WO2017131183A1 - Film conducteur transparent multicouche, film de câblage multicouche et procédé de fabrication de film de câblage multicouche - Google Patents

Film conducteur transparent multicouche, film de câblage multicouche et procédé de fabrication de film de câblage multicouche Download PDF

Info

Publication number
WO2017131183A1
WO2017131183A1 PCT/JP2017/002998 JP2017002998W WO2017131183A1 WO 2017131183 A1 WO2017131183 A1 WO 2017131183A1 JP 2017002998 W JP2017002998 W JP 2017002998W WO 2017131183 A1 WO2017131183 A1 WO 2017131183A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
transparent conductive
laminated
atomic
conductive oxide
Prior art date
Application number
PCT/JP2017/002998
Other languages
English (en)
Japanese (ja)
Inventor
弘実 中澤
石井　博
悠人 歳森
齋藤　淳
Original Assignee
三菱マテリアル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017003349A external-priority patent/JP6870332B2/ja
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Publication of WO2017131183A1 publication Critical patent/WO2017131183A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • 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
    • 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

Definitions

  • the present invention relates to a laminated transparent conductive film that can be used as a transparent electrode film such as a display or a touch panel, a laminated wiring film comprising the laminated transparent conductive film, and a method for producing the laminated wiring film.
  • a transparent conductive film as shown in, for example, Patent Documents 1-4 is provided as a transparent electrode film.
  • This transparent conductive film is required to have a high light transmittance in the visible light region and a low electrical resistance.
  • Patent Document 1 an ITO film made of ITO (In 2 O 3 + Sn), which is a kind of transparent conductive oxide, is used as the transparent conductive film.
  • ITO film the electrical resistance is lowered.
  • the transmittance in the visible light region is lowered. Therefore, it is difficult to achieve both high transmittance and low electrical resistance.
  • Patent Document 2 a metal mesh material such as Cu is used, but in order to reduce the electrical resistance in this metal mesh material, it is necessary to widen the width of the metal portion, and the transmittance is also low. There was a problem of being lowered. In addition, since the metal mesh material may be visually recognized due to light reflection, it is necessary to form a blackened film or the like on the surface of the metal mesh material.
  • Patent Documents 3 and 4 propose a laminated transparent conductive film in which an Ag film and a transparent conductive oxide film are laminated.
  • this laminated transparent conductive film since the conductivity is ensured by the Ag film, it is not necessary to form a thick transparent conductive oxide film in order to reduce the electrical resistance, and a relatively high transmittance can be obtained. It becomes possible.
  • Japanese Unexamined Patent Publication No. 2008-310550 A) Japanese Unexamined Patent Publication No. 2006-344163 (A) Japanese Unexamined Patent Publication No. Sho 63-110507 (A) Japanese Laid-Open Patent Publication No. 09-232278 (A)
  • the barrier property against moisture of the transparent conductive oxide film is low, moisture reaches the Ag film in a high humidity environment, Ag aggregation is promoted in the Ag film, and the transmittance and conductivity are reduced. There was a risk of it.
  • the above-described laminated transparent conductive film it is necessary to form a wiring pattern on the laminated transparent conductive film. In this case, after the resist film is formed and the wiring pattern is formed, the resist film is removed. When removing the resist film, an alkaline resist removing solution is used. However, in the conventional laminated transparent conductive film, the alkali resistance is insufficient, and the characteristics of the laminated transparent conductive film are removed when removing the resist film. There has been a problem of deterioration.
  • the present invention has been made in view of the circumstances described above, and has a sufficiently high transmittance, a sufficiently low electrical resistance, and a laminated transparent conductive film excellent in environmental resistance and alkali resistance. It is an object of the present invention to provide a laminated wiring film made of a conductive film and a method for producing the laminated wiring film.
  • a laminated transparent conductive film according to one embodiment of the present invention includes an Ag film made of Ag or an Ag alloy, and both surfaces of the Ag film.
  • the transparent conductive oxide film is made of an oxide containing Zn, Ga, Y, and Sn.
  • the transparent conductive oxide film made of an oxide containing Zn, Ga, Y and Sn is formed on both surfaces of the Ag film.
  • Ag wettability of the Ag film is improved, and Ag aggregation in the Ag film can be suppressed even when the Ag film is formed thin.
  • the above-mentioned transparent conductive oxide film is excellent in environmental resistance (durability in a high-temperature and high-humidity environment), even when used in a high-humidity environment, The formed transparent conductive oxide film can suppress the intrusion of moisture into the Ag film and suppress the aggregation of Ag.
  • a transparent conductive oxide film having a sufficiently high transmittance and a sufficiently low electric resistance.
  • an acidic mixed solution containing phosphoric acid and acetic acid is used as an etchant, the difference in etching rate between the Ag film and the transparent conductive oxide film is small, and the accuracy can be obtained even when the laminated transparent conductive film is collectively etched.
  • a wiring pattern can be formed well.
  • this transparent conductive oxide film has high alkali resistance, even when the resist film is removed using an alkaline resist removing solution when forming a wiring pattern, the deterioration of the characteristics of the laminated transparent conductive film is suppressed. Can do.
  • the atomic ratio of all metal elements contained in the transparent conductive oxide film is Ga: 0.9 atomic% or more and 26.1 atomic% or less, Y; It is preferable that 2 atomic% or more and 9.5 atomic% or less, Sn; 0.1 atomic% or more and 4.7 atomic% or less, and the remaining Zn.
  • the Ga content in all the metal elements contained in the transparent conductive oxide film is in the range of 0.9 atomic% or more and 26.1 atomic% or less, an increase in electrical resistance is suppressed. Can do.
  • the alkali resistance can be improved while suppressing an increase in electrical resistance.
  • the Sn content is in the range of 0.1 atomic% or more and 4.7 atomic% or less, it is possible to improve environmental resistance while suppressing an increase in electrical resistance.
  • the Ag film includes Cu, Sn, Sb, Ti, Mg, Zn, Ge, In, Al, Ga, Pd, Au, Pt, Bi, Mn, Sc, and Y. Nd, Sm, Eu, Gd, Tb, Er, containing a total of 0.2 atomic percent or more and 10.0 atomic percent or less, and the balance is an Ag alloy composed of Ag and inevitable impurities It is preferable to be configured.
  • the thickness of the Ag film is preferably 10 nm or less.
  • the transmittance can be improved.
  • the transparent conductive oxide film described above is formed on both sides of the Ag film, even if the thickness of the Ag film is 10 nm or less, the Ag film does not aggregate and becomes a continuous film. it can.
  • the average transmittance in the visible light region having a wavelength of 400 to 800 nm is 85% or more, and the sheet resistance value is 10 ⁇ / sq. It is preferable that it is (square) or less. In this case, the average transmittance in the visible light region is 85% or more, and the sheet resistance value is 10 ⁇ / sq. Therefore, it has a sufficiently high transmittance and a sufficiently low electric resistance, and can be used as a miniaturized transparent electrode film or transparent wiring film.
  • a multilayer wiring film according to another aspect of the present invention (hereinafter referred to as “laminated wiring film of the present invention”) is formed of the above-described laminated transparent conductive film and has a wiring pattern. According to the laminated wiring film of the present invention, since it is composed of the above-described laminated transparent conductive film, it has low electrical resistance and high transmittance.
  • a method for manufacturing a laminated wiring film according to another aspect of the present invention is the above-described method for manufacturing a laminated wiring film, wherein A laminated transparent conductive film forming step for forming the laminated transparent conductive film including the Ag film and the transparent conductive oxide film, and a resist film for forming a wiring pattern resist film on the laminated transparent conductive film An etching process for performing etching in a batch using an acidic mixed solution containing phosphoric acid and acetic acid as an etchant, and an alkaline process after etching. And a resist film removing step of removing the resist film with a resist removing solution.
  • the difference in etching rate between the Ag film and the transparent conductive oxide film is small. Even if this laminated transparent conductive film is etched at once, the occurrence of overetching OE of the Ag film, the residue R of the transparent conductive oxide film, and the like can be suppressed, and the wiring pattern can be formed with high accuracy.
  • the alkali resistance of the transparent conductive oxide film is improved by adding Y, even if the resist film is removed using an alkaline resist removing solution in the resist film removing step, the characteristics of the laminated wiring film are deteriorated. Can be suppressed.
  • the manufacturing method of the laminated wiring film of the present invention is a manufacturing method of the above-described laminated wiring film, wherein a resist film forming step of forming a resist film having a reverse pattern of the wiring pattern on the film forming surface of the substrate; A laminated transparent conductive film forming step of forming the laminated transparent conductive film including the Ag film and the transparent conductive oxide film on a film forming surface of the base material on which the resist film is formed; and the resist film And a resist film removing step to be removed.
  • a resist film is formed in a reverse pattern of a wiring pattern on the film forming surface of the base material, and the layered film is formed on the film forming surface of the base material on which the resist film is formed.
  • a transparent conductive film is formed.
  • the alkali resistance of the transparent conductive oxide film is improved by adding Y, even if the resist film is removed using an alkaline resist removing solution in the resist film removing step, the characteristics of the laminated wiring film are deteriorated. Can be suppressed.
  • the laminated transparent conductive film of the present invention having sufficiently high transmittance, sufficiently low electrical resistance, excellent environmental resistance and alkali resistance, and laminated wiring comprising the laminated transparent conductive film It is possible to provide a method for manufacturing a film and a laminated wiring film.
  • the laminated transparent conductive film 10 in the present embodiment is used as a transparent electrode film of various displays and touch panels, and is particularly used in a capacitive type touch panel of tablet size or larger.
  • FIG. 1 shows a laminated transparent conductive film 10 according to this embodiment.
  • the laminated transparent conductive film 10 includes, for example, a first transparent conductive oxide film 11 formed on one surface of the substrate 20 as an underlayer, and an Ag film 12 formed on the first transparent conductive oxide film 11. And a second transparent conductive oxide film 13 formed on the Ag film 12.
  • substrate 20 a glass substrate, a resin film, etc. can be used, for example.
  • the laminated transparent conductive film 10 has an average transmittance of 85% or more in the visible light region having a wavelength of 400 to 800 nm and a sheet resistance value of 10 ⁇ / sq. It is as follows.
  • the average transmittance of the laminated transparent conductive film 10 in the visible light region with a wavelength of 400 to 800 nm is preferably 85% or more, and more preferably 86% or more.
  • the sheet resistance value of the laminated transparent conductive film 10 is 10 ⁇ / sq. Or less, preferably 5 ⁇ / sq. More preferably, it is as follows.
  • the Ag film 12 is made of Ag or an Ag alloy.
  • As Ag or an Ag alloy constituting the Ag film 12 pure Ag having a purity of 99.9% by mass or more, or Cu, Sn, Sb, Zn, Ge, In, Al, Ga, Ti, Mg, Pd, Au , Pt, Bi, Mn, Sc, Y, Nd, Sm, Eu, Gd, Tb, and an Ag alloy containing an additive element such as Er may be used.
  • the content of the additive element is desirably limited to 10.0 atomic% or less from the viewpoint of suppressing an increase in the absorptivity (decrease in transmittance) of the Ag film 12 and an increase in electrical resistance. More preferably, it is at most atomic%.
  • Nd, Sm, Eu, Gd, Tb, and Er are elements that have an effect of improving the wettability of the Ag film 12 with respect to the first transparent conductive oxide film 11, and are obtained when the Ag film 12 is formed thin. Also, Ag aggregation can be suppressed.
  • the transmittance of the Ag film 12 may decrease and the resistance value may increase.
  • the total content of one or more of Sc, Y, Nd, Sm, Eu, Gd, Tb, and Er is defined within a range of 0.2 atomic% to 10.0 atomic%.
  • Cu, Sn, Sb, Zn, Ge, In, Al, Ga, Ti, Mg, Pd, Au, Pt, Ag in the Ag alloy constituting the Ag film 12 are used. It is preferable that the lower limit of the total content of one or more of Bi, Mn, Sc, Y, Nd, Sm, Eu, Gd, Tb, and Er is 0.5 atomic% or more.
  • the upper limit of the total content of one kind or two or more kinds is 2.0 atomic% or less.
  • the Ag alloy constituting the Ag film 12 preferably contains at least one or more of Cu, Sn, and Sb among the above-described additive elements.
  • the content of at least one or more of Cu, Sn, and Sb is preferably in the range of 0.2 atomic% or more and 2.0 atomic% or less.
  • the first transparent conductive oxide film 11 and the second transparent conductive oxide film 13 are made of an oxide containing Zn, Ga, Y, and Sn, that is, Zn, Ga, Y, and Sn. Is supposed to be added.
  • the first transparent conductive oxide film 11 and the second transparent conductive oxide film 13 are configured such that the atomic ratio of Ga, Y, and Sn in all metal elements contained in each transparent conductive oxide film is Ga. 0.9 atom% or more and 26.1 atom% or less, Y: 0.2 atom% or more and 9.5 atom% or less, Sn: 0.1 atom% or more and 4.7 atom% or less.
  • the 1st transparent conductive oxide film 11 and the 2nd transparent conductive oxide film 13 do not need to be the same composition, and should just be set to the range of the above-mentioned composition.
  • the Ag content in the Ag film 12 is increased. Aggregation can be suppressed, and an increase in electrical resistance in the laminated transparent conductive film 10 can be suppressed.
  • the Ga content is 26.1 atomic% or less, an increase in electrical resistance in the first transparent conductive oxide film 11 and the second transparent conductive oxide film 13 can be suppressed.
  • the lower limit of the Ga content is preferably 0.9 atomic% or more, and more preferably 2.0 atomic% or more.
  • the upper limit of the Ga content should be 26.1 atomic% or less. Preferably, it is 20.0 atomic% or less.
  • the first transparent conductive oxide film is formed by setting the content of Y in all metal elements contained in the first transparent conductive oxide film 11 and the second transparent conductive oxide film 13 to 0.2 atomic% or more. 11 and the alkali resistance of the second transparent conductive oxide film 13 can be improved. On the other hand, by setting the Y content to 9.5 atomic% or less, an increase in electrical resistance in the first transparent conductive oxide film 11 and the second transparent conductive oxide film 13 can be suppressed.
  • the lower limit of the Y content is preferably 0.2 atomic% or more, More preferably, it is 1.0 atomic% or more.
  • the upper limit of the Y content should be 9.5 atomic% or less. Preferably, it is more preferably 8.0 atomic% or less.
  • the resistance of the transparent conductive oxide film is increased.
  • Environmental performance can be improved.
  • the Sn content is 4.7 atomic% or less, an increase in electrical resistance in the first transparent conductive oxide film 11 and the second transparent conductive oxide film 13 can be suppressed.
  • the lower limit of the Sn content is 0.1 atomic% or more. And more preferably 0.5 atomic% or more.
  • the upper limit of Sn content being 4.7 atomic% or less.
  • it is 4.0 atomic% or less.
  • the total content of Ga, Y, and Sn is 37.5 atomic% or less. It is preferable to make it 30.0 atomic% or less.
  • the film thickness t2 of the Ag film 12 is set to 10 nm or less in order to improve the transmittance.
  • the thickness t2 of the Ag film 12 is preferably 10 nm or less, and more preferably 8 nm or less.
  • the lower limit of the film thickness t2 of the Ag film 12 is preferably 3 nm or more, and more preferably 4 nm or more.
  • the film thickness t1 of the first transparent conductive oxide film 11 and the film thickness t3 of the second transparent conductive oxide film 13 are obtained by using optical constants (refractive index and extinction coefficient) in each single-phase film.
  • An optical simulation is performed with a three-layer structure of 1 transparent conductive oxide film / Ag film (Ag alloy film) / second transparent conductive oxide film, and the film thickness is such that the transmittance in the visible light region is improved by the optical interference effect. .
  • the film thickness t1 of the first transparent conductive oxide film 11 and the film thickness t3 of the second transparent conductive oxide film 13 are preferably set to film thicknesses in the following ranges.
  • n1 and n3 are the refractive index (n1) of the first transparent conductive oxide film 11 and the refractive index (n3) of the second transparent conductive oxide film 13.
  • K1 and k3 are the coefficient (k1) of the first transparent conductive oxide film 11 and the coefficient (k3) of the second transparent conductive oxide film 13, respectively.
  • the optimum values of the coefficients k1 and k3 differ depending on the transparent conductive oxide, but the coefficients k1 and k3 are preferably in the range of 0.2 to 0.8, and in the range of 0.4 to 0.7. More preferably. In particular, when the coefficients k1 and k3 are about 0.6, the transmittance in the visible light region is improved regardless of the type of the transparent conductive oxide.
  • the film thickness t1 of the first transparent conductive oxide film 11 and the film thickness t3 of the second transparent conductive oxide film 13 are set to 40 nm. These film thicknesses are the film thicknesses when the coefficients k1 and k3 are 0.6.
  • the laminated wiring film 30 according to the present embodiment has a wiring pattern formed on the laminated transparent conductive film 10 shown in FIG. 1.
  • the wiring pattern has a width of the line L and a width S of the space S between the lines L within a range of 1 ⁇ m to 900 ⁇ m.
  • the laminated wiring film 30 described above is manufactured as follows. First, the laminated transparent conductive film 10 according to the present embodiment is deposited on the deposition surface of the substrate 20 (laminated transparent conductive film deposition step S11). In the laminated transparent conductive film forming step S ⁇ b> 11, the first transparent conductive oxide film 11 is formed on the substrate 20 as a base layer. The first transparent conductive oxide film 11 is preferably formed by DC sputtering using a sintered target whose film composition is easy to control. Next, an Ag film 12 is formed on the formed first transparent conductive oxide film 11 by DC sputtering using an Ag target. This Ag target has a composition corresponding to the composition of the Ag film 12 to be formed.
  • the second transparent conductive oxide film 13 is formed on the formed Ag film 12 by DC sputtering using a transparent conductive oxide target.
  • the transparent conductive oxide target is preferably a sintered target whose film composition is easily controlled. In this manner, the laminated transparent conductive film 10 according to this embodiment is formed.
  • a resist film 41 is formed on the laminated transparent conductive film 10 formed on the surface of the substrate 20, and the resist film 41 is exposed and developed to form a wiring pattern (resist film forming step S12). ).
  • the laminated transparent conductive film 10 on which the resist film 41 is formed is collectively etched using an acidic mixed solution containing phosphoric acid and acetic acid as an etchant (etching step S13).
  • the content of phosphoric acid is preferably 55% by volume or less, and the content of acetic acid is preferably 30% by volume or less.
  • the resist film 41 is removed using an alkaline resist removing solution (resist film removing step S14). Thereby, the laminated transparent conductive film 10 located below the wiring pattern-shaped resist film 41 remains, and the laminated wiring film 30 having the wiring pattern is formed.
  • a first transparent conductive oxide film 11 is formed on the surface of the substrate 20 as an underlayer, and the first transparent conductive oxide film 11 is formed. Since the Ag film 12 is formed thereon, the wettability of the Ag film 12 is improved, and aggregation of Ag is suppressed even when the Ag film 12 is thinly formed. Furthermore, since the first transparent conductive oxide film 11 and the second transparent conductive oxide film 13 are excellent in environmental resistance, even when used in a high humidity environment, Intrusion of moisture can be suppressed, and aggregation of Ag can be suppressed. Therefore, generation of surface plasmon absorption due to Ag aggregation in the Ag film 12 can be prevented, and high transmittance can be obtained. Further, since the Ag film 12 is a continuous film, the electrical resistance can be lowered.
  • the first transparent conductive oxide film 11 and the second transparent conductive oxide film 13 are made by adding Ga, Y, and Sn to the Zn oxide.
  • the atomic ratio of Ga, Y and Sn in all metal elements contained in the material film is Ga: 0.9 atomic% or more and 26.1 atomic% or less, Y: 0.2 atomic% or more and 9.5 atomic% or less, Sn: Since it is 0.1 atomic% or more and 4.7 atomic% or less, aggregation of Ag can be suppressed by addition of Ga, and an increase in electrical resistance can be suppressed.
  • alkali resistance can be improved by addition of Y.
  • environmental resistance can be improved by addition of Sn.
  • the thickness t2 of the Ag film 12 is set to 10 nm or less, the transmittance can be improved.
  • the first transparent conductive oxide film 11 is formed on the surface of the substrate 20 as an underlayer, even if the thickness of the Ag film 12 is 10 nm or less, Ag is not agglomerated and becomes a continuous film, and the electrical resistance is lowered. be able to.
  • the Ag film 12 is made of Cu, Sn, Sb, Zn, Ge, In, Al, Ga, Ti, Mg, Pd, Au, Pt, Bi, Mn, Sc, Y, Nd, Sm, One or two or more of Eu, Gd, Tb and Er are contained in a total of 0.2 atomic% to 10.0 atomic%, and the balance is composed of an Ag alloy composed of Ag and inevitable impurities. Therefore, aggregation of the Ag film 12 is further suppressed, and even if the Ag film 12 is formed thinner, it becomes a continuous film, and both high transmittance and low resistance can be achieved.
  • the average transmittance in the visible light region having a wavelength of 400 to 800 nm is 85% or more, and the sheet resistance value is 10 ⁇ / sq. Since it has a sufficiently high transmittance and low electrical resistance, it can be used as a miniaturized transparent electrode film or transparent wiring film.
  • the laminated wiring film 30 according to the present embodiment has a low electrical resistance and a high transmittance since the wiring pattern is formed on the laminated transparent conductive film 10 according to the present embodiment.
  • the Ag film 12, the first transparent conductive oxide film 11, and the second transparent conductive oxide are used. Since the difference in etching rate with the film 13 is small, overetching OE of the Ag film 12, the first transparent conductive oxide film 11, and the second transparent conductive oxide film even if the laminated transparent conductive film 10 is collectively etched. 13 residue R and the like can be suppressed, and a wiring pattern can be formed with high accuracy.
  • the alkali resistance of the first transparent conductive oxide film 11 and the second transparent conductive oxide film 13 is improved by adding Y, an alkaline resist removal solution is used in the resist film removal step S14. Even if the resist film is removed by using, deterioration of characteristics of the laminated wiring film 30 can be suppressed.
  • the Ag film 12 is made of Cu, Sn, Sb, Zn, Ge, In, Al, Ga, Ti, Mg, Pd, Au, Pt, Bi, Mn, Sc, Y, Nd, Sm, Eu. , Gd, Tb, and Er are included in a total of 0.2 atomic% to 10.0 atomic%, with the balance being composed of an Ag alloy composed of Ag and inevitable impurities.
  • the present invention is not limited to this, and it may be pure Ag or an Ag alloy containing another metal element that is dissolved in Ag.
  • the first transparent conductive oxide film 11 and the second transparent conductive oxide film 13 have been described as having a thickness of about 40 nm.
  • the present invention is not limited to this, and other film thicknesses are possible. It is good.
  • the laminated wiring film 30 is described as being manufactured by an etching method.
  • the present invention is not limited to this, and as shown in FIGS. 5 and 6, the laminated wiring film 30 is formed by a lift-off method. It may be manufactured.
  • a resist film 41 is formed on the film forming surface of the substrate 20, and the resist film 41 is exposed and developed to reverse the wiring pattern. The reversed pattern thus formed is formed (resist film forming step S21).
  • the first transparent conductive oxide film 11, the Ag film 12, and the second transparent conductive oxide film 13 are sequentially formed on the substrate 20 on which the resist film 41 having the reverse pattern is formed by sputtering.
  • the laminated transparent conductive film 10 is formed on the resist film 41 and the substrate 20 (laminated transparent conductive film forming step S22).
  • the resist film 41 is removed using an alkaline resist removing solution (resist film removing step S23).
  • resist film removing step S23 As a result, the laminated transparent conductive film 10 formed on the resist film 41 having the inverted pattern is removed, and a laminated wiring film 30 having a wiring pattern is formed.
  • the wiring pattern can be formed with high accuracy without performing the etching process.
  • the alkali resistance of the first transparent conductive oxide film 11 and the second transparent conductive oxide film 13 is improved by the addition of Y, in the resist film removing step S23, a resist film is used by using an alkaline resist removing solution. Even if this is removed, the deterioration of the characteristics of the laminated wiring film 30 can be suppressed.
  • a laminated transparent conductive film having a structure shown in Table 1-3 was formed on the surface of a glass substrate (non-alkali glass: 50 mm ⁇ 50 mm ⁇ 1 mmt) by sputtering.
  • a glass substrate non-alkali glass: 50 mm ⁇ 50 mm ⁇ 1 mmt
  • an ITO single layer film was formed by sputtering.
  • the glass substrate was heated to 200 ° C. to form a film.
  • the composition of the ITO film (oxide obtained by adding Sn to In 2 O 3 ) is In: 35.6 atomic%, Sn: 3.6 atomic%, and O: 60.8 atomic%.
  • the composition of the GZO film (oxide obtained by adding Ga to ZnO) is Zn: 47.3 atomic%, Ga: 2.2 atomic%, and O: 50.5 atomic%.
  • the composition of the GZTO film (oxide obtained by adding Ga and Sn to ZnO) is Zn: 40.0 atomic%, Ga: 6.7 atomic%, Sn: 1.1 atomic%, O: 52.2 atomic%. is there.
  • the composition of the GZYO film (oxide obtained by adding Ga and Y to ZnO) is Zn: 39.1 atomic%, Ga: 6.5 atomic%, Y: 2.2 atomic%, O: 52.2 atomic%. is there.
  • the composition of the ZTYO film (oxide obtained by adding Sn and Y to ZnO) is Zn: 40.9 atomic%, Sn: 2.3 atomic%, Y: 4.6 atomic%, O: 52.2 atomic% is there.
  • the composition of the GTYO film (oxide obtained by adding Ga and Y to SnO2) is Sn: 30.5 atomic%, Ga: 1.7 atomic%, Y: 1.7 atomic%, O: 66.1 atomic%. is there.
  • the film thickness of the transparent conductive oxide film is the optical simulation described in the embodiment, and the film thickness at which the transmittance in the visible light region is improved by the optical interference effect is selected. All were 40 nm.
  • membrane and the transparent conductive oxide film in the Example of this invention and a comparative example was measured using the film thickness meter (DEKTAK by ULVAC).
  • the compositions of the transparent conductive oxide film and the Ag alloy film were determined by quantitative analysis of elements using an ICP emission spectrometer (ICP emission spectrometer STS-3500DD manufactured by Hitachi High-Tech Science Co., Ltd.).
  • an oxide sintered compact target having the composition described in Table 1-3 and above was used for the production of the transparent conductive oxide film.
  • an Ag target having the composition described in Table 1-3 was used for the preparation of the Ag film.
  • a laminated film transparent conductive film using a Cu film and an Al film instead of the Ag film was prepared using a Cu target and an Al target. The film forming conditions for each film are shown below.
  • Sputtering apparatus DC magnetron sputtering apparatus (ULVAC CS-200) Magnetic field strength: 1000 Gauss (directly above the target, vertical component) Ultimate vacuum: 5 ⁇ 10 ⁇ 5 Pa or less Sputtering gas: Ar + O 2 mixed gas (O 2 mixing ratio 2%) Sputtering gas pressure: 0.4 Pa Sputtering power: DC100W
  • Sputtering apparatus DC magnetron sputtering apparatus (ULVAC CS-200) Magnetic field strength: 1000 Gauss (directly above the target, vertical component) Ultimate vacuum: 5 ⁇ 10 ⁇ 5 Pa or less Sputtering gas: Ar Sputtering gas pressure: 0.5 Pa Sputtering power: DC100W
  • permeability after film-forming were evaluated.
  • the sheet resistance and transmittance after the constant temperature and humidity test, and the sheet resistance and transmittance after the alkali resistance test were evaluated.
  • the obtained laminated transparent conductive film was subjected to a patterning test by an etching method and a patterning test by a lift-off method. The evaluation method is shown below.
  • Sheet resistance was measured by a four-probe method using a surface resistance measuring instrument (Loresta AP MCP-T400 manufactured by Mitsubishi Yuka Co., Ltd.).
  • ⁇ Transmissivity> Using a spectrophotometer (U4100 manufactured by Hitachi High-Technologies Corporation), a transmittance spectrum in a wavelength range of 400 nm to 800 nm was measured, and an average transmittance (transmittance) was obtained.
  • ⁇ Constant temperature and humidity test> The sample was left in a constant temperature and humidity chamber of 85 ° C. and 85% humidity for 250 hours, and the transmittance and sheet resistance after the test were measured to evaluate the rate of change from before the test.
  • ⁇ Alkali resistance test> The film was immersed in an alkaline resist removing solution (pH 9, TOK-104 manufactured by Tokyo Ohka Kogyo Co., Ltd.) at a temperature of 40 ° C. for 10 minutes, and the transmittance and sheet resistance after immersion were measured to evaluate the rate of change from before immersion.
  • an alkaline resist removing solution pH 9, TOK-104 manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • ⁇ Patterning test by etching method About the above-mentioned laminated transparent conductive film, a resist film was formed on the laminated transparent conductive film in a wiring pattern shape of line width / space width: 30 ⁇ m / 30 ⁇ m by photolithography. This was batch etched using a mixed solution containing phosphoric acid and acetic acid (SEA-5 manufactured by Kanto Chemical Co., Inc.) as an etchant. The etching was performed without heating and with an appropriate etching time (20 seconds to 120 seconds). Further, the phosphoric acid content in the mixed solution was 55% by volume or less, and the acetic acid content was 30% by volume or less.
  • SEA-5 manufactured by Kanto Chemical Co., Inc.
  • FIG. 7A shows the observation result of Example 4 of the present invention
  • FIG. 7B shows the observation result of Comparative Example 12.
  • ⁇ Patterning test by lift-off method First, a resist solution is applied to the substrate, a photomask on which a wiring pattern of line width / space width: 30 ⁇ m / 30 ⁇ m is formed, exposed to ultraviolet rays with an exposure machine, and then the portion exposed to the developer is removed. Then, a reversal pattern was formed by photolithography. Next, a laminated transparent conductive film was formed on the substrate on which the reverse pattern was formed using the sputtering apparatus as described above. Next, after immersing in a resist removing solution to remove the laminated transparent conductive film formed on the resist film, the formed wiring pattern was observed with an optical microscope.
  • the average transmittance after film formation exceeds 85%, and the sheet resistance after film formation is 10 ⁇ / sq. It was confirmed that a laminated transparent conductive film having excellent transmittance and sufficiently low resistance was obtained.
  • the average transmittance after film formation is 85% or less, and the sheet resistance after film formation is higher than that of the present invention example when compared with the samples having the same composition and film thickness of the Ag film. It was. It is presumed that Ag aggregation occurred in the Ag film.
  • the sheet resistance is 10 ⁇ / sq.
  • the sheet resistance is 10 ⁇ / sq.
  • the average transmittance was greatly deteriorated to 76.4%.
  • Comparative Example B by heating the glass substrate to 200 ° C., the film thickness is 180 nm and the sheet resistance is 10 ⁇ / sq. The average transmittance was 85% or less.
  • the transmittance after the alkali resistance test and the change rate of the sheet resistance are small, the average transmittance after the test is 85% or more, and the alkali resistance is excellent. confirmed.
  • the comparative example many samples with a large change rate of transmittance or sheet resistance after the alkali resistance test were observed, and many samples had insufficient alkali resistance. Even in the samples having a small change rate, the average transmittance after the test was 85% or less.
  • the wiring pattern can be formed with high accuracy in the example of the present invention.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Human Computer Interaction (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention porte sur un film conducteur transparent multicouche qui est caractérisé en ce qu'il comprend un film d'Ag (12) qui est constitué d'Ag ou d'un alliage d'Ag et des films d'oxyde conducteur transparent (11, 13) qui sont disposés sur les deux faces du film d'Ag (12), et est également caractérisé en ce que les films d'oxyde conducteur transparent (11, 13) sont constitués d'un oxyde contenant Zn, Ga, Y et Sn. Il est préférable que ce film conducteur transparent multicouche présente une transmittance moyenne supérieure ou égale à 85 % pour la plage de longueurs d'onde de lumière visible allant de 400 à 800 nm et une résistance de couche inférieure ou égale à 10 ohms par carré.
PCT/JP2017/002998 2016-01-28 2017-01-27 Film conducteur transparent multicouche, film de câblage multicouche et procédé de fabrication de film de câblage multicouche WO2017131183A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016-014703 2016-01-28
JP2016014703 2016-01-28
JP2017-003349 2017-01-12
JP2017003349A JP6870332B2 (ja) 2016-01-28 2017-01-12 積層透明導電膜、積層配線膜及び積層配線膜の製造方法

Publications (1)

Publication Number Publication Date
WO2017131183A1 true WO2017131183A1 (fr) 2017-08-03

Family

ID=59399099

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/002998 WO2017131183A1 (fr) 2016-01-28 2017-01-27 Film conducteur transparent multicouche, film de câblage multicouche et procédé de fabrication de film de câblage multicouche

Country Status (1)

Country Link
WO (1) WO2017131183A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113345644A (zh) * 2021-06-07 2021-09-03 北方民族大学 一种柔性Ag/Zn导电薄膜及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011504639A (ja) * 2007-11-22 2011-02-10 サン−ゴバン グラス フランス 電極を支持している基材、該基材を含む有機エレクトロルミネセントデバイス及びその製造
JP2015228363A (ja) * 2014-05-07 2015-12-17 Tdk株式会社 積層型透明導電膜
JP2016040411A (ja) * 2014-08-12 2016-03-24 三菱マテリアル株式会社 積層膜、積層配線膜及び積層配線膜の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011504639A (ja) * 2007-11-22 2011-02-10 サン−ゴバン グラス フランス 電極を支持している基材、該基材を含む有機エレクトロルミネセントデバイス及びその製造
JP2015228363A (ja) * 2014-05-07 2015-12-17 Tdk株式会社 積層型透明導電膜
JP2016040411A (ja) * 2014-08-12 2016-03-24 三菱マテリアル株式会社 積層膜、積層配線膜及び積層配線膜の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113345644A (zh) * 2021-06-07 2021-09-03 北方民族大学 一种柔性Ag/Zn导电薄膜及其制备方法和应用

Similar Documents

Publication Publication Date Title
JP6888318B2 (ja) 積層透明導電膜、積層配線膜及び積層配線膜の製造方法
WO2016024615A1 (fr) Film stratifié, film de câblage stratifié, et procédé de fabrication d'un film de câblage stratifié
JP2007250430A (ja) 透明導電膜、およびこれを用いた透明導電性フィルム
KR101358529B1 (ko) 전자부품용 적층 배선막 및 피복층 형성용 스퍼터링 타겟재
JP4971618B2 (ja) 表示用電極パターン製造方法
KR102327961B1 (ko) 적층 반사 전극막, 적층 반사 전극 패턴, 적층 반사 전극 패턴의 제조 방법
WO1998004406A1 (fr) Pellicule conductrice transparente et procede pour former une electrode transparente
KR101777549B1 (ko) 투명 도전 배선 및 투명 도전 배선의 제조 방법
JP6870332B2 (ja) 積層透明導電膜、積層配線膜及び積層配線膜の製造方法
JP5023745B2 (ja) 透明導電膜、この透明導電膜を用いた透明導電性基板、透明導電性フィルム、並びに近赤外線遮断フィルター、および、この透明導電膜の製造方法
JP2006310814A (ja) 薄膜配線層
WO2017131183A1 (fr) Film conducteur transparent multicouche, film de câblage multicouche et procédé de fabrication de film de câblage multicouche
WO2016111202A1 (fr) Film multicouche
KR101350648B1 (ko) 전자부품용 적층 배선막 및 피복층 형성용 스퍼터링 타겟재
WO2017164209A1 (fr) Film conducteur transparent stratifié, film de câblage stratifié, et procédé de fabrication d'un film de câblage stratifié
JP6565666B2 (ja) 積層透明導電膜、積層配線膜及び積層配線膜の製造方法
JP6597284B2 (ja) 積層透明導電膜、積層配線膜及び積層配線膜の製造方法
JP2016130010A (ja) 積層膜
WO2017164211A1 (fr) Film d'électrode réfléchissante stratifiée, motif d'électrode réfléchissante stratifiée et procédé de production d'un motif d'électrode réfléchissante stratifiée
WO2016136953A1 (fr) Fil conducteur transparent et procédé de fabrication de fil conducteur transparent
JPH11262968A (ja) 透明導電膜
JP2018087360A (ja) 酸化物スパッタリングターゲット
WO2021095550A1 (fr) Structure stratifiée
JP6123285B2 (ja) 積層膜

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17744413

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17744413

Country of ref document: EP

Kind code of ref document: A1