WO2016136953A1 - Fil conducteur transparent et procédé de fabrication de fil conducteur transparent - Google Patents

Fil conducteur transparent et procédé de fabrication de fil conducteur transparent Download PDF

Info

Publication number
WO2016136953A1
WO2016136953A1 PCT/JP2016/055855 JP2016055855W WO2016136953A1 WO 2016136953 A1 WO2016136953 A1 WO 2016136953A1 JP 2016055855 W JP2016055855 W JP 2016055855W WO 2016136953 A1 WO2016136953 A1 WO 2016136953A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
transparent conductive
conductive oxide
oxide film
wiring
Prior art date
Application number
PCT/JP2016/055855
Other languages
English (en)
Japanese (ja)
Inventor
一郎 塩野
悠人 歳森
野中　荘平
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 JP2016034768A external-priority patent/JP6020750B1/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
Priority to CN201680002259.7A priority Critical patent/CN106796885B/zh
Priority to KR1020177004671A priority patent/KR101777549B1/ko
Publication of WO2016136953A1 publication Critical patent/WO2016136953A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present invention relates to a transparent conductive wiring used for, for example, a display or a touch panel, and a method for manufacturing the transparent conductive wiring.
  • the present application includes Japanese Patent Application No. 2015-37950 filed in Japan on February 27, 2015, Japanese Patent Application No. 2015-217683 filed in Japan on November 5, 2015, and Japan on February 25, 2016. Priority is claimed based on Japanese Patent Application No. 2016-34768 filed in Japan, the contents of which are incorporated herein by reference.
  • a transparent conductive wiring having a laminated structure of a transparent conductive oxide film and a metal film is applied as the wiring as shown in, for example, Patent Document 1-3. Yes.
  • the transparent conductive wiring is required to have a high light transmittance in the visible light region (hereinafter referred to as luminous transmittance) and a low electrical resistance.
  • Patent Document 3-5 when a wiring pattern is formed on a laminated film of a transparent conductive oxide film and a metal film to form a transparent conductive wiring, an etching process is performed on the above-described laminated film as shown in Patent Document 3-5. It is common.
  • Patent Documents 3-5 as a means for etching a laminated film of a transparent conductive oxide film and a metal film, etching is performed in two stages using an etching solution for the transparent conductive oxide film and an etching solution for the metal film.
  • the transparent conductive wiring is required to further improve the luminous transmittance, and therefore, it is necessary to form a metal film thinner than before.
  • the conventional etching method described above causes the metal film to be preferentially etched over the transparent conductive oxide film, which increases the amount of overetching of the metal film. was there.
  • the width of the wiring is recently reduced due to the miniaturization of the wiring, there is a possibility that sufficient conductivity cannot be secured if the amount of over-etching of the metal film increases.
  • the present invention has been made in view of the above-described circumstances, and has a high luminous transmittance, a transparent conductive wiring in which the amount of overetching of a metal film is suppressed, and conductivity is sufficiently secured, and It aims at providing the manufacturing method of this transparent conductive wiring.
  • the transparent conductive wiring of the present invention has an Ag film made of Ag or an Ag alloy and a transparent conductive oxide film laminated on the Ag film, and a wiring pattern is formed by an etching process.
  • the transparent conductive wiring is characterized in that the thickness of the Ag film is 15 nm or less, and the amount of overetching of the Ag film with respect to the transparent conductive oxide film is 1 ⁇ m or less.
  • the transparent conductive wiring of the present invention since the thickness of the Ag film is 15 nm or less, the luminous transmittance is excellent. In the transparent conductive wiring according to the present invention, the over-etching amount of the Ag film is suppressed to 1 ⁇ m or less. Therefore, even when the wiring width is narrow, the width of the metal film is ensured to ensure conductivity. Can be secured.
  • the Ag film has a total of 0.05 atomic% or more, 10.0% or more of Sn, In, Mg, or Ti as an additive element. It is preferable that it is made of an Ag alloy having a composition that includes atomic percent or less and the balance of Ag and inevitable impurities. According to the transparent conductive wiring of this configuration, the Ag film has a total amount of 0.05 atomic% or more and 10.0 atomic% or less of any one element or two or more elements of Sn, In, Mg, and Ti as additive elements. Since the remaining portion is made of an Ag alloy composed of Ag and inevitable impurities, the wettability of the Ag film with respect to the substrate and the oxide film can be improved.
  • the thickness of the Ag film formed on the substrate or the oxide film is relatively thin, such as 15 nm or less, the aggregation of the film can be suppressed, the electrical resistance is low, and the visual feeling The transmittance can be improved.
  • the additive element further contains one or both of Sb: 0.01 atomic% or more and Cu: 0.1 atomic% or more, and the total of all additive elements May be 10.0 atomic% or less, and the balance may be composed of an Ag alloy having a composition including Ag and inevitable impurities.
  • the additive element further includes one or both of Sb: 0.01 atomic% or more and Cu: 0.1 atomic% or more, and the total of all additive elements is Since it is 10.0 atomic% or less, and the balance is composed of an Ag alloy having a composition composed of Ag and inevitable impurities, the addition of Sb and Cu can further suppress the aggregation of the film and reduce the electrical resistance. In addition, the luminous transmittance can be improved.
  • the transparent conductive oxide film is preferably an amorphous film. According to the transparent conductive wiring of this configuration, since the transparent conductive oxide film is an amorphous film, it can be reliably etched with an oxalic acid etchant described later, and the amount of overetching of the Ag film is reduced. be able to.
  • the method for producing a transparent conductive wiring according to the present invention is a method for producing a transparent conductive wiring having an Ag film made of Ag or an Ag alloy and a transparent conductive oxide film laminated on the Ag film, and having a wiring pattern formed thereon. And an etching process step of forming a wiring pattern by performing an etching process on the laminated film including the Ag film and the transparent conductive oxide film, wherein the thickness of the Ag film is 15 nm or less. In the etching process, the transparent conductive oxide film and the Ag film are dissolved together using an oxalic acid etching solution.
  • an oxalic acid etching solution in the etching process step of forming a wiring pattern by performing an etching process on the laminated film having the Ag film and the transparent conductive oxide film, an oxalic acid etching solution , The transparent conductive oxide film and the Ag film are dissolved together. Normally, it is difficult to etch an Ag film with an oxalic acid etchant. However, in the present invention, the Ag film is formed as thin as 15 nm or less. The film can be removed. Further, this oxalic acid etching solution is inferior to the etching property of the Ag film as compared with the transparent conductive oxide film, so that overetching of the Ag film can be suppressed.
  • the oxalic acid etching solution is preferably an oxalic acid aqueous solution having an oxalic acid concentration within a range of 3 mass% to 7 mass%.
  • the oxalic acid aqueous solution having an oxalic acid concentration in the range of 3% by mass to 7% by mass is used as the oxalic acid etching solution,
  • the transparent conductive oxide film can be etched at once, and the amount of overetching of the Ag film can be reliably reduced.
  • a transparent conductive wiring having high luminous transmittance, a reduced amount of over-etching of a metal film, and sufficient conductivity, and a method for manufacturing the transparent conductive wiring. Is possible.
  • the transparent conductive wiring 10 which is embodiment of this invention, and the manufacturing method of a transparent conductive wiring are demonstrated with reference to the attached figure.
  • the transparent conductive wiring 10 in this embodiment is used in various displays and touch panels.
  • the transparent conductive wiring 10 according to the present embodiment includes, for example, an Ag film 11 formed on one surface of a substrate 30, and a transparent conductive oxide film 12 formed on the Ag film 11. And.
  • a glass substrate such as alkali-free glass or borosilicate glass, or a resin film such as a PET film can be used.
  • the transparent conductive wiring 10 a wiring pattern is formed by performing an etching process on the laminated film having the Ag film 11 and the transparent conductive oxide film 12.
  • the transparent conductive wiring 10 has an overetching amount L of the Ag film 11 with respect to the transparent conductive oxide film 12 of 1 ⁇ m or less. Specifically, as shown in FIG. 2, when a cross section of the etched wiring is observed, the distance between the end surface 12e of the transparent conductive oxide film 12 and the end surface 11e of the Ag film 11 is 1 ⁇ m or less. It is.
  • the overetching amount L of the Ag film 11 with respect to the transparent conductive oxide film 12 is more preferably 0.8 ⁇ m or less.
  • the film thickness ta of the Ag film 11 is in the range of 3 nm to 15 nm. Further, the film thickness to of the transparent conductive oxide film 12 is in the range of 5 nm to 80 nm. In the present embodiment, the width of the transparent conductive wiring 10 is set within a range of 10 ⁇ m to 100 ⁇ m.
  • the Ag film 11 is made of pure Ag or an Ag alloy.
  • the Ag alloy includes any one or more elements of Sn, In, Mg, and Ti as additive elements in a total range of 0.05 atomic% or more and 10.0 atomic% or less.
  • the balance is composed of an Ag alloy having a composition comprising Ag and inevitable impurities.
  • Inevitable impurities include, for example, 500 ppm or less of Fe, Pb, Bi, Al, Zn, and the like.
  • Sn, In, Mg, and Ti contained in the Ag alloy constituting the Ag film 11 are elements having an effect of improving the wettability of the Ag film 11.
  • Sn, In, Mg, and Ti have the effect of further improving the adhesion between the Ag film 11 and the transparent conductive oxide film 12.
  • Sn, In, Mg, and Ti are elements that greatly increase the electrical resistance, so that one or more of Sn, In, Mg, and Ti exceeds 10.0 atomic% in total. There is a risk that the electrical resistance becomes high and the conductivity deteriorates.
  • the contents of the additive elements Sn, In, Mg, and Ti are defined within a range of 0.05 atomic% to 10.0 atomic% in total.
  • the content of Sn, In, Mg, and Ti is more preferably in the range of 0.1 atomic% to 5.0 atomic%.
  • the Ag alloy constituting the Ag film 11 may further contain Sb and Cu as additive elements.
  • Sb and Cu are elements having an effect of further improving the environmental resistance by suppressing Ag aggregation of the Ag film 11 without greatly reducing the luminous transmittance and without greatly increasing the resistance.
  • Sb is less than 0.01 atomic% and Cu is less than 0.1 atomic%, the above-described effects may not be sufficiently achieved.
  • Sb when Sb is added, the Sb content is 0.01 atomic% or more, and when Cu is added, the Cu content is 0.1 atomic% or more. It is set.
  • Sb and Cu are elements that greatly increase the resistance as well as Sn, In, Mg, and Ti.
  • the sum total of content of Sn, In, Mg, Ti, Sb, and Cu which are addition elements is set to 10 atomic% or less.
  • the total content of Sn, In, Mg, Ti, Sb, and Cu is more preferably 7.0 atomic percent or less.
  • the transparent conductive oxide constituting the transparent conductive oxide film 12 includes In—Sn oxide (ITO), Al—Zn oxide (AZO), In—Zn oxide (IZO), and Zn—Sn oxide (ZTO). Zn—Sn—Al oxide (AZTO).
  • ITO In—Sn oxide
  • AZO Al—Zn oxide
  • IZO In—Zn oxide
  • ZTO Zn—Sn oxide
  • ZTO Zn—Sn—Al oxide
  • the transparent conductive oxide film 12 is preferably an amorphous film. Specifically, in the X-ray diffraction measurement of the transparent conductive oxide film 12, it is more clear as shown in FIG. 3B than the crystalline film in which a clear crystal peak exists as shown in FIG. It is preferable to use an amorphous film in which no crystal peak exists.
  • the transparent conductive oxide film 12 is an amorphous film of In—Sn oxide (ITO).
  • the transparent conductive wiring 10 according to this embodiment has a luminous transmittance of 70% or more in the visible light region in the state of the laminated film before performing the etching process. Further, the transparent conductive wiring 10 according to the present embodiment has a sheet resistance of 40 ⁇ / sq or less in the state of the laminated film before performing the etching process.
  • the Ag film 11 is formed on the substrate 30 using an Ag alloy sputtering target.
  • the composition of the Ag alloy sputtering target used when forming the Ag film 11 is adjusted according to the composition of the Ag film 11 to be formed.
  • the Ag alloy sputtering target in the present embodiment is manufactured as follows. As raw materials, Ag having a purity of 99.9% by mass or more and Sn, In, Mg, Ti, Sb, Cu having a purity of 99.9% by mass or more are prepared. Next, in a melting furnace, Ag is melted in a high vacuum or an inert gas atmosphere, and the resulting molten metal is one or more of Sn, In, Mg, Ti, or any of Sb and Cu. One or two or more kinds are added in a predetermined amount. Then, it melt
  • the melting of Ag is performed in an atmosphere in which the atmosphere inside the melting furnace is once evacuated and then replaced with Ar, and after melting, Sn, In, Mg, Ti, Sb, It is preferable to add Cu.
  • Sn, In, Mg, Ti, Sb, and Cu may be added in the form of a mother alloy prepared in advance. After the obtained Ag alloy ingot is cold-rolled, it is subjected to heat treatment at 600 ° C. for 2 hours in the atmosphere, and then machined to produce an Ag alloy sputtering target having a predetermined size.
  • the above-described Ag alloy sputtering target is soldered to a backing plate made of oxygen-free copper, and this is mounted on a DC magnetron sputtering apparatus.
  • the substrate 30 is disposed opposite to the Ag alloy sputtering target and at a predetermined interval.
  • Ar gas is introduced to obtain a predetermined sputtering gas pressure, A 50 W direct current sputtering power is applied. Thereby, plasma is generated between the substrate 30 and the Ag alloy sputtering target, and the Ag film 11 is formed on the substrate 30.
  • Transparent conductive oxide film forming step S02 Transparent conductive oxide film forming step S02
  • sputtering is performed on the formed Ag film 11 using a sputtering target made of a transparent conductive oxide, and a transparent conductive oxide film 12 is formed on the Ag film 11.
  • a transparent conductive oxide film 12 is formed on the Ag film 11.
  • an ITO film is formed as the transparent conductive oxide film 12
  • a crystalline film and an amorphous film can be selected and formed depending on the film forming conditions.
  • a laminated film in which the Ag film 11 and the transparent conductive oxide film 12 are laminated is formed.
  • an oxalic acid aqueous solution having an oxalic acid concentration in the range of 3 mass% to 7 mass% is used as the oxalic acid etching solution.
  • the temperature of the oxalic acid etching solution was set to 40 to 60 ° C.
  • the oxalic acid concentration is less than 3% by mass, the etching rate becomes slow, and it may not be possible to perform the etching process efficiently.
  • the oxalic acid concentration exceeds 7% by mass, oxalic acid may be precipitated in the liquid.
  • the oxalic acid concentration in the oxalic acid aqueous solution is set in the range of 3 mass% or more and 7 mass% or less.
  • the oxalic acid concentration in the oxalic acid aqueous solution is more preferably 3% by mass or more and 5% by mass or less.
  • an organic additive may be added in order to suppress the generation of etching residues.
  • the content of additives other than oxalic acid and water (solvent) is preferably limited to 4% by mass or less.
  • resist stripping step S04 After the etching treatment step S03, the resist film is removed by dipping in a resist remover. Thereby, the transparent conductive wiring 10 having a predetermined wiring pattern is manufactured.
  • the overetching amount L of the Ag film 11 with respect to the transparent conductive oxide film 12 is 1 ⁇ m or less, so the wiring in the etching process step S03 Even if the wiring width of the pattern shape is narrow, the width of the Ag film can be ensured and the conductivity can be ensured. Moreover, since the film thickness ta of the Ag film 11 is in the range of 3 nm or more and 15 nm or less, the luminous transmittance is excellent and the conductivity of the transparent conductive wiring 10 can be ensured. Therefore, it is particularly suitable as wiring for various displays and touch panels.
  • the Ag film 11 has a total range of 0.05 atomic% or more and 10.0 atomic% or less of any one or two or more elements of Sn, In, Mg, and Ti as additive elements. And the balance is made of an Ag alloy having a composition comprising Ag and inevitable impurities. Therefore, the wettability of the Ag film is improved, and the aggregation of the film can be suppressed even when the film thickness ta of the Ag film 11 is relatively thin as 15 nm or less. Therefore, the electrical resistance of the transparent conductive wiring 10 can be lowered and the luminous transmittance can be improved.
  • the Ag alloy that constitutes the Ag film 11 contains one or both of Sb: 0.01 atomic% or more and Cu: 0.1 atomic% or more in addition to the above-described additive elements.
  • the total of all additive elements is 10.0 atomic% or less, and the balance is composed of Ag and inevitable impurities.
  • the addition of Sb and Cu can further suppress the aggregation of the film, further lower the electrical resistance of the transparent conductive wiring 10 and further improve the luminous transmittance.
  • the luminous transmittance in the visible light region is set to 70% or more and the sheet resistance is 40 ⁇ / sq in the laminated film before the etching process step S03 is performed. Since it is set as the following, it can apply to various displays and a touch panel as the transparent conductive wiring 10 excellent in visibility and electroconductivity.
  • the transparent conductive oxide film 12 is an amorphous ITO film, it can be reliably etched using an oxalic acid etchant in the etching process step S03. Therefore, the overetching amount L of the Ag film 11 can be reliably suppressed.
  • the film thickness ta of the Ag film 11 is relatively thin in the range of 3 nm or more and 15 nm or less. Therefore, in the etching process step S03, oxalic acid etching is performed. Even when a liquid is used, the Ag film 11 can be removed and a wiring pattern can be formed.
  • the oxalic acid etching solution an oxalic acid aqueous solution having an oxalic acid concentration in the range of 3% by mass to 7% by mass is used. Therefore, the Ag film 11 and the transparent conductive oxide film 12 are used. Can be etched at once, and the over-etching amount L of the Ag film 11 can be reliably reduced.
  • the film thickness to of the transparent conductive oxide film 12 is in the range of 5 nm to 80 nm, the conductivity and luminous transmittance of the transparent conductive oxide film 12 are Can be secured.
  • the film thickness to of the transparent conductive oxide film 12 is optical in a two-layer structure of Ag film 11 / transparent conductive oxide film 12 using optical constants (refractive index and extinction coefficient) of each single-phase film. Simulation is performed to set the film thickness so that the transmittance in the visible light region is improved by the optical interference effect.
  • the Ag film 11 and the transparent conductive oxide film 12 are formed in this order on one surface of the substrate 30, but not limited to this, the transparent conductive oxide film is formed on one surface of the substrate 30.
  • a structure in which the material film 12 and the Ag film 11 are formed in this order may be employed.
  • a transparent conductive wiring 110 may be formed in which transparent conductive oxide films 112A and 112B are formed on one side and the other side of the Ag film 111, respectively.
  • the environmental resistance can be further improved.
  • the transparent conductive oxide film 112A and the transparent conductive oxide film 112B may be formed of transparent conductive oxides having different compositions. Further, an arbitrary number of four or more Ag films and transparent conductive oxide films may be stacked.
  • Example 1 A laminated film having a structure shown in Table 1 (a three-layer structure of transparent conductive oxide film / Ag film / transparent conductive oxide film) was produced as follows. When forming the Ag film, a sputtering target having a composition corresponding to the Ag film shown in Table 1 was prepared. The target size was 4 inches ⁇ ⁇ 6 mmt.
  • ITO In and Sn oxide sintered compact target containing 10 atomic% of Sn with respect to the sum of In and Sn.
  • IZO In and Zn oxide sintered compact target containing 30 atomic% of Zn with respect to the sum of In and Zn.
  • ZTO Zn and Sn oxide sintered compact target containing 50 atomic% of Sn with respect to the total of Zn and Sn.
  • AZO Zn and Al oxide sintered compact target containing 2 atomic% of Al with respect to the total of Zn and Al.
  • AZTO an oxide sintered compact target of Zn, Al, and Sn containing 2 atomic% of Al and 10 atomic% of Sn with respect to the total of Zn, Al, and Sn.
  • crystalline has a clear crystal peak observed by X-ray diffraction measurement as shown in FIG.
  • Amorphous means that no clear crystal peak was observed by X-ray diffraction measurement as shown in FIG.
  • the film forming conditions of the transparent conductive oxide film are as follows.
  • Substrate Washed glass substrate (Corning Eagle XG thickness 0.7mm)
  • Gas used Ar + 2% by volume oxygen
  • Gas pressure 0.67 Pa
  • Sputtering power DC 300W Target / substrate distance: 70 mm
  • the film forming conditions for the Ag film are as follows. Ultimate vacuum: 5 ⁇ 10 ⁇ 5 Pa or less Gas used: Ar Gas pressure: 0.67Pa Sputtering power: DC 200W Target / substrate distance: 70 mm
  • the obtained laminated film was etched as follows. First, a resist solution (OFPR-8600 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dropped on the laminated film, the resist was spin-coated, and prebaked in the atmosphere at 110 ° C. for 90 seconds to form a resist film.
  • a resist solution OFPR-8600 manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • the resist film was exposed by an exposure machine with a wiring pattern in which the wiring width and the wiring interval were each 30 ⁇ m.
  • the exposed laminate film was immersed in a developer (NMD-W manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 100 seconds at room temperature to remove the resist film in the exposed portion. Then, it post-baked on the conditions of 150 degreeC * 300 second in air
  • etching was performed by immersing in an oxalic acid etching solution (an oxalic acid aqueous solution having an oxalic acid concentration of 4 mass%) at a temperature of 40 ° C. for 100 to 400 seconds.
  • an oxalic acid etching solution an oxalic acid aqueous solution having an oxalic acid concentration of 4 mass
  • etching was performed by immersing in a mixed acid composed of phosphoric acid, nitric acid and acetic acid (ITO-02 manufactured by Kanto Chemical Co., Ltd.) at a temperature of 40 ° C. for 30 to 80 seconds.
  • a mixed acid composed of phosphoric acid, nitric acid and acetic acid (ITO-02 manufactured by Kanto Chemical Co., Ltd.) at a temperature of 40 ° C. for 30 to 80 seconds.
  • the obtained transparent conductive wiring was cleaved in order to observe the wiring cross section, and the cross section was observed using an electron microscope. And the difference of the position in the direction parallel to the film
  • Example 2 Next, in No. A transparent conductive wiring having the structure shown in Table 2 (a three-layer structure of transparent conductive oxide film / Ag film / transparent conductive oxide film) was produced in the same manner as in 1-7. About the obtained transparent conductive wiring, the propriety of the etching with an oxalic acid etching liquid was evaluated. The transparent conductive wiring after etching was observed with an optical microscope and SEM, and a residue was not confirmed and an overetching amount of 1 ⁇ m or less was “A”, and etching was possible.
  • Table 2 a three-layer structure of transparent conductive oxide film / Ag film / transparent conductive oxide film
  • the film thickness of the Ag film is thicker than the range of the present invention.
  • the Ag film could not be etched sufficiently.
  • the film thickness of the Ag film is No. in which the film thickness is set within the range of the present invention.
  • the Ag film can be sufficiently etched even when an oxalic acid etchant is used. there were. From the above experimental results, it was confirmed that etching can be performed with an oxalic acid etching solution by setting the film thickness of the Ag film within a range of 15 nm or less.
  • Example 3 Next, No. 1 of Example 1 was used. A transparent conductive wiring having a structure shown in Table 3 (a three-layer structure of transparent conductive oxide film / Ag film / transparent conductive oxide film) was produced in the same manner as in 1-7. About the obtained transparent conductive wiring, the propriety of the etching with an oxalic acid etching liquid was evaluated. The evaluation contents were the same as in Example 2. The evaluation results are shown in Table 3.
  • a crystalline ITO film was formed as a transparent conductive oxide film.
  • No. 92 having an amorphous ITO film formed thereon.
  • the etching property by the oxalic acid aqueous solution is inferior.
  • No. 1 in which a crystalline ITO film was formed as a transparent conductive oxide film.
  • No. 93 also had good etching properties. From the above experimental results, it was confirmed that the transparent conductive oxide film is preferably an amorphous film when an oxalic acid aqueous solution is used as the etching solution.
  • Example 4 Next, No. 1 of Example 1 was used. A transparent conductive wiring having the structure shown in Table 4 was produced in the same manner as in 1-7.
  • Example 4 a transparent conductive oxide film was formed on a glass substrate, and an Ag film was formed on the transparent conductive oxide film.
  • No. In No. 101-117 no residue was observed after the etching treatment with the oxalic acid etching solution, and the overetching amount was 1 ⁇ m or less.
  • the sheet resistance value was measured about the obtained transparent conductive wiring. The sheet resistance value was measured by a four-probe method using a surface resistance measuring instrument (Loresta AP MCP-T400, manufactured by Mitsubishi Yuka Co., Ltd.). The evaluation results are shown in Table 4.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

Fil conducteur transparent (10) comprenant un film d'Ag (11), constitué d'Ag ou d'un alliage d'Ag, et un film d'oxyde conducteur transparent (12) empilé sur le film d'Ag (11). Un motif de fil du fil conducteur transparent (10) est formé par gravure. Le film d'Ag (11) a une épaisseur ta de 15 nm ou moins, et une quantité de sur-gravure L du film d'Ag (11) par rapport au film d'oxyde conducteur transparente (12) est de 1 µm ou moins.
PCT/JP2016/055855 2015-02-27 2016-02-26 Fil conducteur transparent et procédé de fabrication de fil conducteur transparent WO2016136953A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201680002259.7A CN106796885B (zh) 2015-02-27 2016-02-26 透明导电配线及透明导电配线的制造方法
KR1020177004671A KR101777549B1 (ko) 2015-02-27 2016-02-26 투명 도전 배선 및 투명 도전 배선의 제조 방법

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2015-037950 2015-02-27
JP2015037950 2015-02-27
JP2015-217683 2015-11-05
JP2015217683 2015-11-05
JP2016034768A JP6020750B1 (ja) 2015-02-27 2016-02-25 透明導電配線、及び、透明導電配線の製造方法
JP2016-034768 2016-02-25

Publications (1)

Publication Number Publication Date
WO2016136953A1 true WO2016136953A1 (fr) 2016-09-01

Family

ID=56788764

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/055855 WO2016136953A1 (fr) 2015-02-27 2016-02-26 Fil conducteur transparent et procédé de fabrication de fil conducteur transparent

Country Status (1)

Country Link
WO (1) WO2016136953A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018139402A1 (fr) * 2017-01-25 2018-08-02 Tdk株式会社 Film conducteur transparent pour antennes

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07114841A (ja) * 1993-10-18 1995-05-02 Toshiba Corp 透明導電膜、その形成方法および透明導電膜の加工方法
JPH09123337A (ja) * 1995-03-22 1997-05-13 Toppan Printing Co Ltd 多層導電膜、並びにこれを用いた透明電極板および液晶表示装置
JPH11302876A (ja) * 1998-04-16 1999-11-02 Nippon Sheet Glass Co Ltd 透明導電膜の電極パターン加工方法
JP2005250191A (ja) * 2004-03-05 2005-09-15 Idemitsu Kosan Co Ltd 半透過・半反射電極基板、及びその製造方法、及びその半透過・半反射電極基板を用いた液晶表示装置
JP2015030896A (ja) * 2013-08-05 2015-02-16 出光興産株式会社 スパッタリングターゲット及び酸化物透明導電膜

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07114841A (ja) * 1993-10-18 1995-05-02 Toshiba Corp 透明導電膜、その形成方法および透明導電膜の加工方法
JPH09123337A (ja) * 1995-03-22 1997-05-13 Toppan Printing Co Ltd 多層導電膜、並びにこれを用いた透明電極板および液晶表示装置
JPH11302876A (ja) * 1998-04-16 1999-11-02 Nippon Sheet Glass Co Ltd 透明導電膜の電極パターン加工方法
JP2005250191A (ja) * 2004-03-05 2005-09-15 Idemitsu Kosan Co Ltd 半透過・半反射電極基板、及びその製造方法、及びその半透過・半反射電極基板を用いた液晶表示装置
JP2015030896A (ja) * 2013-08-05 2015-02-16 出光興産株式会社 スパッタリングターゲット及び酸化物透明導電膜

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018139402A1 (fr) * 2017-01-25 2018-08-02 Tdk株式会社 Film conducteur transparent pour antennes
JPWO2018139402A1 (ja) * 2017-01-25 2019-11-21 Ｔｄｋ株式会社 アンテナ用透明導電フィルム

Similar Documents

Publication Publication Date Title
WO2016024615A1 (fr) Film stratifié, film de câblage stratifié, et procédé de fabrication d'un film de câblage stratifié
JP6020750B1 (ja) 透明導電配線、及び、透明導電配線の製造方法
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
KR101951045B1 (ko) 액정표시장치용 어레이 기판의 제조방법
JP6135275B2 (ja) 保護膜形成用スパッタリングターゲット
JP2013060655A (ja) 電子部品用積層配線膜および被覆層形成用スパッタリングターゲット材
JP4655281B2 (ja) 薄膜配線層
JP2019203194A (ja) 積層膜、及び、Ａｇ合金スパッタリングターゲット
KR102189087B1 (ko) 보호막 형성용 스퍼터링 타깃 및 적층 배선막
JP6250614B2 (ja) Ｃｕ積層膜、およびＣｕ合金スパッタリングターゲット
JP5724998B2 (ja) 保護膜形成用スパッタリングターゲットおよび積層配線膜
JP5757318B2 (ja) 保護膜形成用スパッタリングターゲットおよび積層配線膜
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
WO2016136953A1 (fr) Fil conducteur transparent et procédé de fabrication de fil conducteur transparent
WO2016111202A1 (fr) Film multicouche
JP6398594B2 (ja) スパッタリングターゲット
JP6037208B2 (ja) 電子部品用積層配線膜および被覆層形成用スパッタリングターゲット材
JP2019131850A (ja) 積層膜、及び、Ａｇ合金スパッタリングターゲット
WO2016132847A1 (fr) FILM D'ALLIAGE DE Cu ET FILM MULTICOUCHE DE Cu
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
WO2017131183A1 (fr) Film conducteur transparent multicouche, film de câblage multicouche et procédé de fabrication de film de câblage multicouche
JP2018087360A (ja) 酸化物スパッタリングターゲット
KR102245555B1 (ko) 식각액 조성물 및 이를 이용한 투명 전극의 형성방법

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: 16755697

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20177004671

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16755697

Country of ref document: EP

Kind code of ref document: A1