Konica Minolta, Inc.).
  • the a * value and the b * value in the L * a * b * color system are preferably within ⁇ 30, more preferably in any region. Is within ⁇ 5, more preferably within ⁇ 3.0, and particularly preferably the a * value is in the range of ⁇ 0.5 to 0 and the b * value is in the range of 0 to 2.0. L * a * b * if a * and b * values is within ⁇ 30 in the color system, any region of the conductive region and an insulating region b is also colorless and transparent observed.
  • the a * value and b * value in the L * a * b * color system are measured with a spectrophotometer.
  • the surface electric resistance of the conductive region of the transparent conductor is preferably 50 ⁇ / ⁇ or less, more preferably 30 ⁇ / ⁇ or less.
  • a transparent conductor having a surface electric resistance value of 50 ⁇ / ⁇ or less in the conduction region can be applied to a transparent conductive panel for a capacitive touch panel.
  • the surface electrical resistance value of the conduction region is adjusted by the thickness of the conductive layer and the like.
  • the surface electrical resistance value of the conduction region is measured in accordance with, for example, JIS K7194-1994, 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 can be applied to touch sensors for various types of touch panels (hereinafter also referred to as “touch sensor electrode portions”). For example, it can be used in a surface capacitive touch panel, a projected capacitive touch panel, a resistive touch panel, and the like.
  • the layer structure of the touch sensor unit is a bonding method in which two transparent conductors are bonded as a transparent electrode, a method in which a transparent conductor is provided as a transparent electrode on both surfaces of a single substrate, a single-sided jumper or a through-hole method Or it is preferable that it is either a one area layer system.
  • the projected capacitive touch sensor is preferably AC driven rather than DC driven, and more preferably a drive method that requires less time to apply voltage to the electrodes.
  • FIG. 3 is a schematic view showing the entire patterned transparent conductor.
  • the transparent conductor according to the present invention is applied to a touch sensor, for example, as shown in FIG. 3, the transparent conductor has a pattern including a plurality of conductive regions a and a line-shaped insulating region b separating the conductive regions a. It can be molded and used as an electrode.
  • the touch panel 200 can be manufactured by further bonding the display panel 16, the transparent conductor 100, and the flexible substrate 8 having the wiring pattern 14 with the adhesive 15 (FIG. 4). reference).
  • the transparent conductive layer is electrically connected from the electrode 7 provided on the circuit board to the wiring pattern 14 by the connection wiring 6.
  • a region surrounded by a broken line shown in FIG. 3 functions as the touch sensor unit 13.
  • Method for forming transparent conductor having electrode pattern A method for forming a pattern composed of a conductive region a and an insulating region b as shown in FIG. 3 will be described for the transparent conductor according to the present invention.
  • the first high-refractive index layer 2, the conductive layer 3, and the insulating layer (second high-refractive index layer) 4 are formed on the substrate 1 by the above method. After being laminated in order, it is preferable to pattern the transparent conductor 100 into a predetermined shape to form a metal electrode.
  • an electrode pattern as shown in FIG. 3 is preferably formed by photolithography using an etching solution.
  • the line width of the electrode to be formed is preferably 50 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • the photolithographic method applied to the present invention includes resist coating such as curable resin, preheating, exposure, development (removal of uncured resin), rinsing, etching treatment with an etching solution, and resist stripping.
  • the silver thin film layer can be processed into a pattern as shown in FIG. 3, for example, and the shape of the pattern can be changed as appropriate.
  • a conventionally known general photolithography method can be used as appropriate.
  • the resist either positive or negative resist can be used.
  • preheating or prebaking can be performed as necessary.
  • a pattern mask having a predetermined pattern may be disposed, and light having a wavelength suitable for the resist used, generally ultraviolet rays, electron beams, or the like may be irradiated thereon.
  • development is performed with a developer suitable for the resist used.
  • the resist pattern is formed by stopping the development with a rinse solution such as water and washing.
  • the formed resist pattern is pretreated or post-baked as necessary, and then is etched with an etching solution containing an organic solvent to dissolve the intermediate layer in a region not protected by the resist and to form a silver thin film electrode Remove. After etching, the remaining resist is peeled to obtain a transparent electrode having a predetermined pattern.
  • the applied photolithography method is a method generally recognized by those skilled in the art, and a specific application mode can be easily selected by a person skilled in the art according to a predetermined purpose.
  • a resist film composed of a photosensitive resin composition or the like is uniformly coated on the laminate.
  • a photosensitive resin composition a negative photosensitive resin composition or a positive photosensitive resin composition can be used.
  • a coating method it is applied on a laminate by a known method such as micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, etc., and a heating device such as a hot plate or oven. Can be pre-baked. Pre-baking can be performed, for example, using a hot plate or the like within a range of 50 to 150 ° C. for 30 seconds to 30 minutes.
  • the exposure step through a mask manufactured by predetermined electrode patterns, a stepper, a mirror projection mask aligner (MPA), using an exposure apparatus, such as a parallel light mask aligner, 10 ⁇ 4000J / m 2 approximately (wavelength 365nm
  • An exposure apparatus such as a parallel light mask aligner, 10 ⁇ 4000J / m 2 approximately (wavelength 365nm
  • the resist film to be removed in the next step is irradiated with light in terms of exposure amount.
  • the exposure light source is not limited, and ultraviolet rays, electron beams, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.
  • the exposed transparent conductor is immersed in a developer to dissolve the resist film in the region irradiated with light.
  • the developing method it is preferable to immerse in the developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle.
  • a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include aqueous solutions containing one or more quaternary ammonium salts such as side and choline.
  • etching solution a solution containing an inorganic acid or an organic acid is preferable, and oxalic acid, hydrochloric acid, acetic acid, and phosphoric acid can be mentioned, and oxalic acid, acetic acid, and phosphoric acid are particularly preferable.
  • a laminate having a resist film is immersed in an etching solution containing an organic acid or the like, and the laminate of the insulating region b not protected by the resist film is dissolved and protected by the resist film.
  • region a is formed as a predetermined electrode pattern.
  • a resist film remover for example, N-300 manufactured by Nagase ChemteX Corporation, and the resist film is removed to produce a laminate having an electrode pattern.
  • the image display device used for the touch sensor according to the present invention is not particularly limited, and a liquid crystal display device or an organic EL device that is usually used for a small electronic terminal can be used.
  • Transparent conductors include various types of displays such as liquid crystal, plasma, organic electroluminescence, field emission, touch panel, mobile phone, electronic paper, various solar cells, various optoelectronic device substrates such as various electroluminescence dimming elements, etc. Can be preferably used. In particular, it can be preferably applied to electrodes for touch panels.
  • conductive layer (Ag) As a vacuum sputtering apparatus, a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., Ltd. was used, and Ar was 20 sccm, sputtering pressure 0.5 Pa, room temperature, target-side power 150 W, film formation rate 14 ⁇ / sec. .56 MHz). The target-substrate distance was 90 mm. The layer thickness of the Ag layer was 7 nm.
  • the target (ZnS—SiO 2 fired body) was radio frequency (RF) sputtered (frequency) at Ar 20 sccm, O 2 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, and deposition rate 3.8 ⁇ / sec. 13.56 MHz).
  • RF radio frequency
  • the target-substrate distance was 90 mm.
  • the layer thickness was 40 nm.
  • the volume ratio of ZnS to SiO 2 in the second high refractive index layer was measured using X-ray photoelectron spectroscopy (XPS). As a result, the volume ratio of ZnS to SiO 2 was 80:20. It was confirmed that.
  • a resist layer is formed in a pattern by a photolithography method, and a conductive layer and an insulating layer (second high refractive index layer) are separated from a plurality of conductive regions by using an etchant, and in a line shape that divides this Etching was performed in a pattern including the insulating region.
  • the plurality of conductive regions are arranged on the connection terminals 11 via the lead wires 12 respectively.
  • etching solution “mixed liquid SEA-5” (phosphoric acid: 55 mass%, acetic acid: 30 mass%, water and other components: 15 mass%) manufactured by Kanto Chemical Co., Ltd. was used. Only the substrate was included in the insulating region. The width of the line-shaped insulating region was 16 ⁇ m.
  • the transparent conductor 1 was produced through the following conduction process. A specific manufacturing method will be described.
  • ⁇ Conduction process> For each connection wiring, a voltage of 3V and a frequency are applied to the connection wiring portion where only one conductive paste is applied and to the connection wiring portion where only the other conductive paste is applied via a laminate (conductive layer). An AC voltage of 100 Hz was applied for 3 seconds. The application of the AC voltage was performed using HIOKI LCR HiTester (manufactured by Hioki Electric Co., Ltd., model number 3522-50). Thus, the transparent conductor 1 was produced.
  • ⁇ substrate ⁇ Film PET film with clear hard coat manufactured by Kimoto Co., Ltd. Glass: BK7 (thickness 2 mm) manufactured by Yamanaka Hutech Co., Ltd.
  • [Formation of first high refractive index layer] (Formation of ZnS layer)
  • a vacuum sputtering apparatus a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., Ltd. was used.
  • the fired body was radio frequency (RF) sputtered (frequency 13.56 MHz).
  • the target-substrate distance was 90 mm.
  • the layer thickness was 40 nm.
  • a magnetron sputtering apparatus As a vacuum sputtering apparatus, a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., Ltd. is used. Ar (20 Zn), Ar 20 sccm, O 2 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, deposition rate 3.8 ⁇ / sec. the SiO 2 sintered body) was radio frequency (RF) sputtering (frequency 13.56 MHz). The target-substrate distance was 90 mm. The layer thickness was 40 nm.
  • RF radio frequency
  • the volume ratio of ZnS to SiO 2 in the first high refractive index layer was measured using X-ray photoelectron spectroscopy (XPS). As a result, the volume ratio of ZnS to SiO 2 was 80:20. It was confirmed that.
  • ZnS-GZO represents GZO (ZnO containing 10 mass% Ga) and further containing 4 at% ZnS.
  • Ar 20 sccm, O 2 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.07 nm / second, layer thickness 40 nm, and composition ratio GZO (gallium / zinc oxide) and ZnS were radio-frequency (RF) sputtered (frequency 13.56 MHz) so as to achieve the above.
  • the target-substrate distance was 86 mm.
  • ZnO layer As a vacuum sputtering apparatus, a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., Ltd. is used. ArO 20 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, film formation rate 1.1 ⁇ / sec. 13.56 MHz). The target-substrate distance was 90 mm. The thickness of the ZnO layer was 3 nm.
  • ZTO layer As a vacuum sputtering apparatus, a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., Ltd. was used, and ZTO was radio frequency (RF) sputtered with Ar 20 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, film formation rate 1.1 ⁇ ⁇ ⁇ / sec ( (Frequency 13.56 MHz). The target-substrate distance was 90 mm. The layer thickness of the ZTO layer was 3 nm.
  • RF radio frequency
  • the formation of the ZnS layer, the TiO 2 layer, and the ZnS-GZO layer were performed in the same manner as described in the formation of the first high refractive index layer.
  • the conductive paste was used in the same manner as the connection wiring forming step and the sintering step in the production of the transparent conductor 1.
  • the conductive paste used in the production of the transparent conductor 1 is shown in Tables 1 and 2 as * 1.
  • the following three types were used as other conductive pastes. They are described as * 2, * 3, and * 4, respectively.
  • the sintering time and temperature were changed as follows.
  • Evaporated Cu wiring 6 Sputtered Cu wiring 7: Evaporated Cr wiring (Formation of evaporated Cu wiring)
  • Masking was performed with a SUS plate having a thickness of 0.1 mm other than the portion to be connected and wiring formed with a pattern hole, and Cu was deposited using a vapor deposition machine BMC-800T (manufactured by Syncron Co., Ltd.). Vapor deposition was performed by resistance heating using a tungsten boat, and 50 nm deposition was performed at a current value of 200 A at a rate of 10 ⁇ / sec.
  • EAGLE XG thinness 7 mm ⁇ length 30 mm ⁇ width 30 mm
  • the measurement light is incident on the conduction region from an angle inclined by 5 ° with respect to the normal of the surface of the alkali-free glass substrate, and the light transmittance is measured by Hitachi High-Technologies Corporation: Spectrophotometer U4100. And the reflectance was measured.
  • the transmittance is measured in consideration of the value obtained by subtracting the reflection (4%) 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 (4%).
  • a value obtained by adding 8% to the value was defined as each average transmittance of the transparent conductor. Based on the above measured values, the following ranking was performed.
  • Measurement was performed by a two-terminal method using a CDM-2000D manufactured by Custom. Specifically, it was confirmed that the connection terminals 11a and 11b shown in FIG. 3 among the plurality of connection terminals are connected by applying CDM-2000D manufactured by Custom Co., Ltd. This was performed for all connection wirings.
  • All of the 14 connection terminals 11 of the 10 electrode patterns in FIG. 3 are electrically connected and are 70% or more and less than 90%. Less than 70% of all the 14 connection terminals 11 of the 10 electrode patterns in FIG. 3 are electrically conductive
  • the resistance value of the insulating layer was measured separately and confirmed to be a value exceeding 10 times the theoretical value of the conductive layer.
  • the transparent conductor produced by the production method of the present invention was excellent in light transmittance and conductivity, and was useful as an electrode for a touch panel.
  • Example 2 In the production of the transparent conductor 13 of Example 1, the transparent conductors were respectively produced in the same manner as the transparent conductor 13 by changing the kind of the conductive paste, the sintering temperature, and the sintering time as follows.
  • each of the produced transparent conductors was evaluated for light transmittance, conductivity, and moisture resistance. As a result, good results similar to those of the transparent conductor 13 were obtained.
  • the transparent conductor produced by the method for producing a transparent conductor of the present invention is excellent in light transmittance, and has good conductivity between the connection wiring and the conductive layer, and is a liquid crystal display, plasma display, inorganic and organic EL (electroluminescence).
  • the present invention can be preferably applied to various devices such as a display device such as a display, a touch panel, and a solar cell.

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Abstract

La présente invention aborde le problème de mise en œuvre d'un procédé de fabrication d'un conducteur transparent, lequel présente une excellente transmissivité de lumière, et une excellente conductivité entre un câblage de connexion et une couche conductrice. L'invention concerne un procédé de fabrication d'un conducteur transparent qui comporte au moins une couche conductrice, une couche isolante, et du câblage de connexion électriquement connecté à la couche conductrice. Le procédé est caractérisé par la connexion électrique de la couche conductrice et du câblage de connexion entre eux au moyen d'une étape de connexion selon laquelle le câblage de connexion est formé sur une section d'extrémité de surface de la couche isolante, puis une tension en courant alternatif est appliquée entre la couche conductrice et le câblage de connexion.
PCT/JP2015/064154 2014-06-12 2015-05-18 Procédé de fabrication de conducteur transparent Ceased WO2015190227A1 (fr)

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CN102677012A (zh) * 2012-05-18 2012-09-19 中国科学院上海光学精密机械研究所 多层透明导电薄膜的制备方法

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CN102677012A (zh) * 2012-05-18 2012-09-19 中国科学院上海光学精密机械研究所 多层透明导电薄膜的制备方法

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