WO2015166963A1 - 透明導電性フィルム及びその製造方法 - Google Patents
透明導電性フィルム及びその製造方法 Download PDFInfo
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- WO2015166963A1 WO2015166963A1 PCT/JP2015/062881 JP2015062881W WO2015166963A1 WO 2015166963 A1 WO2015166963 A1 WO 2015166963A1 JP 2015062881 W JP2015062881 W JP 2015062881W WO 2015166963 A1 WO2015166963 A1 WO 2015166963A1
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- 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
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- 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
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- 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
- C23C14/10—Glass or silica
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/354—Introduction of auxiliary energy into the plasma
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
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- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- 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
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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- 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
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- C—CHEMISTRY; METALLURGY
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
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- 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
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
Definitions
- the present invention relates to a transparent conductive film and a method for producing the same.
- the transparent conductive film so-called conductive glass in which an ITO film (indium-tin composite oxide film) is formed on a glass substrate is well known.
- a glass substrate is inferior in flexibility and workability, and may not be used depending on applications.
- ITO films have been formed on various polymer film substrates such as polyethylene terephthalate film due to advantages such as flexibility and workability, as well as excellent impact resistance and light weight.
- a transparent conductive film has been proposed.
- a transparent conductive material represented by a touch panel is required to have characteristics such as high transparency, high transmission, and high durability.
- a structure is known in which sputtering is performed so that the constituent atoms of the sputtering gas in the thin film are 0.05 atomic% or less when the transparent thin film is formed by sputtering ( Patent Document 1).
- the ITO film formed on the polymer film substrate has reduced specific resistance and surface resistance for high sensitivity (improved operability) and low power consumption in order to cope with the large screen of the touch panel.
- the demand is growing.
- a technique for forming an ITO film on a film substrate by a magnetron sputtering method in which a horizontal magnetic field on a target material is 50 mT or more has been proposed. (See Patent Document 2).
- FIG. 3 is a conceptual diagram schematically showing a process of forming an ITO film by sputtering.
- the ions (particularly argon ions 4) generated in this way collide with the target 13, and the ejected target particles 2 'are deposited on the polymer film substrate 1, whereby the transparent conductive layer 2 is formed.
- the transparent conductive layer 2 may incorporate hydrogen atoms 6 and carbon atoms derived from moisture and organic components contained in the polymer film substrate 1 or moisture in the sputtering atmosphere.
- the inventors of the present invention have repeatedly studied based on the prediction that hydrogen atoms, carbon atoms and the like incorporated in the transparent conductive layer act as impurities and influence these on the resistance characteristics.
- An object of the present invention is to provide a transparent conductive film that realizes the low resistance characteristics of a transparent conductive layer.
- the present inventors have found that there is a certain correlation between the impurity contained in the transparent conductive layer and the resistance value, and this is controlled.
- the present invention has been completed based on the new technical knowledge that the above-described object can be achieved.
- the present invention comprises a polymer film substrate, A transparent conductive film comprising a transparent conductive layer formed on at least one surface side of the polymer film substrate,
- the atomic weight of carbon atoms in the transparent conductive layer is 3 ⁇ 10 20 atoms / cm 3 or less
- the present invention relates to a transparent conductive film comprising an inorganic undercoat layer formed by a vacuum film formation method between the polymer film substrate and the transparent conductive layer.
- the present invention also includes a polymer film substrate, A transparent conductive film comprising a transparent conductive layer formed on at least one surface side of the polymer film substrate, Between the polymer film substrate and the transparent conductive layer, provided with an inorganic undercoat layer formed by a vacuum film formation method, The present invention relates to a transparent conductive film in which the atomic weight of hydrogen atoms in the transparent conductive layer is 3.7 ⁇ 10 20 atoms / cm 3 or less.
- the existing atomic weight of carbon atoms in the transparent conductive layer (hereinafter also simply referred to as “abundance”) is set to 3 ⁇ 10 20 atoms / cm 3 or lower, or the existing atomic weight of hydrogen atoms is set to 3. Since it is 7 ⁇ 10 20 atoms / cm 3 or less, the resistance of the transparent conductive layer can be reduced efficiently. Although this reason is not limited to any theory, it is guessed as follows. At the time of sputtering, carbon atoms and hydrogen atoms derived mainly from organic components contained in the polymer film substrate may be taken into the transparent conductive layer.
- Carbon atoms or hydrogen atoms taken into the transparent conductive layer in the sputtering process act as impurities.
- the resistance characteristics of a transparent conductive layer depend on the intrinsic mobility and carrier density of the material, but generally impurities in the transparent conductive layer cause inhibition of crystal growth and decrease in mobility due to neutron scattering. It is considered that when the abundance of incorporated carbon atoms or hydrogen atoms is large, the resistance value of the transparent conductive layer increases and the crystal conversion time also increases.
- the transparent conductive film since the abundance of carbon atoms or hydrogen atoms in the transparent conductive layer is kept low, the mobility of the transparent conductive layer can be increased, thereby effectively reducing the transparency of the transparent conductive layer. Resistance can be achieved, and even when crystal conversion of the transparent conductive layer is performed, it can be completed in a short time.
- the transparent conductive film includes an inorganic undercoat layer formed by a vacuum film forming method between the polymer film substrate and the transparent conductive layer.
- an inorganic undercoat layer formed by a vacuum film forming method between the polymer film substrate and the transparent conductive layer.
- the specific resistance of the transparent conductive layer is preferably in the range of 1.1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm to 2.8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. Thereby, it can contribute to low resistance of a transparent conductive film.
- the transparent conductive layer is preferably an indium-tin composite oxide layer.
- the transparent conductive layer is an indium-tin composite oxide (hereinafter also referred to as “ITO”) layer, a transparent conductive layer having a lower resistance can be formed.
- ITO indium-tin composite oxide
- the transparent conductive layer is crystalline. By making the transparent conductive layer crystalline, there are advantages that transparency is improved, resistance change after the humidifying heat test is small, and humidifying heat reliability is improved.
- the content of tin oxide in the indium-tin composite oxide layer is preferably 0.5% by weight to 15% by weight with respect to the total amount of tin oxide and indium oxide.
- the carrier density can be increased and the specific resistance can be further reduced.
- Content of the said tin oxide can be suitably selected in the said range according to the specific resistance of a transparent conductive layer.
- the transparent conductive layer has a structure in which a plurality of indium-tin composite oxide layers are laminated, It is preferable that at least two of the plurality of indium-tin composite oxide layers have different amounts of tin. Not only the abundance of argon atoms and hydrogen atoms in the transparent conductive layer, but also the transparent conductive layer having such a specific layer structure promotes shortening of the crystal conversion time and further lowering the resistance of the transparent conductive layer. be able to.
- all of the indium-tin composite oxide layer is crystalline. Since all indium-tin composite oxide layers are crystalline, the transparency of the transparent conductive film is improved, the resistance change after the humidification heat test is small, and the humidification heat reliability is improved. Brought about.
- the transparent conductive layer has a first indium-tin composite oxide layer and a second indium-tin composite oxide layer in this order from the polymer film substrate side.
- the content of tin oxide in the first indium-tin composite oxide layer is 6% by weight to 15% by weight with respect to the total amount of tin oxide and indium oxide
- the second indium-tin composite oxide The content of tin oxide in the layer is preferably 0.5% by weight to 5.5% by weight with respect to the total amount of tin oxide and indium oxide.
- the transparent conductive film includes an organic undercoat layer formed by a wet coating method between the polymer film substrate and the transparent conductive layer.
- the surface of the polymer film substrate tends to be smoothed, so that the ITO film formed thereon is also smoothed.
- it contributes to the reduction in resistance of the ITO film. it can.
- an optical characteristic can also be improved.
- the transparent conductive film includes an organic undercoat layer formed by a wet coating method on at least one surface side of the polymer film, An inorganic undercoat layer formed by a vacuum film formation method; The transparent conductive layer is provided in this order.
- the present invention is also a method for producing the transparent conductive film, A step A in which the polymer film substrate is placed under a vacuum with an ultimate vacuum of 3.5 ⁇ 10 ⁇ 4 Pa or less, and a transparent conductive layer is formed by sputtering on at least one surface side of the polymer film substrate.
- Process B Including After the step A and before the step B, the transparent conductive film includes a step of forming an inorganic undercoat layer by a vacuum film forming method on the surface side of the polymer film substrate on which the transparent conductive layer is formed.
- the present invention relates to a film manufacturing method.
- the manufacturing method includes the step A for evacuating the polymer film substrate to a predetermined ultimate vacuum, the amount of moisture and organic components in the polymer film substrate and the sputtering atmosphere can be reduced. As a result, the amount of carbon atoms taken into the transparent conductive layer can be reduced.
- an inorganic undercoat layer is formed on the surface of the polymer film substrate on which the transparent conductive layer is formed by a vacuum film formation method.
- Process. Blocking moisture and organic atom-derived hydrogen atoms and carbon atoms derived from the polymer film substrate into the transparent conductive layer by interposing an inorganic undercoat layer between the polymer film substrate and the transparent conductive layer Thus, the specific resistance of the transparent conductive layer can be reduced more efficiently.
- the production method preferably includes a step of crystal conversion by heating the transparent conductive layer.
- the transparent conductive layer 2 is formed on one surface side of the polymer film substrate 1.
- the transparent conductive layer may be formed on both sides of the substrate 1.
- one or two or more undercoat layers may be provided between the polymer film substrate 1 and the transparent conductive layer 2.
- the undercoat layers 3 and 4 are provided from the polymer film substrate 1 side.
- the polymer film substrate 1 has a strength necessary for handleability and has transparency in the visible light region.
- a film excellent in transparency, heat resistance, and surface smoothness is preferably used.
- polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins, polycycloolefins, polycarbonates, Examples thereof include single component polymers such as polyether sulfone, polyarylate, polyimide, polyamide, polystyrene, norbornene, and copolymerized polymers with other components.
- polyester resins are preferably used because they are excellent in transparency, heat resistance, and mechanical properties.
- polyester resin polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and the like are particularly suitable.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- the polymer film substrate is preferably stretched from the viewpoint of strength, and more preferably biaxially stretched. It does not specifically limit as a extending
- the thickness of the polymer film substrate is not particularly limited, but is preferably in the range of 2 to 200 ⁇ m, more preferably in the range of 2 to 150 ⁇ m, and further preferably in the range of 20 to 150 ⁇ m. preferable.
- the thickness of the film is less than 2 ⁇ m, the mechanical strength may be insufficient, and it may be difficult to continuously form the transparent conductive layer 2 in a roll shape.
- the thickness of the film exceeds 200 ⁇ m, the scratch resistance of the transparent conductive layer 2 and the dot characteristics when a touch panel is formed may not be achieved.
- the surface of the substrate is preliminarily subjected to etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, and undercoating treatment, and adhesion to the transparent conductive layer 2 formed on the substrate. You may make it improve property.
- etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, and undercoating treatment, and adhesion to the transparent conductive layer 2 formed on the substrate. You may make it improve property.
- the surface of the base material may be removed and cleaned by solvent cleaning or ultrasonic cleaning as necessary.
- the polymer film as the substrate 1 is provided as a roll of a long film, and the transparent conductive layer 2 is continuously formed thereon by a roll-to-roll method. A transparent conductive film can be obtained.
- the transparent conductive layer 2 is formed on at least one surface side of the polymer film substrate 1.
- Presence atomic weight of carbon atoms in the transparent conductive layer 2 is preferably 3 ⁇ 10 20 atoms / cm 3 or less, more preferably 2 ⁇ 10 20 atoms / cm 3 or less, more preferably 1 ⁇ 10 20 atoms / cm 3 or less, 0.5 ⁇ 10 20 atoms / cm 3 or less is particularly preferable.
- the lower limit of the existing atom concentration of carbon atoms is preferable, it is preferably 0.001 ⁇ 10 20 atoms / cm 3 or more, and more preferably 0.01 ⁇ 10 20 atoms / cm 3 or more. .
- Carbon atoms as impurities that may be contained in the transparent conductive layer are included in the undercoat layer when the lower layer has an undercoat layer formed of an organic component or organic substance contained in the polymer film substrate. It is thought to be derived from organic components.
- Carbon atoms in the transparent conductive layer are quantified by measuring the amount of impurities in the depth direction by secondary ion mass spectrometry (Secondary Ion Mass Spectrometry) while sequentially sputtering the transparent conductive layer from the surface using Cs + ions.
- This analytical method is commonly referred to as dynamic SIMS.
- As the amount of impurities contained in the ITO layer data at the center point of the ITO film thickness (25 nm point if the ITO layer is 50 nm) is adopted.
- the carbon atom can detect the element contained in the transparent conductive layer without being contaminated on the surface of the transparent conductive layer or affected by the element contained in the substrate. Details of the measurement method are as described in the examples.
- the existing atomic weight of hydrogen atoms in the transparent conductive layer 2 is preferably 3.7 ⁇ 10 20 atoms / cm 3 or less, more preferably 2 ⁇ 10 20 atoms / cm 3 or less, and 1.5 ⁇ 10 20 atoms / cm 3 or less. Is more preferable, and 1 ⁇ 10 20 atoms / cm 3 or less is particularly preferable.
- the lower limit of the existing atom concentration of hydrogen atoms is preferable, it is preferably 0.001 ⁇ 10 20 atoms / cm 3 or more, more preferably 0.05 ⁇ 10 20 atoms / cm 3 or more. .
- hydrogen atoms as impurities that can be contained in the transparent conductive layer include moisture and organic components contained in the polymer film substrate, moisture in the sputtering atmosphere, and an undercoat layer formed of organic matter in the lower layer. Is considered to be derived from moisture and organic components contained in the undercoat layer.
- Quantification of hydrogen atoms in the transparent conductive layer can be performed in the same procedure as the quantification of carbon atoms.
- the constituent material of the transparent conductive layer 2 is not particularly limited, and is at least selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W.
- a metal oxide of one kind of metal is preferably used.
- the metal oxide may further contain a metal atom shown in the above group, if necessary.
- ITO indium-tin composite oxide
- ATO antimony-tin composite oxide
- the content of tin oxide (SnO 2 ) in the metal oxide is that of tin oxide and indium oxide (In 2 O 3 ).
- the total amount is preferably 0.5 to 15% by weight, more preferably 3 to 15% by weight, still more preferably 5 to 12% by weight, and 6 to 12% by weight. It is particularly preferred that If the amount of tin oxide is too small, the durability of the ITO film may be inferior. Moreover, when there is too much quantity of a tin oxide, an ITO film
- ITO in this specification may be a complex oxide containing at least indium (In) and tin (Sn), and may contain additional components other than these.
- additional component include metal elements other than In and Sn. Specifically, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe , Pb, Ni, Nb, Cr, Ga, and combinations thereof.
- the content of the additional component is not particularly limited, but may be 3% by weight or less.
- the transparent conductive layer 2 may have a structure in which a plurality of indium-tin composite oxide layers having different amounts of tin are laminated.
- the ITO layer may be two layers or three or more layers.
- the tin oxide content in the first indium-tin composite oxide layer is preferably 6 to 15% by weight, more preferably 6 to 12% by weight, based on the total amount of tin oxide and indium oxide. Preferably, it is 6.5 to 10.5% by weight.
- the tin oxide content in the second indium-tin composite oxide layer is preferably 0.5% by weight to 5.5% by weight with respect to the total amount of tin oxide and indium oxide. It is more preferably 5% by weight, and further preferably 1 to 5% by weight.
- the transparent conductive layer 2 has a first indium-tin composite oxide layer, a second indium-tin composite oxide layer, and a third indium-tin composite oxide layer in this order from the polymer film substrate 1 side.
- the tin oxide content in the first indium-tin composite oxide layer is 0.5 wt% to 5.5 wt% with respect to the total amount of tin oxide and indium oxide. It is preferably 1 to 4% by weight, more preferably 2 to 4% by weight.
- the tin oxide content in the second indium-tin composite oxide layer is preferably 6 to 15% by weight, and preferably 7 to 12% by weight with respect to the total amount of tin oxide and indium oxide.
- the tin oxide content in the third indium-tin composite oxide layer is preferably 0.5 wt% to 5.5 wt% with respect to the total amount of tin oxide and indium oxide, and is 1 to 4 wt%. %, More preferably 2 to 4% by weight.
- the thickness of the transparent conductive layer 2 can be suitably applied to touch panel applications by setting the thickness to 15 nm to 40 nm, preferably 15 nm to 35 nm.
- the transparent conductive layer 2 may be crystalline or amorphous.
- an ITO film is formed as a transparent conductive layer by a sputtering method
- the base material 1 is a polymer film
- there is a restriction due to heat resistance so that sputtering film formation at a high temperature cannot be performed.
- the ITO immediately after film formation is substantially an amorphous film (some of which may be crystallized).
- Such an amorphous ITO film has a lower transmittance than a crystalline ITO film, and may cause problems such as a large resistance change after a humidification heat test.
- the transparent conductive layer may be converted into a crystalline film by annealing in the presence of oxygen in the atmosphere.
- the transparent conductive layer may be a semi-crystalline film that is not completely converted into a crystalline film. If it is a semi-crystalline film, the above advantages can be obtained more easily than an amorphous film.
- the transparent conductive layer 2 is a crystalline film because the transparent conductive layer 2 is immersed in 20 ° C. hydrochloric acid (concentration 5% by weight) for 15 minutes, washed with water and dried, and the resistance between terminals is about 15 mm. It can be judged by measuring. In the present specification, it is assumed that the crystal conversion of the ITO film is completed when the inter-terminal resistance between 15 mm does not exceed 10 k ⁇ after immersion in hydrochloric acid, washing with water, and drying.
- the time required for crystal conversion of the amorphous transparent conductive layer by heating is short, but when obtaining a low resistivity film, the crystal conversion time tends to be long.
- the specific resistance can be greatly reduced by increasing the amount of tin oxide added (for example, 15% by weight).
- increasing the dopant concentration is a suitable means for reducing the specific resistance.
- the dopant acts as an impurity with respect to the host (main component)
- an ideal crystal structure can be obtained by increasing the dopant addition amount. Is difficult to form and requires a lot of energy for crystallization, so that the time required for the crystal conversion treatment becomes long.
- the heating time for crystal conversion of the amorphous transparent conductive layer can be appropriately set. However, in consideration of productivity in industrial use, it is preferably 10 minutes or more and 90 minutes or less, and preferably 10 minutes or more and 60 minutes or less. Is more preferable, and 10 minutes or more and 30 minutes or less are still more preferable. By setting within this range, crystal conversion can be completed while ensuring productivity.
- the heating temperature for crystal conversion of the amorphous transparent conductive layer is preferably 110 ° C. to 180 ° C., but from the viewpoint of problems caused by the high temperature (eg, precipitation of oligomers in a PET film), the heating temperature is 110 ° C. or higher and 150 ° C. ° C or lower is preferable, and 110 ° C or higher and 140 ° C or lower is more preferable. By setting to this range, it is possible to complete the crystal conversion of the transparent conductive layer while suppressing defects of the film base material.
- the surface resistance value of the transparent conductive layer after the amorphous transparent conductive layer is converted to crystalline by heating is preferably 200 ⁇ / ⁇ or less, more preferably 150 ⁇ / ⁇ or less, and 90 ⁇ / ⁇ . More preferably, it is as follows.
- the transparent conductive layer 2 preferably has a low specific resistance value of 1.1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm to 2.8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the specific resistance value of the transparent conductive layer after crystal conversion should be in the above range.
- the specific resistance value is preferably 1.1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or more and 2.5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, and 1.1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or more and 2.4 ⁇ 10 ⁇ It is more preferably 4 ⁇ ⁇ cm or less, and further preferably 1.1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or more and 2.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less.
- the transparent conductive layer 2 may be patterned by etching or the like.
- the transparent conductive layer 2 is preferably patterned in a stripe shape.
- the annealing treatment of the transparent conductive layer 2 may be performed after the transparent conductive layer 2 is patterned.
- an undercoat layer may be formed between the substrate 1 and the transparent conductive layer 2 in consideration of optical characteristics, electrical characteristics, mechanical characteristics, and the like.
- the layer structure of the undercoat layer may be a single layer structure or a multilayer structure in which two or more layers are laminated.
- the numerical value in the parenthesis indicates the refractive index
- an organic substance such as an acrylic resin, urethane resin, melamine resin, alkyd resin, siloxane polymer, organosilane condensate having a refractive index of about 1.4 to 1.6, or the above
- a mixture of an inorganic substance and the organic substance can be given.
- the undercoat layer may be an inorganic undercoat layer formed of the inorganic material, or may be an organic undercoat layer formed of the organic material or a mixture of the organic material and the inorganic material. Good.
- an inorganic undercoat layer may be laminated, an organic undercoat layer may be laminated, or a combination of an inorganic undercoat layer and an organic undercoat layer may be laminated. It may be.
- the surface roughness of the organic undercoat layer 3 formed on the polymer film substrate 1 is preferably 0.1 nm to 5 nm, more preferably 0.1 nm to 3 nm, and 0.1 nm to 1.5 nm. Is more preferable.
- the surface roughness Ra can be measured by AFM observation using a scanning probe microscope (SPI3800) manufactured by Seiko Instruments Inc., and made of Si 3 N 4 (spring constant 0.09 N / m in contact mode). ), The surface roughness (Ra) can be measured by 1 ⁇ m square scan.
- the thickness of the organic undercoat layer 3 can be appropriately set within a suitable range, but is preferably 15 nm to 1500 nm, more preferably 20 nm to 1000 nm, and most preferably 20 nm to 800 nm. Since the surface roughness can be sufficiently suppressed by setting to the above range, a high effect can be obtained with respect to a reduction in specific resistance. Moreover, the organic undercoat layer which laminated
- an inorganic undercoat layer 4 formed by a vacuum film forming method (for example, a sputtering method or a vacuum evaporation method) is provided between the polymer film substrate 1 and the transparent conductive layer 2.
- a vacuum film forming method for example, a sputtering method or a vacuum evaporation method
- the inorganic undercoat layer 4 having a high density by a vacuum film formation method it suppresses impurity gases such as water and organic gas released from the polymer film substrate when the transparent conductive layer 2 is formed by sputtering. can do. As a result, the amount of impurity gas taken into the transparent conductive layer can be reduced, which can contribute to suppression of specific resistance.
- the thickness of the inorganic undercoat layer 3 is preferably 2 nm to 100 nm, more preferably 3 nm to 50 nm, and most preferably 4 nm to 30 nm. By setting the above range, the emission of impurity gas can be suppressed. Moreover, the inorganic undercoat layer which laminated
- the transparent conductive film 10 includes an organic undercoat layer 3 formed by wet coating on at least one surface side of the polymer film 1 and an inorganic formed by vacuum film formation. It is preferable to provide the undercoat layer 4 and the transparent conductive layer 2 in this order.
- the surface becomes smooth and the impurity gas during sputtering can be suppressed, and the specific resistance of the transparent conductive layer can be effectively reduced. It becomes.
- each thickness of the said organic undercoat layer and the said inorganic undercoat layer can be suitably set from the said range.
- an undercoat layer on the transparent conductive layer forming surface side of the polymer film substrate 1, for example, even when the transparent conductive layer 2 is patterned into a plurality of transparent electrodes, the transparent conductive layer is formed. It is possible to reduce the difference in visibility between the region and the region where the transparent conductive layer is not formed.
- an undercoat layer can act also as a sealing layer which suppresses precipitation of low molecular weight components, such as an oligomer from a polymer film.
- a surface of the polymer film substrate 1 opposite to the surface on which the transparent conductive layer 2 is formed may be provided with a hard coat layer, an easy adhesion layer, an anti-blocking layer, or the like as necessary.
- those with other substrates bonded using appropriate adhesive means such as pressure-sensitive adhesives, or those in which a protective layer such as a separator is temporarily attached to a pressure-sensitive adhesive layer for bonding with other substrates It may be.
- the method for producing a transparent conductive film of the present embodiment includes a step A in which a polymer film substrate is placed under a vacuum having an ultimate vacuum of 3.5 ⁇ 10 ⁇ 4 Pa or less, and at least one of the polymer film substrates.
- the transparent conductive layer of the polymer film base material is formed after the step A and before the step B.
- a known vacuum film forming method such as a sputtering method or a vacuum vapor deposition method can be employed.
- FIG. 2 is a conceptual diagram showing a configuration of a sputter deposition apparatus according to an embodiment of the present invention.
- the base 1 is fed from a feed roll 53, is conveyed by a temperature control roll 52 through a guide roll 55, and is wound by a take-up roll 54 through a guide roll 56.
- the roll method is adopted.
- the inside of the sputter deposition apparatus 100 is evacuated to a predetermined pressure or less (exhaust means is not shown).
- the temperature adjustment roll 52 can be controlled to reach a predetermined temperature.
- the sputter deposition apparatus 100 of this embodiment includes one sputter chamber 11.
- the sputter chamber 11 is a region surrounded by the casing 101 of the sputter deposition apparatus 100, the partition wall 12, and the temperature control roll 52, and can be set to an independent sputter atmosphere during sputter deposition.
- the sputtering chamber 11 includes an indium-tin composite oxide (ITO) target 13 and a magnet electrode 14 that generates a horizontal magnetic field on the target 13.
- the ITO target 13 is connected to a DC power source 16 and an RF power source 17 and is discharged from each of these power sources, and a transparent conductive layer is formed on the substrate 1.
- the shape of the ITO target 13 may be a flat plate type (planar) as shown in FIG. 2 or a cylindrical type (rotary).
- a target containing an indium-tin composite oxide (In 2 O 3 —SnO 2 target) is preferably used.
- the amount of tin oxide (SnO 2 ) in the metal oxide target is the sum of tin oxide (SnO 2 ) and indium oxide (In 2 O 3 ).
- the weight is preferably 0.5 to 15% by weight, more preferably 3 to 15% by weight, still more preferably 5 to 12% by weight, and 6 to 12% by weight. It is particularly preferred. If the amount of tin oxide in the target is too small, the durability of the ITO film may be inferior. Moreover, when there is too much quantity of a tin oxide, an ITO film
- the ultimate vacuum in the sputter deposition apparatus 100 is preferably 3.5 ⁇ 10 ⁇ 4 Pa or less, more preferably 1.0 ⁇ 10 ⁇ 4 Pa. It exhausts until it becomes the following, and puts the polymer film base material 1 in a vacuum environment (process A). Thereby, it can be set as the atmosphere which removed impurities, such as the water in the sputter film-forming apparatus 100, and the organic gas generated from a polymer film base material. The presence of moisture and organic gas terminates dangling bonds generated during sputter deposition and prevents crystal growth of conductive oxides such as ITO, and causes carrier scattering in the transparent conductive layer to increase mobility. It is because it lowers.
- an inert gas such as Ar as a sputtering gas and an oxygen gas which is a reactive gas, if necessary, are introduced to perform sputtering film formation under a reduced pressure of 1 Pa or less.
- the discharge pressure in the sputtering chamber 11 during film formation is preferably 0.09 Pa to 1 Pa, and more preferably 0.1 Pa to 0.8 Pa. If the discharge pressure is too high, the sputtering rate tends to decrease. Conversely, if the discharge pressure is too low, the discharge may become unstable.
- the incorporation of argon atoms as impurities into the transparent conductive layer 2 is suppressed by lowering the discharge voltage.
- the reason why the incorporation of impurities can be suppressed by suppressing the discharge voltage is not clear, but is estimated to be as follows.
- argon ions moving towards the target have a high kinetic energy.
- argon recoiling from the target collides with the transparent conductive layer 2 while having high energy, so that it is considered that the amount of argon atoms taken into the transparent conductive layer 2 increases.
- the power source is an RF superimposed DC power source, and the sputtering pressure (discharge pressure) is set high within a preferable range (for example, 0. 6 Pa), increasing the horizontal magnetic field strength of the magnet (for example, 100 mT), and setting the discharge output within a preferable range.
- a preferable range for example 0. 6 Pa
- an RF superimposed DC power source is adopted as a power source to lower the effective discharge voltage, and a relatively high horizontal magnetic field is generated on the target 13 by the magnet electrode 14 to generate plasma in the system.
- the type of power source installed in the sputtering apparatus of this embodiment is not limited, and may be the RF superimposed DC power source described with reference to the drawings, and may be the RF power source, whether it is a DC power source or an MF power source. These power sources may be combined.
- An RF superimposed DC power source is preferable from the viewpoint of efficient reduction of the discharge voltage.
- the discharge voltage (absolute value) is preferably from 100 V to 400 V, more preferably from 120 V to 380 V, more preferably from 120 V to 300 V, and even more preferably from 120 V to 250 V. By setting it as these ranges, the amount of impurities taken into the transparent conductive layer 2 can be reduced while securing the film formation rate.
- the strength of the horizontal magnetic field on the target surface can be set in consideration of the amount of argon atoms taken in, the film formation speed, etc., preferably 20 mT or more and 200 mT or less, more preferably 60 mT or more and 150 mT or less, and more preferably 80 mT or more and 130 mT or less. Further preferred.
- the partial pressure of water in the film formation atmosphere is preferably small. .
- the partial pressure of water during film formation is preferably 1.0% or less, more preferably 0.8% or less, and 0.1% or less with respect to the partial pressure of the inert gas. Is more preferable.
- the water pressure during film formation can be within the above range, and An atmosphere in which impurities such as organic gas generated from the material are removed can be obtained.
- the film substrate temperature at the time of forming the transparent conductive layer is not particularly limited. Usually, the temperature can be set to ⁇ 40 ° C. or more and 200 ° C. or less. Conventionally, it is known that, by setting the substrate temperature to a high temperature exceeding, for example, 100 ° C. and not more than 200 ° C., the crystal conversion property of the transparent conductive film can be improved and the resistance can be reduced. On the other hand, since the transparent conductive film of the present invention has the amount of impurities such as argon atoms and hydrogen atoms within a predetermined range, there is little inhibition of crystal conversion of the transparent conductive layer due to such impurities, and the substrate temperature is low. Even if the film is formed at a low temperature of 100 ° C. or lower, the crystal conversion property is good and a low specific resistance can be realized.
- the film substrate temperature is, for example, more than 100 ° C and 200 ° C or less, preferably 120 ° C or more and 180 ° C or less, more preferably 130 ° C or more and 160 ° C or less. .
- the film substrate temperature is, for example, ⁇ 40 ° C. or higher, preferably ⁇ 30 ° C. or higher, more preferably -20 ° C or higher, more preferably -15 ° C or higher, for example, 80 ° C or lower, preferably 40 ° C or lower, more preferably 30 ° C or lower, still more preferably, It is 20 degrees C or less, Most preferably, it is 10 degrees C or less.
- the film base material temperature is a set temperature of the base of the base material at the time of sputtering film formation.
- the film substrate temperature in the case where film formation is continuously performed by a roll sputtering apparatus including a film formation drum is a film formation drum on which sputter film formation is performed. It is the temperature of the surface.
- the film base material temperature in the case of performing sputter film formation with a batch-type sputtering apparatus is the temperature of the base material holder surface on which the film base material is placed.
- thermosetting resin composition containing a melamine resin: alkyd resin: organosilane condensate in a weight ratio of 2: 2: 1 in terms of solid content was diluted with methyl ethyl ketone so that the solid content concentration was 8% by weight.
- the obtained diluted composition was applied to one main surface of a polymer film substrate made of a 50 ⁇ m thick PET film (trade name “Diafoil”, manufactured by Mitsubishi Plastics), and heat-cured at 150 ° C. for 2 minutes to form a film.
- An organic undercoat layer having a thickness of 35 nm was formed.
- Ra was 0.5 nm. Furthermore, a SiO 2 layer having a thickness of 5 nm was formed as an inorganic undercoat layer on the organic undercoat layer by sputtering using an MF power source.
- an RF superimposed DC magnetron sputtering method discharge voltage 150 V, RF frequency 13.56 MHz, A second transparent conductor layer made of an indium-tin composite oxide layer having a thickness of 5 nm was formed at a ratio of RF power to DC power (RF power / DC power) of 0.8).
- the transparent conductive layer formed by laminating the first transparent conductor layer and the second transparent conductor layer was produced.
- the produced transparent conductive layer was heated in a 150 ° C. hot air oven to perform a crystal conversion treatment, thereby obtaining a transparent conductive film having a crystalline transparent conductive layer.
- Example 2 On the organic undercoat layer, a SiO 2 layer having a thickness of 10 nm was formed as an inorganic undercoat layer by sputtering using an MF power source, and the sputtering power source was a DC power source, and the flow ratio of Ar and O 2 was Ar.
- Example 3 A transparent conductive layer and a transparent conductive layer were formed in the same manner as in Example 2 except that a single transparent conductive layer having a thickness of 25 nm was formed using a sintered body of 10% by weight tin oxide and 90% by weight indium oxide as a target. A transparent conductive film was produced.
- Example 1 A transparent conductive layer and a transparent conductive film were formed in the same manner as in Example 3 except that the inorganic undercoat layer was not formed and the ultimate vacuum in the degassing treatment of the film was 3.9 ⁇ 10 ⁇ 4 Pa. Produced.
- Example 2 The transparent conductive layer and the transparent conductive film were formed in the same manner as in Example 3 except that the inorganic undercoat layer was not formed and the ultimate vacuum in the degassing treatment of the film was 4.8 ⁇ 10 ⁇ 4 Pa. Produced.
- Example 1 A transparent conductive layer and a transparent conductive film were produced in the same manner as in Example 1 except that the inorganic undercoat layer was not formed.
- Reference Example 2 Reference Example, except that an inorganic undercoat layer was not formed and a sintered body of 10% by weight tin oxide and 90% by weight indium oxide was used as a target to form a single transparent conductive layer having a thickness of 25 nm. In the same manner as in Example 1, a transparent conductive layer and a transparent conductive film were produced.
- the film thickness of the ITO film was measured under the following measurement conditions using a powder X-ray diffractometer (“RINT-2000” manufactured by Rigaku Corporation) using the X-ray reflectivity method as a measurement principle.
- the film thickness was calculated by measuring the X-ray reflectivity and analyzing the acquired measurement data with analysis software (“GXRR3” manufactured by Rigaku Corporation).
- the analysis conditions are as follows, and a two-layer model of a film base and an ITO thin film with a density of 7.1 g / cm 3 is adopted, and the least square fitting is performed with the film thickness and surface roughness of the ITO film as variables.
- the film thickness of the ITO film was analyzed.
- FIG. 4 is a depth profile of carbon atoms detected in this measurement.
- the left end is the surface
- the right end is the substrate side
- the right end portion of the In peak is the end in the depth direction of the ITO film.
- the surface contamination components and carbon atoms contained in the film are detected.
- the amount of carbon atoms detected at almost the central point of the film thickness of the transparent conductive layer, which is not affected by the carbon component contained in the contamination component or film base material, is the present atomic amount of carbon atoms in the ITO film thickness. It was.
- the method for determining the central point is as follows. As described above, in FIG. 4, the left end is the surface, the right end is the substrate side, and the right end portion of the In peak is the end in the depth direction of the ITO film. As for the central point of the ITO film thickness, the positions where the In detection intensity was halved on the surface side and the substrate side with respect to the peak intensity were the outermost surface part and the deepest part of the ITO layer, and the intermediate point was the central point.
- a transparent conductive film having an ITO film formed on a polymer film substrate is heated in a hot air oven at 150 ° C. to carry out a crystal conversion treatment, and hydrochloric acid at 20 ° C. and a concentration of 5% by weight. After dipping for 15 minutes, it was washed with water and dried, and the resistance between terminals between 15 mm was measured with a tester. In this specification, after immersion in hydrochloric acid, washing with water, and drying, when the inter-terminal resistance between 15 mm does not exceed 10 k ⁇ , the crystal conversion of the ITO film is completed. Moreover, the said measurement was implemented every 30 minutes of heating time, and the time which the crystallization completion was able to be confirmed was evaluated as crystal conversion time.
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Abstract
Description
前記高分子フィルム基材の少なくとも一方の面側に形成された透明導電層とを備える透明導電フィルムであって、
前記透明導電層中の炭素原子の存在原子量が3×1020atoms/cm3以下であり、
前記高分子フィルム基材と前記透明導電層との間に、真空成膜法にて形成された無機アンダーコート層を備える透明導電性フィルムに関する。
前記高分子フィルム基材の少なくとも一方の面側に形成された透明導電層を備える透明導電性フィルムであって、
前記高分子フィルム基材と前記透明導電層との間に、真空成膜法にて形成された無機アンダーコート層を備え、
前記透明導電層中の水素原子の存在原子量が3.7×1020atoms/cm3以下である透明導電性フィルムに関する。
前記複数のインジウム-スズ複合酸化物層のうち少なくとも2層では互いにスズの存在量が異なることが好ましい。透明導電層におけるアルゴン原子及び水素原子の存在量のみならず、透明導電層をこのような特定の層構造とすることにより、結晶転化時間の短縮化や透明導電層のさらなる低抵抗化を促進することができる。
湿式塗工法にて形成された有機アンダーコート層と、
真空成膜法にて形成された無機アンダーコート層と、
前記透明導電層とをこの順で備える。
高分子フィルム基材を到達真空度が3.5×10-4Pa以下の真空下に置く工程A、及び
前記高分子フィルム基材の少なくとも一方の面側にスパッタリング法により透明導電層を形成する工程B
を含み、
前記工程Aの後であって前記工程Bの前に、前記高分子フィルム基材の前記透明導電層が形成される面側に真空成膜法により無機アンダーコート層を形成する工程を含む透明導電フィルムの製造方法に関する。
図1に示すように、透明導電性フィルム10では、高分子フィルム基材1の一方の面側に透明導電層2が形成されている。なお、透明導電層は基材1の両面側に形成されていてもよい。また、高分子フィルム基材1と透明導電層2との間に、1層又は2層以上のアンダーコート層を備えていてもよい。図1に示す態様では、高分子フィルム基材1側からアンダーコート層3及び4を備えている。
高分子フィルム基材1は、取り扱い性に必要な強度を有し、かつ可視光領域において透明性を有する。高分子フィルム基材としては、透明性、耐熱性、表面平滑性に優れたフィルムが好ましく用いられ、例えば、その材料として、ポリエチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル、ポリオレフィン、ポリシクロオレフィン、ポリカーボネート、ポリエーテルスルフォン、ポリアリレート、ポリイミド、ポリアミド、ポリスチレン、ノルボルネンなどの単一成分の高分子または他の成分との共重合高分子等が挙げられる。中でも、ポリエステル系樹脂は、透明性、耐熱性、および機械特性に優れることから好適に用いられる。ポリエステル系樹脂としては、ポリエチレンテレフタレート(PET)やポリエチレンナフタレート(PEN)等が特に好適である。また、高分子フィルム基材は強度の観点から延伸処理が行われていることが好ましく、二軸延伸処理されていることがより好ましい。延伸処理としては特に限定されず、公知の延伸処理を採用することができる。
透明導電層2は、高分子フィルム基材1の少なくとも一方の面側に形成されている。
また、基材1と透明導電層2との間には、光学特性や電気特性、機械的特性等を考慮してアンダーコート層が形成されていてもよい。アンダーコート層の層構造としては単層構造であってもよく、2層以上が積層された多層構造であってもよい。
本実施形態の透明導電性フィルムの製造方法は、高分子フィルム基材を到達真空度が3.5×10-4Pa以下の真空下に置く工程A、及び前記高分子フィルム基材の少なくとも一方の面側にスパッタリング法により透明導電層を形成する工程Bを含み、さらに、前記工程Aの後であって前記工程Bの前に、前記高分子フィルム基材の前記透明導電層が形成される面側に真空成膜法により無機アンダーコート層を形成する工程を含む。
従来、基材温度を、例えば100℃を超え200℃以下の高温とすることで、透明導電性フィルムの結晶転化性を向上でき、低抵抗化に寄与することが知られている。一方、本発明の透明導電性フィルムは、アルゴン原子や水素原子等の不純物量を所定の範囲内としているので、このような不純物に起因する透明導電層の結晶転化阻害が少なく、基材温度が100℃以下の低温で製膜されたものであっても、結晶転化性が良好であり、低比抵抗を実現できる。
また、バッチ式のスパッタ装置でスパッタ成膜を行う場合のフィルム基材温度とは、フィルム基材を載置するための基材ホルダー表面の温度である。
(アンダーコート層の形成)
メラミン樹脂:アルキド樹脂:有機シラン縮合物を、固形分で2:2:1の重量比で含む熱硬化型樹脂組成物を、固形分濃度が8重量%となるようにメチルエチルケトンで希釈した。得られた希釈組成物を、厚み50μmのPETフィルム(三菱樹脂製、商品名「ダイアホイル」)からなる高分子フィルム基材の一方主面に塗布し、150℃で2分間加熱硬化させ、膜厚35nmの有機アンダーコート層を形成した。形成した有機アンダーコート層の表面粗さをAFM(セイコーインスツルメンツ社製、「SPI3800」)で測定したところ、Raが0.5nmであった。さらに、有機アンダーコート層上に、無機アンダーコート層として、厚み5nmのSiO2層を、MF電源を用いたスパッタリングにより形成した
上記有機アンダーコート層を形成した高分子フィルム基材を真空スパッタ装置に設置し、到達真空度が0.9×10-4Paとなるよう十分に真空排気し、フィルムの脱ガス処理を行った。その後、Ar及びO2(流量比はAr:O2=99.9:0.1)を導入した真空雰囲気下(0.40Pa)で、10重量%の酸化スズと90重量%の酸化インジウムとの焼結体をターゲットとして用いて、フィルム基材温度を130℃とし、水平磁場を100mTとするRF重畳DCマグネトロンスパッタリング法(放電電圧150V、RF周波数13.56MHz、DC電力に対するRF電力の比(RF電力/DC電力)は0.8)により、厚み20nmのインジウム-スズ複合酸化物層からなる第1透明導電体層を形成した。この第1透明導電体層上に、Ar及びO2(流量比はAr:O2=99.9:0.1)を導入した真空雰囲気下(0.40Pa)で、3重量%の酸化スズと97重量%の酸化インジウムとの焼結体をターゲットとして用いて、フィルム基材温度を130℃とし、水平磁場を100mTとするRF重畳DCマグネトロンスパッタリング法(放電電圧150V、RF周波数13.56MHz、DC電力に対するRF電力の比(RF電力/DC電力)は0.8)により、厚み5nmのインジウム-スズ複合酸化物層からなる第2透明導電体層を形成した。このようにして第1透明導電体層と第2透明導電体層とが積層されてなる透明導電層を作製した。作製した透明導電層を150℃温風オーブンにて加熱して結晶転化処理を行い、結晶質の透明導電層を有する透明導電性フィルムを得た。
前記有機アンダーコート層上に、無機アンダーコート層として、厚み10nmのSiO2層を、MF電源を用いたスパッタリングにより形成したこと、及びスパッタリング電源をDC電源とし、ArとO2の流量比をAr:O2=99:1とし、放電電圧を235Vとして透明導電層を形成したこと以外は、実施例1と同様にして透明導電層及び透明導電性フィルムを作製した。
10重量%の酸化スズと90重量%の酸化インジウムとの焼結体をターゲットとして用いて厚み25nmの単層の透明導電層を形成したこと以外は、実施例2と同様にして透明導電層及び透明導電性フィルムを作製した。
無機アンダーコート層を形成せず、フィルムの脱ガス処理における、到達真空度を3.9×10-4Paとしたこと以外は、実施例3と同様にして透明導電層及び透明導電性フィルムを作製した。
無機アンダーコート層を形成せず、フィルムの脱ガス処理における、到達真空度を4.8×10-4Paとしたこと以外は、実施例3と同様にして透明導電層及び透明導電性フィルムを作製した。
無機アンダーコート層を形成しなかったこと以外は、実施例1と同様にして透明導電層及び透明導電性フィルムを作製した。
無機アンダーコート層を形成せず、10重量%の酸化スズと90重量%の酸化インジウムとの焼結体をターゲットとして用いて厚み25nmの単層の透明導電層を形成したこと以外は、参考例1と同様にして透明導電層及び透明導電性フィルムを作製した。
有機アンダーコート層及び無機アンダーコート層をともに形成してしない、Raが2.1nmのPETフィルムを高分子フィルム基材とした以外は、参考例2と同様にして透明導電層及び透明導電性フィルムを作製した。
無機アンダーコート層を形成しなかったこと以外は、実施例2と同様にして透明導電層及び透明導電性フィルムを作製した。
無機アンダーコート層を形成しなかったこと以外は、実施例3と同様にして透明導電層及び透明導電性フィルムを作製した。
実施例、比較例及び参考例において作製した透明導電性フィルムに対する測定ないし評価方法は以下のとおりである。各評価結果を表1~4に示す。
ITO膜の膜厚は、X線反射率法を測定原理とし、粉末X線回折装置(リガク社製、「RINT-2000」)を用いて、以下の測定条件にてX線反射率を測定し、取得した測定データを解析ソフト(リガク社製、「GXRR3」)で解析することで膜厚を算出した。解析条件は以下の条件とし、フィルム基材と密度7.1g/cm3のITO薄膜の2層モデルを採用し、ITO膜の膜厚と表面粗さを変数として、最小自乗フィッティングを行うことで、ITO膜の膜厚を解析した。
光源:Cu-Kα線(波長:1,5418Å)、40kV、40mA
光学系:平行ビーム光学系
発散スリット:0.05mm
受光スリット:0.05mm
単色化・平行化:多層ゲーベルミラー使用
測定モード:θ/2θスキャンモード
測定範囲(2θ):0.3~2.0°
<解析条件>
解析手法:最小自乗フィッティング
解析範囲(2θ):2θ=0.3~2.0°
ダイナミックSIMSを測定原理とする装置(装置:PHI ADEPT-1010、アルバック・ファイ社製)を用いて、0.15nmピッチで深さ方向の炭素原子の存在量(atoms/cm3)を測定した。図4は、本測定で検出される炭素原子のデプスプロファイルである。この図において、左端が表面、右端が基材側であり、Inピークの右終端部がすなわちITO膜の深さ方向の末端である。本測定では、図4に示す透明導電層の表面側及びフィルム基材側では、表面のコンタミ成分やフィルムに含まれる炭素原子を含めて検出してしまう。
透明導電性フィルムを150℃で加熱処理して透明導電層を結晶転化させた後、透明導電層の表面抵抗(Ω/□)をJIS K7194(1994年)に準じて四端子法により測定した。上記(1)膜厚の測定にて求めた透明導電層の厚みと前記表面抵抗から比抵抗を算出した。
高分子フィルム基材上にITO膜が形成された透明導電性フィルムを、150℃の熱風オーブンで加熱して結晶転化処理を行い、20℃、濃度5重量%の塩酸に15分間浸漬した後、水洗・乾燥し、15mm間の端子間抵抗をテスタにて測定した。本明細書においては、塩酸への浸漬・水洗・乾燥後に、15mm間の端子間抵抗が10kΩを超えない場合、ITO膜の結晶転化が完了したものとした。また、加熱時間30分ごとに上記測定を実施し、結晶化完了が確認できた時間を結晶転化時間として評価した。
実施例1~3では透明導電層中の炭素原子及び水素原子の各存在原子量がいずれも所定範囲以下まで低減され、透明導電層の結晶転化後の比抵抗も2.8×10-4Ω・cm以下と低い値となっており、炭素原子の存在量の点からも水素原子の存在量の点からも透明導電層の低抵抗化が達成されたことが分かる。一方、比較例1では、炭素原子及び水素原子の存在原子量が多くなっていたことから、比抵抗が高くなっていた。また、炭素原子及び水素原子による結晶成長阻害作用により結晶転化に要した時間も長くなっていた。比較例2では、炭素原子及び水素原子の存在原子量が高すぎたため、ITO膜が結晶化せずに比抵抗が高くなっていた。
2 透明導電層
10 透明導電性フィルム
11 スパッタ室
13 ターゲット
14 マグネット電極
16 DC電源
17 RF電極
100 スパッタ成膜装置
Claims (13)
- 高分子フィルム基材と、
前記高分子フィルム基材の少なくとも一方の面側に形成された透明導電層を備える透明導電性フィルムであって、
前記高分子フィルム基材と前記透明導電層との間に、真空成膜法にて形成された無機アンダーコート層を備え、
前記透明導電層中の炭素原子の存在原子量が3×1020atoms/cm3以下である透明導電性フィルム。 - 高分子フィルム基材と、
前記高分子フィルム基材の少なくとも一方の面側に形成された透明導電層を備える透明導電性フィルムであって、
前記高分子フィルム基材と前記透明導電層との間に、真空成膜法にて形成された無機アンダーコート層を備え、
前記透明導電層中の水素原子の存在原子量が3.7×1020atoms/cm3以下である透明導電性フィルム。 - 前記透明導電層の比抵抗が1.1×10-4Ω・cm以上2.8×10-4Ω・cm以下である請求項1又は2に記載の透明導電性フィルム。
- 前記透明導電層は、インジウム-スズ複合酸化物層である請求項1~3のいずれか1項に記載の透明導電フィルム。
- 前記透明導電層が結晶質である請求項1~4のいずれか1項に記載の透明導電フィルム。
- 前記インジウム-スズ複合酸化物層における酸化スズの含有量が、酸化スズ及び酸化インジウムの合計量に対し0.5重量%~15重量%である請求項4に記載の透明導電フィルム。
- 前記透明導電層は、複数のインジウム-スズ複合酸化物層が積層された構造を有し、
前記複数のインジウム-スズ複合酸化物層のうち少なくとも2層では互いにスズの存在量が異なる請求項1~3のいずれか1項に記載の透明導電フィルム。 - 前記インジウム-スズ複合酸化物層の全てが結晶質である請求項7に記載の透明導電フィルム。
- 前記透明導電層は、前記高分子フィルム基材側から、第1のインジウム-スズ複合酸化物層及び第2のインジウム-スズ複合酸化物層をこの順で有し、
前記第1のインジウム-スズ複合酸化物層における酸化スズの含有量が、酸化スズ及び酸化インジウムの合計量に対し6重量%~15重量%であり、
前記第2のインジウム-スズ複合酸化物層における酸化スズの含有量が、酸化スズ及び酸化インジウムの合計量に対し0.5重量%~5.5重量%である請求項7又は8に記載の透明導電フィルム。 - 前記高分子フィルム基材と前記透明導電層との間に、湿式塗工法にて形成された有機アンダーコート層を備える請求項1~9のいずれか1項に記載の透明導電フィルム。
- 前記高分子フィルムの少なくとも一方の面側に
湿式塗工法にて形成された有機アンダーコート層と、
真空成膜法にて形成された無機アンダーコート層と、
前記透明導電層とをこの順で備える請求項1~9のいずれか1項に記載の透明導電フィルム。 - 請求項1~9のいずれか1項に記載の透明導電性フィルムの製造方法であって、
高分子フィルム基材を到達真空度が3.5×10-4Pa以下の真空下に置く工程A、及び
前記高分子フィルム基材の少なくとも一方の面側にスパッタリング法により透明導電層を形成する工程B
を含み、
前記工程Aの後であって前記工程Bの前に、前記高分子フィルム基材の前記透明導電層が形成される面側に真空成膜法により無機アンダーコート層を形成する工程を含む透明導電フィルムの製造方法。 - 前記透明導電層を加熱して結晶転化する工程を含む請求項12に記載の透明導電性フィルムの製造方法。
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