WO2013172055A1 - 透明電極付き基板およびその製造方法、ならびにタッチパネル - Google Patents
透明電極付き基板およびその製造方法、ならびにタッチパネル Download PDFInfo
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- WO2013172055A1 WO2013172055A1 PCT/JP2013/051831 JP2013051831W WO2013172055A1 WO 2013172055 A1 WO2013172055 A1 WO 2013172055A1 JP 2013051831 W JP2013051831 W JP 2013051831W WO 2013172055 A1 WO2013172055 A1 WO 2013172055A1
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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
- G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
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- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0448—Details of the electrode shape, e.g. for enhancing the detection of touches, for generating specific electric field shapes, for enhancing display quality
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- C—CHEMISTRY; METALLURGY
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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
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—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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- C—CHEMISTRY; METALLURGY
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C—CHEMISTRY; METALLURGY
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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
- C23C14/06—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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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- C—CHEMISTRY; METALLURGY
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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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
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- G06F1/00—Details not covered by groups G06F3/00 - G06F13/00 and G06F21/00
- G06F1/16—Constructional details or arrangements
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- 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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- G06F2203/04112—Electrode mesh in capacitive digitiser: electrode for touch sensing is formed of a mesh of very fine, normally metallic, interconnected lines that are almost invisible to see. This provides a quite large but transparent electrode surface, without need for ITO or similar transparent conductive material
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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
- G06F3/0412—Digitisers structurally integrated in a display
Definitions
- This invention relates to the board
- a substrate with a transparent electrode in which a transparent electrode layer is formed on a transparent substrate such as a film or glass is used as a transparent electrode for a display such as a touch panel, a light-emitting element, or a photoelectric conversion element.
- a substrate with a transparent electrode is used for position detection of a capacitive touch panel, fine patterning is performed on the transparent electrode layer.
- the patterning method for example, a method is used in which a transparent electrode layer is formed on substantially the entire surface of a transparent substrate, and then the transparent electrode layer is removed by etching or the like in a part of the surface.
- a substrate with a transparent electrode having a transparent electrode layer patterned into an electrode layer forming part (also referred to as “non-etching part”) and an electrode layer non-forming part (also referred to as “etching part”) is obtained on the substrate. It is done.
- the substrate with transparent electrodes In order to display the display image clearly, it is important to improve the transparency of the substrate with transparent electrodes. Furthermore, in the substrate with a transparent electrode in which the transparent electrode layer is patterned, it is required that the pattern of the transparent electrode layer is difficult to be visually recognized.
- Patent Documents 1 and 2 propose a substrate with a transparent electrode in which a transparent electrode layer is formed on a transparent film via two transparent dielectric layers.
- Patent Document 1 proposes to reduce the transmittance difference and ⁇ b * between the electrode layer forming part and the electrode layer non-forming part by setting the film thickness and refractive index of each transparent dielectric layer to predetermined values.
- Patent Document 2 by setting the film thickness and refractive index of each transparent dielectric layer to predetermined values, the difference in reflectance between the electrode layer forming part and the electrode layer non-forming part is reduced, and the visual recognition of the pattern is suppressed. It has been proposed to do.
- a substrate with a transparent electrode having a thin film layer of three layers having a predetermined film thickness and a refractive index between a transparent film and a transparent electrode layer has a high transmittance and a predetermined range.
- a transmitted light b * of the inner it is disclosed that is suitable as a substrate for a resistive touch panel.
- no examination is made regarding the pattern visual recognition when the transparent electrode layer is patterned.
- the pattern does not change. It turned out that it might be visually recognized. Further examination was performed in view of the problem of such pattern visibility. As a result, the substrate with a transparent electrode having a patterned transparent conductive layer had wrinkles along the pattern of the transparent electrode layer. It was found that the pattern tends to be visually recognized because of the reflection.
- the present inventors patterned the transparent electrode layer of the substrate with a transparent electrode provided with the three thin film layers as disclosed in Patent Documents 3 and 4 above, and confirmed the visibility of the substrate with the transparent electrode. As a result, it was found that wrinkles were formed along the pattern of the transparent electrode layer, and the pattern was visually recognized.
- an object of the present invention is to provide a substrate with a transparent electrode in which the generation of wrinkles along the pattern of the transparent electrode layer is suppressed and the pattern is hardly visible. Furthermore, this invention aims at providing the board
- a transparent dielectric layer having a predetermined refractive index and film thickness is provided between the transparent film and the transparent electrode layer, and the transparent electrode layer has a predetermined refractive index and resistivity.
- the pattern visual recognition of the transparent electrode layer was suppressed.
- a transparent electrode layer having predetermined characteristics has a low resistance.
- the transparent electrode layer pattern is more difficult to visually recognize in the substrate with a transparent electrode having the transparent electrode layer in which the low-resistance transparent electrode layer is formed on the dielectric layer.
- the present invention relates to a substrate with a transparent electrode having a transparent dielectric layer mainly composed of an oxide and a transparent electrode layer in this order on at least one surface of a transparent film, and a method for producing the same.
- the transparent dielectric layer has a first dielectric layer, a second dielectric layer, and a third dielectric layer in this order from the transparent film side.
- the first dielectric layer is a silicon oxide layer whose main component is SiO x (x ⁇ 1.5).
- the second dielectric layer is a metal oxide layer mainly composed of an oxide of one or more metals selected from the group consisting of Nb, Ta, Ti, Zr, Zn, and Hf.
- the third dielectric layer is a silicon oxide layer containing SiO y (y> x) as a main component.
- the transparent electrode layer is a conductive metal oxide layer mainly composed of indium / tin composite oxide.
- the second dielectric layer is preferably a metal oxide layer containing Nb 2 O 5 as a main component.
- the film thickness of the first dielectric layer is 1 nm to 25 nm
- the film thickness of the second dielectric layer is 5 nm or more and less than 10 nm
- the film thickness of the third dielectric layer is 35 nm. It is preferable that the thickness of the transparent electrode layer is 20 nm to 35 nm.
- the thickness of the third dielectric layer is preferably more than 55 nm and not more than 80 m.
- the refractive index n 1 of the first dielectric layer, the refractive index n 2 of the second dielectric layer, and the refractive index n 3 of the third dielectric layer satisfy the relationship of n 3 ⁇ n 1 ⁇ n 2.
- the refractive index n 4 of the transparent electrode layer is preferably larger than the refractive index n 1 of the first dielectric layer and smaller than the refractive index n 2 of the second dielectric layer. That is, it is preferable that n 3 ⁇ n 1 ⁇ n 4 ⁇ n 2 .
- the transparent electrode layer preferably has a resistivity of 5.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less.
- the transparent electrode layer preferably has a refractive index of 1.88 or less.
- the transparent electrode layer preferably contains 4 to 14 parts by weight of tin oxide with respect to 100 parts by weight of the total of indium oxide and tin oxide.
- the content of tin oxide in the transparent electrode layer is preferably 8 parts by weight or less.
- the transparent electrode layer is patterned into an electrode layer forming part and an electrode layer non-forming part. It is preferable that the transmittance
- the arithmetic average roughness of the third dielectric layer on the transparent electrode layer side interface is preferably 1 nm or less.
- the third dielectric layer is preferably formed by sputtering under a pressure of less than 0.4 Pa.
- the first dielectric layer is also formed by a sputtering method under a pressure of less than 0.4 Pa.
- the average crystal grain size of the indium / tin composite oxide in the transparent electrode layer is 110 nm to 700 nm.
- the coefficient of variation of the crystal grain size is 0.35 or more.
- Such a low-resistivity transparent electrode layer is formed on a transparent film substrate by using an amorphous indium tin composite oxide as a main component by sputtering with a target surface magnetic flux density of 30 mT or more.
- the electrode layer is preferably produced by a method of crystallizing the amorphous transparent electrode layer after forming the electrode layer.
- the present invention relates to a capacitive touch panel comprising the substrate with transparent electrodes.
- the substrate with a transparent electrode of the present invention includes a transparent dielectric layer having a predetermined refractive index and a film thickness between the transparent film and the transparent electrode layer.
- the transparent electrode layer has the predetermined crystal grain size, the resistance of the transparent electrode layer is further reduced, and the generation of wrinkles along the pattern of the transparent electrode layer is further suppressed. Therefore, it is possible to provide a capacitive touch panel that excels in visibility and response speed.
- FIG. 1 is a cross-sectional view schematically showing a substrate with a transparent electrode according to an embodiment of the present invention.
- the transparent electrode-bearing substrate 100 on the transparent film 1 the refractive index first dielectric layer 21 of n 1, the third dielectric of the second dielectric layer 22 and the refractive index n 3 of the refractive index n 2
- the transparent dielectric layer 2 including the three layers 23 and the transparent electrode layer 4 having a refractive index n 4 are provided in this order.
- the transparent electrode layer 4 is patterned into an electrode layer forming portion 4a and an electrode layer non-forming portion 4b.
- Such a substrate with a transparent electrode is formed by, for example, etching after the first dielectric layer 21, the second dielectric layer 22, the third dielectric layer 23, and the transparent electrode layer 4 are formed on the transparent film 1.
- the transparent electrode layer 4 is formed by patterning.
- the material of the transparent film 1 is not particularly limited as long as it is colorless and transparent at least in the visible light region and has heat resistance at the transparent electrode layer forming temperature.
- transparent film materials include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), cycloolefin resins, polycarbonate resins, polyimide resins, and cellulose resins. It is done. Among these, polyethylene terephthalate and cycloolefin resin are preferably used.
- the thickness of the transparent film 1 is not particularly limited, but is preferably 10 ⁇ m to 400 ⁇ m, and more preferably 25 ⁇ m to 200 ⁇ m. If the thickness is within the above range, the transparent film 1 can have durability and appropriate flexibility, so that each transparent dielectric layer and transparent electrode layer can be produced with high productivity by a roll-to-roll method. It is possible to form a film.
- the transparent film 1 may have a functional layer (not shown) such as a hard coat layer formed on one side or both sides.
- a functional layer such as a hard coat layer formed on one side or both sides.
- the thickness of the hard coat layer is preferably 2 to 10 ⁇ m, more preferably 3 to 9 ⁇ m, and even more preferably 5 to 8 ⁇ m.
- the material of the hard coat layer is not particularly limited, and a material obtained by applying and curing a urethane resin, an acrylic resin, a silicone resin, or the like can be appropriately used.
- a transparent dielectric layer 2 mainly composed of an oxide is formed.
- the transparent dielectric layer 2 can act as a gas barrier layer that suppresses volatilization of moisture and organic substances from the transparent film 1 when the transparent electrode layer 4 is formed thereon, and also serves as an underlayer for film growth. Can also work.
- the resistance of the transparent electrode layer can be reduced by forming the transparent electrode layer on the transparent dielectric layer.
- the thickness of the transparent dielectric layer 2 is preferably 5 nm or more, more preferably 30 nm or more, More preferably, it is 55 nm or more.
- the thickness of the dielectric layer 2 is preferably 100 nm or less, more preferably 85 nm or less, and even more preferably 70 nm or less.
- the oxide constituting the transparent dielectric layer 2 is preferably colorless and transparent at least in the visible light region and preferably has a resistivity of 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm or more.
- Si, Nb, Ta, Ti An oxide of one or more elements selected from the group consisting of Zr and Hf is preferably used. Of these, silicon oxide and niobium oxide are preferable.
- “having a main component” a substance means that the content of the substance is 51% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight. As long as the function of the present invention is not impaired, each layer may contain components other than the main component.
- the transparent dielectric layer 2 may be composed of only one layer or may be composed of two or more layers. When the transparent dielectric layer is composed of two or more layers, by adjusting the film thickness and refractive index of each layer, the transmittance and reflectance of the substrate with a transparent electrode can be adjusted to improve the visibility of the display device. . Below, what formed the transparent dielectric material layer 2 on the transparent film 1 may be called a "transparent film base material.”
- a part of the surface of the transparent electrode layer 4 is patterned by etching or the like.
- the electrode layer forming portion 4a that remains without being etched, and the electrode layer non-formed portion where the electrode layer is removed by etching It is possible to reduce the transmittance difference, the reflectance difference, and the color difference with respect to 4b and suppress the visual recognition of the electrode pattern.
- the transparent dielectric layer 2 has a first dielectric layer 21, a second dielectric layer 22, and a third dielectric layer 23 in this order from the transparent film 1 side.
- the surface of the transparent film may be subjected to a surface treatment such as corona discharge treatment or plasma treatment prior to the formation of the first dielectric layer. .
- the refractive index n 1 of the first dielectric layer, the refractive index n 2 of the second dielectric layer, and the refractive index n 3 of the third dielectric layer are: It is preferable to satisfy the relationship of n 3 ⁇ n 1 ⁇ n 2 . Since the refractive index of each transparent dielectric layer has such a magnitude relationship, the reflectance at the interface of the transparent dielectric layer is appropriately controlled, and a substrate with a transparent electrode having excellent visibility is obtained.
- the refractive index of each transparent dielectric layer and transparent electrode layer is a refractive index for light having a wavelength of 550 nm measured by spectroscopic ellipsometry. The film thickness of each layer is determined by observing the cross section with a transmission electron microscope (TEM).
- the film thickness d 1 of the first dielectric layer 21 is preferably 1 nm to 25 nm.
- d 1 is preferably 2 nm or more, more preferably 3 nm or more, and further preferably 4 nm or more.
- d 1 is preferably 22 nm or less, more preferably 20 nm or less, and even more preferably 15 nm or less.
- the refractive index n 1 of the first dielectric layer is preferably 1.45 to 1.95, more preferably 1.47 to 1.85, and even more preferably 1.49 to 1.75.
- the metal oxide layer having a high refractive index is directly formed on the transparent film 1
- wrinkles along the pattern are generated when the transparent electrode layer is patterned.
- the silicon oxide layer is formed on the transparent film 1, the generation of pattern wrinkles is suppressed, and the pattern is hardly visually recognized.
- a metal oxide layer is preferably formed as the second dielectric layer 22.
- the refractive index n 2 of the second dielectric layer is preferably 2.00 to 2.35, more preferably 2.05 to 2.30, and even more preferably 2.10 to 2.25.
- a metal oxide having such a refractive index a metal oxide selected from the group consisting of Nb, Ta, Ti, Zr, Zn, and Hf, or a composite oxide of these metals is a main component. Those are preferred.
- the second dielectric layer 22 preferably has a small absorption in the short wavelength region of visible light.
- the material of the second dielectric layer 22 is preferably niobium oxide (Nb 2 O 5 ), tantalum oxide (Ta 2 O 5 ), titanium oxide (TiO 2 ), or zirconium oxide (ZrO 2 ).
- Niobium oxide is preferably used.
- the above materials have high transmittance on the short wavelength side compared to oxides of metals such as indium oxide, tin oxide, cerium oxide, or composite metal oxides thereof. It is easy to adjust b * of light within a preferable range.
- a silicon oxide layer mainly composed of SiO y is preferably formed.
- the silicon oxide SiO y used for the third dielectric layer has a larger oxygen content than the silicon oxide SiO x used for the first dielectric layer. That is, y> x.
- the refractive index n 3 of the third dielectric layer is made higher than the refractive index n 1 of the first dielectric layer. Can be small.
- x is preferably 1.5 or more.
- the oxygen composition ratios x and y of SiO x that is the main component of the first dielectric layer and SiO y that is the main component of the third dielectric layer satisfy 1.5 ⁇ x ⁇ y. . Since the stoichiometric composition of silicon oxide is SiO 2 , the theoretical upper limit of y is 2.
- the film thickness d 3 of the third dielectric layer 23 is preferably 35 nm to 80 nm.
- the transmittance of the substrate with a transparent electrode is increased, the generation of pattern wrinkles when the transparent electrode layer 4 is patterned is suppressed, and the pattern is visually recognized.
- a difficult substrate with a transparent electrode is obtained.
- thickness d 3 of the third dielectric layer is more preferably greater than 55 nm, further preferably not less than 57 nm.
- the thickness d 3 of the third dielectric layer is larger thickness d 3 of, decrease the transmittance of the transparent electrode substrate, there are cases where the pattern of the transparent electrode layer is likely to be visually recognized. Therefore, the thickness d 3 of the third dielectric layer, more preferably at most 75 nm, more preferably 70nm or less.
- the thickness d 3 of the third dielectric layer is controlled by controlling the film characteristics of the transparent electrode layer 4, the generation of wrinkles tends to be suppressed and the transmittance of the electrode layer forming portion 4a tends to be increased.
- the thickness of the third dielectric layer is large, wrinkles tend to be more effectively suppressed. Therefore, in the range where the thickness d 3 of the third dielectric layer 23 exceeds 55 nm, it is possible to visually recognize the pattern of the transparent electrode layer to obtain a more Suppressed transparent electrode-bearing substrate.
- the refractive index n 3 of the third dielectric layer is preferably 1.43 or more, more preferably 1.45 or more, and further preferably 1.47 or more.
- the third dielectric layer has the refractive index, pattern wrinkles tend to be reduced.
- the refractive index tends to increase as the film becomes denser.
- the third dielectric layer formed immediately below the transparent electrode layer is a dense film, so that it is presumed that the stress at the interface is reduced and the pattern wrinkles are reduced.
- the refractive index n 3 of the third dielectric layer is preferably 1.51 or less, more preferably 1.50 or less 1.49 or less is more preferable.
- the film thickness of each of the transparent dielectric layers 21, 22, and 23 is adjusted within the above range, thereby suppressing generation of wrinkles along the pattern when the transparent electrode layer 4 is patterned. Is done. Therefore, when the substrate with a transparent electrode having the above configuration is used for a capacitive touch panel, the visibility of the display can be improved.
- the substrate with a transparent electrode adjusts the refractive index within the above range, thereby allowing multiple interference of light at the interface. Is moderately adjusted. Therefore, even when the transparent electrode layer is patterned, the color difference between the transmitted light and the reflected light between the electrode layer forming part 4a and the electrode layer non-forming part 4b is reduced, and the visual recognition of the pattern of the transparent electrode layer is suppressed.
- the optical film thickness n 1 d 1 represented by the product of the refractive index n 1 and the film thickness d 1 is preferably 2 nm to 40 nm.
- n 1 d 1 is more preferably 4 nm or more, and further preferably 6 nm or more.
- n 1 d 1 is more preferably 36 nm or less, and even more preferably 32 nm or less.
- the optical film thickness n 2 d 2 of the second dielectric layer is preferably 11 nm to 20 nm.
- n 2 d 2 is more preferably 12 nm or more, and further preferably 13 nm or more. n 2 d 2 is more preferably 19 nm or less, and further preferably 18 nm or less.
- the optical film thickness n 3 d 3 of the third dielectric layer is preferably 50 nm to 110 nm. n 3 d 3 is more preferably 55 nm or more, and further preferably 60 nm or more. n 3 d 3 is more preferably 100 nm or less, further preferably 90 nm or less, and particularly preferably 80 nm or less.
- the arithmetic average roughness Ra of the surface on the transparent electrode layer 4 forming surface side of the transparent film substrate 10 is preferably 1 nm or less, more preferably 0.8 nm or less, and further preferably 0.6 nm or less.
- the arithmetic average roughness of the surface of the transparent dielectric layer 2 is preferably in the above range.
- the arithmetic average roughness of the surface of the third dielectric layer 23 formed immediately below the transparent electrode layer is within the above range.
- the arithmetic average roughness Ra is calculated in accordance with JIS B0601: 2001 (ISO1302: 2002) based on the surface shape (roughness curve) measured by a non-contact method using a scanning probe microscope.
- the surface of the transparent film substrate 10 By making the surface of the transparent film substrate 10 smooth, crystallization of the transparent electrode layer 4 formed thereon is promoted, and a transparent electrode layer having a low resistivity tends to be easily obtained.
- the transparent electrode layer 4 is formed on the three transparent dielectric layers 21, 22, 23 as shown in FIG. 1, the surface of the third dielectric layer 23 formed immediately below the transparent electrode layer. By smoothing, there is a tendency that pattern wrinkles when the transparent electrode layer is patterned are reduced.
- Transparent electrode layer As the transparent electrode layer 4, a conductive oxide layer mainly composed of indium / tin composite oxide (ITO) is formed.
- the film thickness d 4 of the transparent electrode layer 4 is preferably 15 to 110 nm.
- the film thickness d 4 of the transparent electrode layer 4 is preferably 15 nm to 40 nm, more preferably 21 nm to 35 nm, and 23 nm to 30 nm. More preferably it is.
- d 4 is more preferably 32nm or less, particularly preferably 26 nm.
- the refractive index n 4 of the transparent electrode layer is preferably 1.88 or less. By reducing the refractive index of the transparent electrode layer, the resistance of the transparent electrode layer tends to be reduced. In addition, when a transparent electrode layer having a low refractive index is formed on the transparent dielectric layer 2, the generation of pattern defects after the transparent electrode layer is patterned by etching or the like tends to be suppressed.
- n 4 is more preferably 1.86 or less, and even more preferably 1.84 or less.
- the lower limit of n 4 is not particularly limited. As described in Patent Documents 1 to 4 described above, the refractive index of the ITO thin film formed on the film is generally 1.90 or more. However, in the present invention, the refractive index is lower than those of the prior art. By forming the ITO, the resistance of the transparent electrode layer is reduced, and generation of wrinkles when the transparent electrode layer is patterned is suppressed.
- the refractive index n 4 of the transparent electrode layer 4 is preferably smaller than the refractive index n 2 of the second dielectric layer and larger than the refractive index n 1 of the first dielectric layer. . That is, it is preferable that the refractive index of each layer of the substrate with a transparent electrode of the present invention satisfies the relationship of n 3 ⁇ n 1 ⁇ n 4 ⁇ n 2 . As will be described in detail later, the refractive index n 4 of the transparent electrode layer is adjusted by adjusting the content of tin oxide in ITO, the film forming conditions of the transparent dielectric layer as the underlayer, the surface roughness, and the like. Within the above range.
- the resistivity of the transparent electrode layer 4 is preferably 5.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, more preferably 4.5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, and 3.7 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less. Further preferred. When the resistivity of the transparent electrode layer is within the above range, the response speed can be increased when used as a substrate with a transparent electrode for a capacitive touch panel.
- the sheet resistance of the transparent electrode layer is preferably 250 ⁇ / ⁇ or less, more preferably 200 ⁇ / ⁇ or less, still more preferably 160 ⁇ / ⁇ or less, particularly preferably 145 ⁇ / ⁇ or less, and 130 ⁇ / ⁇ or less. Most preferred.
- a transparent electrode layer is low resistance, it can contribute to the response speed improvement of a capacitive touch panel. Moreover, when a substrate with a transparent electrode is used for organic EL lighting, if the transparent electrode layer has a low resistance, it can contribute to improvement of uniformity of in-plane luminance.
- the resistivity of the transparent electrode layer 4 is preferably 3.7 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less.
- the reason why the generation of wrinkles is suppressed when the resistivity of the transparent electrode layer 4 is small is not certain, but the crystal characteristics of the ITO affect the conductivity, and the transparent electrode layer 4 and the transparent dielectric layer 2 It is presumed that one of the factors is that it also affects the stress at the interface.
- the content of tin oxide in the transparent electrode layer is preferably 4 to 14 parts by weight with respect to 100 parts by weight of indium oxide and tin oxide in total.
- the content of tin oxide is more preferably 5 to 10 parts by weight.
- the amorphous ITO film can be crystallized without heating at a high temperature for a long time, so that the productivity of a substrate with a transparent electrode can be improved. It becomes possible.
- the carrier density of the transparent electrode layer 4 is preferably 5.0 ⁇ 10 20 / cm 3 or more, more preferably 5.5 ⁇ 10 20 / cm 3 or more. 1 ⁇ 10 20 / cm 3 or more is more preferable.
- the hole mobility is preferably 25 cm 3 / V ⁇ S or more, and more preferably 30 cm 3 / V ⁇ S or more.
- the average crystal grain size of the transparent electrode layer 4 is preferably 110 nm to 700 nm, more preferably 150 nm to 550 nm, and further preferably 200 nm to 400 nm.
- the transparent electrode layer tends to have low resistance and high transmittance.
- the crystal grain size is large, the generation efficiency and mobility of carriers are increased by the reduction of the crystal grain boundary, so that the resistivity is considered to decrease.
- the crystal grain size is 700 nm or less, it is easy to obtain a transparent electrode layer having good flexibility and suppressing occurrence of cracks.
- the coefficient of variation of the crystal grain size of the transparent electrode layer 4 is preferably 0.35 or more, more preferably 0.40 or more, and further preferably 0.45 or more.
- the tin oxide content is high Sn content ITO having a content of 10% or more, for example.
- the content of tin oxide is increased, it is difficult to reduce the resistivity of the substrate with a transparent electrode using a film base material because high temperature and long time heating are required for crystallization.
- in addition to increasing the average crystal grain size of the crystal by making the variation coefficient within a predetermined range, it is possible to reduce the resistance even when the tin oxide content of the transparent electrode layer is small. .
- the average crystal grain size of the transparent electrode layer and the coefficient of variation of the crystal grain size are determined by observing the in-plane of the transparent electrode layer 4 under a microscope.
- the ratio of the area occupied by crystal grains during microscopic observation is 70% or more of the observation region as “crystalline”, and the ratio of less than 70% as “amorphous”.
- the crystallization rate of the transparent electrode layer 4 is preferably 80% or more, and more preferably 90% or more.
- the transparent electrode layer has a crystal as described above.
- the transparent electrode layer tends to have low resistivity, and the generation of wrinkles along the pattern of the transparent electrode layer tends to be suppressed.
- the transmittance of the transparent electrode layer is improved, the pattern of the transparent electrode layer tends to be hardly visible. Therefore, when the thickness d 3 is larger and the third dielectric layer 23, even if d 3 is small, the transparent electrode-bearing substrate which is excellent in visibility (transparency) is obtained.
- the third dielectric layer 23 is used.
- the film thickness d 3 is a wider range, there is a tendency that the transparent electrode-bearing substrate 100 having excellent visibility can be obtained.
- the film thickness d 3 of the third dielectric layer is larger than 55 nm, by the transparent electrode layer has a resistivity and crystal properties as described above, occurrence of wrinkles can be effectively suppressed, visibility significantly There is a tendency to improve.
- substrate with a transparent electrode of this invention is between the transparent film 1 and the transparent dielectric material layer 2, on the transparent electrode layer 4, or the surface of the transparent electrode 1 surface side of the transparent film 1 May have other layers.
- the substrate with a transparent electrode of the present invention may have a transparent electrode layer on both sides of the transparent film 1.
- the substrate 100 with a transparent electrode is obtained by forming the transparent dielectric layer 2 and the transparent electrode layer 4 on the transparent film 1.
- the method for forming the transparent dielectric layer 2 is not particularly limited as long as it is a method for forming a uniform thin film.
- the film forming method include PVD methods such as sputtering and vapor deposition, dry coating methods such as various CVD methods, and wet coating methods such as spin coating, roll coating, spray coating, and dipping coating.
- the dry coating method is preferable from the viewpoint of easily forming a nanometer-level thin film.
- the sputtering method is preferable from the viewpoint of controlling the film thickness of each layer in units of several nanometers and suppressing the pattern visibility of the transparent electrode layer.
- a metal, metal oxide, metal carbide, or the like can be used as a target.
- the power source a DC, RF, MF power source or the like can be used. From the viewpoint of productivity, an MF power source is preferable.
- the applied power at the time of film formation is not particularly limited, but is preferably adjusted within a range that does not give excessive heat to the transparent film and does not impair productivity.
- the power at the time of forming the first dielectric layer is preferably 0.5 to 10 W / cm 2
- the power density when forming the second dielectric layer is preferably 0.5 to 8 W / cm 2
- the power density when forming the third dielectric layer is 0.00. 2 to 10 W / cm 2 is preferable.
- Pre-sputtering may be performed for the purpose of removing an oxide film or moisture adhering to the target surface before starting the formation of each dielectric layer.
- pre-sputtering adhesion of contaminated target particles to the base material is suppressed.
- pre-sputtering is preferably performed before the formation of the silicon oxide layer as the third dielectric layer.
- pre-sputtering is performed before the third dielectric layer is formed, so that film quality is improved and generation of wrinkles when the transparent electrode layer 4 is patterned tends to be suppressed.
- pre-sputtering before the formation of the third dielectric layer is performed under a condition where the flow rate of the inert gas is larger than the film formation condition of the third dielectric layer or under a high pressure condition. Preferably, it is done.
- the base material can be subjected to a bombarding step before the start of film formation of each dielectric layer.
- a bombarding step plasma is generated by performing discharge using a SUS target or the like under a gas supply containing an inert gas such as argon as a main component.
- an inert gas such as argon as a main component.
- the film forming pressure of each transparent dielectric layer can be set appropriately.
- the third dielectric layer 23 formed immediately below the transparent electrode layer is under a pressure of less than 0.4. It is preferable to form a film by a sputtering method.
- the film forming pressure of the third dielectric layer is more preferably 0.35 Pa or less, and further preferably 0.25 Pa or less.
- the third dielectric layer When the third dielectric layer is formed under a low pressure condition, there is a tendency that generation of pattern defects when the transparent electrode layer formed thereon is patterned by etching or the like is suppressed.
- the reason why the pattern defect of the transparent electrode layer is suppressed by adjusting the film formation condition of the third dielectric layer is not clear, but the crystallinity, surface shape, surface property, etc. of the third dielectric layer as the underlayer However, it is considered that this influences the film growth of the transparent electrode layer.
- the physical properties of the third dielectric layer affect the crystallinity of the ITO film constituting the transparent electrode layer, the residual stress in the film, etc., and the interface stress imbalance between the electrode layer forming part and the electrode layer non-forming part It is presumed that the elimination of is contributing to the suppression of pattern wrinkles.
- the first dielectric layer 21 is also formed by sputtering under a pressure of less than 0.4. It is preferable.
- the film forming pressure of the first dielectric layer is more preferably 0.35 Pa or less, and further preferably 0.25 Pa or less.
- reducing the deposition pressure of the first dielectric layer tends to suppress the occurrence of pattern defects.
- the pattern defect of the transparent electrode layer is suppressed by adjusting the film formation conditions of the first dielectric layer, the crystallinity, surface shape, surface property, etc. of the first dielectric layer are One of the causes is considered to influence the film growth of the third dielectric layer and the transparent electrode layer via the dielectric layer.
- the ITO is crystallized by heating.
- a sputtering method is preferable.
- a sputtering power source a DC, RF, MF power source or the like can be used.
- an MF power source is preferably used from the viewpoint of productivity and low resistance.
- a metal, metal oxide, or the like is used as a target.
- a gas mainly containing an inert gas such as argon is preferable.
- “mainly containing an inert gas” means containing 50% or more of an inert gas such as argon among the gases used.
- the introduced gas may be an inert gas such as argon alone, or two or more mixed gases.
- a mixed gas of argon and oxygen is preferable.
- the mixed gas of argon and oxygen preferably contains 0.2 to 5% by volume of oxygen, more preferably 1.0 to 4% by volume.
- the transparency and conductivity of the transparent electrode layer can be improved.
- the mixed gas of argon and oxygen may contain other gases as long as the function of the present invention is not impaired.
- pre-sputtering of the target or bombarding of the base material may be performed prior to the formation of the transparent electrode layer.
- the magnetic flux density on the target surface during sputtering film formation is preferably 30 mT or more, more preferably 35 mT or more, and further preferably 40 mT or more.
- ITO is formed in a low magnetic field of about 10 to 20 mT in order to generate a good discharge and increase the utilization efficiency of the target.
- the average value and coefficient of variation of the crystal grain size of the transparent electrode layer can be increased, and a low-resistance ITO transparent electrode layer can be easily obtained. Become.
- the transparency (transmittance) of the transparent electrode layer can be increased by increasing the magnetic flux density on the target surface during sputtering film formation.
- By increasing the transparency of the transparent electrode layer it is possible to reduce the transmittance difference, reflectance difference, color difference, etc. between the electrode layer forming part and the electrode layer non-forming part when the transparent electrode layer is patterned. It is possible to obtain a substrate with a transparent electrode that is difficult to be visually recognized.
- the transparent electrode layer 4 when the transparent electrode layer 4 is formed on a dielectric layer composed of three layers, a first dielectric layer 21, a second dielectric layer 22, and a third dielectric layer 23, By increasing the magnetic flux density on the target surface during sputtering film formation, there is a tendency to suppress pattern wrinkles when the transparent electrode layer is patterned.
- the upper limit of the magnetic flux density is not particularly limited, but even if the magnetic flux density is excessively increased, the effect of suppressing the visual recognition of the pattern of the transparent electrode layer and decreasing the resistivity tend to be saturated. On the other hand, the efficiency of sputtering film formation tends to decrease as the magnetic flux density increases. Therefore, from the viewpoint of film formation efficiency, the magnetic flux density on the target surface during sputtering film formation is preferably less than 100 mT, more preferably less than 90 mT, and even more preferably less than 80 mT.
- the power supply voltage during sputtering film formation is preferably 100 V to 500 V, more preferably 150 V to 450 V, and even more preferably 200 V to 400 V.
- the power supply voltage is preferably 50 V to 250 V, more preferably 75 V to 225 V, and even more preferably 100 V to 200 V.
- the substrate temperature when the transparent electrode layer is formed by sputtering may be in the range where the transparent film 1 has heat resistance.
- the substrate temperature is preferably ⁇ 35 ° C. to 35 ° C., more preferably ⁇ 30 ° C. to 30 ° C., and further preferably ⁇ 25 ° C. to 25 ° C.
- the substrate temperature is preferably ⁇ 35 ° C. to 35 ° C., more preferably ⁇ 30 ° C. to 30 ° C., and further preferably ⁇ 25 ° C. to 25 ° C.
- the transparent electrode layer In order to make the transparent electrode layer an ITO film having a low refractive index and a low resistance, it is preferable that a heat treatment is performed after the film formation.
- the heat treatment causes crystallization of ITO, and the transparent electrode layer tends to have a low refractive index and a low resistance, and the transmittance tends to increase.
- the heat treatment of the transparent electrode layer is performed, for example, in an oven at 120 ° C. to 150 ° C. for 30 to 60 minutes. Alternatively, it may be heated at a relatively low temperature (eg, about 50 ° C. to 120 ° C.) for a long time at a relatively low temperature such as 1 to 3 days.
- the heat treatment of the transparent electrode layer may be performed either before or after patterning of the transparent electrode layer. Further, the heat treatment of the transparent electrode layer may also serve as a heat annealing treatment for touch panel formation such as heat treatment at the time of forming the lead wiring. In the case where heat treatment of the transparent conductive layer is performed, it is preferable that the refractive index n 4 of the transparent conductive layer after the heat treatment falls within the above range. In this case, the refractive index of the transparent conductive layer before the heat treatment may exceed 1.88.
- the patterning is performed, for example, after the transparent electrode layer is formed and in part in the plane Is removed by etching or the like.
- the method for etching the transparent electrode layer may be either a wet process or a dry process, but a wet process is suitable from the viewpoint that only the transparent electrode layer 4 is easily removed selectively.
- the transparent dielectric layer is removed when patterning the transparent electrode layer 4.
- the transparent electrode layer 4 is selectively removed.
- a photolithography method is suitable as the wet process.
- a photoresist a developing solution, and a rinse agent used for photolithography, those that can form a predetermined pattern without damaging the transparent electrode layer 4 can be arbitrarily selected.
- the etching solution one that can remove the transparent electrode layer 4 and does not attack the silicon oxide of the third dielectric layer is preferably used.
- the color difference of transmitted light between the electrode layer forming part and the electrode layer non-forming part is preferably 0.8 or less, more preferably 0.4 or less, further preferably 0.3 or less, and particularly preferably 0.2 or less.
- the color difference of the reflected light between the electrode layer forming part and the electrode layer non-forming part is preferably 2.4 or less, more preferably 1.9 or less, further preferably 1.6 or less, and particularly preferably 1.4 or less.
- the substrate with a transparent electrode of the present invention is preferably blue to colorless with b * of the transmitted light of the electrode layer forming part of ⁇ 2 to 1, It is more preferably from ⁇ 1 to 0.5.
- the color tone is a value defined by JIS Z8730 and can be expressed by CIE lightness L * and color coordinates a * and b * .
- a * Axis represents green to red, minus is green, plus is red.
- b * Axis represents blue to yellow, minus is blue, plus is yellow.
- ⁇ E ⁇ ( ⁇ L * ) 2 + ( ⁇ a * ) 2 + ⁇ b * ) 2 ⁇ 1/2
- the transmittance of the substrate in the electrode layer forming portion is preferably 87% or more, and more preferably 88% or more. If the transmittance
- “transmittance” is the total light transmittance measured according to JIS K7361, and can be measured using a haze meter.
- the substrate with a transparent electrode of the present invention is suitably used as a transparent electrode for a touch panel. Especially, since a pattern is hard to be visually recognized and a transparent electrode layer is low resistance, it is preferably used for a capacitive touch panel.
- a conductive ink or paste is applied on the substrate with the transparent electrode and heat-treated to form a collecting electrode as a wiring for a routing circuit.
- the heat treatment method is not particularly limited, and examples thereof include a heating method using an oven, an IR heater, or the like.
- the temperature and time of the heat treatment are appropriately set in consideration of the temperature and time at which the conductive paste adheres to the transparent electrode. For example, examples include heating at 120 to 150 ° C. for 30 to 60 minutes for heating by an oven and 150 ° C. for 5 minutes for heating by an IR heater.
- the formation method of the circuit wiring is not limited to the above, and may be formed by a dry coating method.
- the wiring for the routing circuit is formed by photolithography, the wiring can be thinned.
- the refractive index of each transparent dielectric layer and transparent electrode layer was determined by spectroscopic ellipsometry measurement and fitting with a cauchy model and a tauc-lorentz model to obtain a value for light having a wavelength of 550 nm.
- a sample in which the transparent conductive layer non-formed surface side surface was polished was used.
- the values obtained by observing the cross section of the substrate with a transparent electrode by a transmission electron microscope (TEM) were used for the film thickness of each transparent dielectric layer and transparent electrode layer. Confirm that the transmittance and reflectance calculated by simulation using the measured values of refractive index, extinction coefficient, and film thickness of each transparent dielectric layer and transparent conductive layer agree with the values measured by the spectrophotometer. The accuracy of the fitting was confirmed.
- the surface resistance of the transparent electrode layer was measured by four-probe pressure measurement using a low resistivity meter Loresta GP (MCP-T710, manufactured by Mitsubishi Chemical Corporation).
- the resistivity of the transparent conductive layer was calculated by the product of the surface resistance value and the film thickness.
- the transmittance (total light transmittance) of the electrode layer forming portion of the substrate with a transparent electrode was measured according to JIS K7361 using a haze meter (NDH5000, manufactured by Nippon Denshoku). Further, b * was measured according to JIS Z8730 using a spectrocolorimeter (CM-3600d, manufactured by Konica Minolta).
- the presence or absence of pattern defects on the substrate with a transparent electrode was determined visually.
- the reflected light from the fluorescent lamp is observed in a state where the pattern formation direction of the transparent electrode layer and the reflected light of the straight tube fluorescent lamp are substantially orthogonal, and the reflected image of the fluorescent lamp looks linear
- the pattern visibility of the transmitted light of the substrate with a transparent electrode was evaluated by observing the substrate with the transparent electrode placed on a light box in a dark room.
- the pattern visibility of the reflected light of the substrate with a transparent electrode was visually evaluated by observing the reflected light from the substrate with the transparent electrode under a fluorescent lamp.
- the surface shape of the transparent dielectric layer surface was measured with a scanning probe microscope (Nano-R manufactured by Pacific® Nanotechnology) using a sample cut out to a 5 mm square.
- the arithmetic average roughness Ra was calculated in accordance with JIS B0601: 2001 (ISO1302: 2002) based on the surface shape (roughness curve) measured in the range of 0.7 ⁇ m by the non-contact mode.
- the carrier density of the transparent electrode layer was measured by the van der pauw method. A sample was cut into a 1 cm square, and metal indium was fused to the four corners as electrodes. The carrier mobility was calculated by measuring the hole mobility based on the potential difference when a current of 1 mA was passed in the diagonal direction of the substrate with a magnetic force of 3500 gauss.
- the average particle diameter of the crystal of the transparent electrode layer and the coefficient of variation of the crystal grain diameter were calculated based on a plane observation photograph of the transparent electrode layer with a scanning transmission electron microscope (STEM) (see FIGS. 2 and 3).
- An observation sample was prepared by argon ion milling with an acceleration voltage of 2.0 kV using an ion milling machine (PIPS TH manufactured by Topcon Technohouse), and an acceleration voltage of 200 kV, 50 using STEM (Hitachi HD-2700). Planar observation was performed at a magnification of 1,000,000.
- Example 1 Using a roll-to-roll type roll-up type sputtering device on one surface of a biaxially stretched PET film having a thickness of 188 ⁇ m and having a hard coat layer (refractive index of 1.53) made of urethane resin formed on both sides
- Medium refractive index transparent dielectric layer (first dielectric layer) made of silicon oxide (SiO x layer), high refractive index transparent dielectric layer (second dielectric layer) made of niobium oxide, and silicon oxide
- a low refractive index dielectric layer (third dielectric layer) made of (SiO 2 ) was sequentially formed.
- the apparatus pressure was 0.2 Pa
- the substrate temperature was ⁇ 20 ° C.
- the power density was 1.4 W / cm 2 .
- Sputtering was performed under conditions.
- the obtained SiO y layer had a thickness of 5 nm and a refractive index of 1.65.
- a high refractive index transparent dielectric layer was formed on the SiO x layer. While using niobium (Nb) as a target and introducing an oxygen / argon (160 sccm / 1600 sccm) mixed gas into the apparatus, the internal pressure was 0.87 Pa, the substrate temperature was ⁇ 20 ° C., and the power density was 8.1 W / cm 2 . Sputtering was performed. The obtained niobium oxide (Nb 2 O 5 ) layer had a thickness of 7 nm and a refractive index of 2.18.
- a low refractive index transparent dielectric layer was formed on the niobium oxide layer.
- the internal pressure was 0.2 Pa
- the substrate temperature was ⁇ 20 ° C.
- the power density was 10.2 W / cm 2 .
- Sputtering was performed.
- the obtained SiO x layer (x 2) had a film thickness of 50 nm, a refractive index of 1.47, and a surface arithmetic average roughness Ra of 0.5 nm.
- An amorphous ITO transparent electrode layer was formed on the transparent dielectric layer of the transparent film substrate by using a roll-to-roll type winding sputtering apparatus equipped with an MF power source.
- Sputter film formation uses indium-tin composite oxide (tin oxide content 5 wt%) as a target, and an oxygen / argon (2 sccm / 1000 sccm) mixed gas is introduced into the apparatus while the apparatus pressure is 0.4 Pa.
- the substrate temperature was ⁇ 20 ° C. and the power density was 5.2 W / cm 2 .
- the obtained transparent electrode layer had a film thickness of 25 nm.
- the magnetic flux density on the target surface was measured by bringing a magnetic flux density meter into contact with the target surface, and it was 46 mT. Further, the voltage of the MF power source during sputtering film formation was 357V.
- a photoresist product name: TSMR-8900 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)
- TSMR-8900 manufactured by Tokyo Ohka Kogyo Co., Ltd.
- a developer product name: NMD-W (manufactured by Tokyo Ohka Kogyo)
- the transparent electrode layer was etched using an etching solution (product name: ITO02 (manufactured by Kanto Chemical)). Finally, the remaining photoresist was removed using a rinse solution (product name: 104 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)).
- Examples 2 to 9 and Comparative Examples 1 to 3 The thickness d 2 of the second dielectric layer, the thickness d 3 of the third dielectric layer, and the thickness of the transparent electrode layer were changed as shown in Table 1. Otherwise, the first dielectric layer, the second dielectric layer, the third dielectric layer, and the transparent electrode layer were sequentially formed in the same manner as in Example 1, followed by patterning and heat treatment of the transparent electrode layer. It was.
- the transmittance of the electrode layer forming portion of the substrate with a transparent electrode of Comparative Example 2 was 88.2%.
- the transmittances of the electrode layer forming portions of the substrates with transparent electrodes of Example 2, Example 4, Example 5 and Example 8 were 89.1%, 89.4%, 88.4% and 88.8%, respectively. Met.
- Example 10 By changing the permanent magnet attached to the sputtering apparatus, the magnetic flux density when forming the transparent electrode layer was adjusted to 16 mT. The voltage of the MF power source during sputtering film formation was 511V. Other than that, the first dielectric layer, the second dielectric layer, the third dielectric layer and the transparent electrode layer were sequentially formed in the same manner as in Example 1, followed by patterning and heat treatment of the transparent electrode layer. It was.
- Example 11 The first dielectric layer, the second dielectric layer, and the third dielectric were the same as in Example 10 except that a target having a tin oxide content of 10% by weight was used as the target for forming the transparent electrode layer. After the body layer and the transparent electrode layer were sequentially formed, patterning and heat treatment of the transparent electrode layer were performed.
- Example 12 A first dielectric layer, a second dielectric layer, a third dielectric layer, and a transparent electrode layer were sequentially formed in the same manner as in Example 10 except that the transparent electrode layer was formed with a thickness of 30 nm. Thereafter, patterning and heat treatment of the transparent electrode layer were performed.
- Example 4 The first dielectric layer, the second dielectric layer, and the third dielectric were the same as in Example 10 except that a target having a tin oxide content of 3% by weight was used as the target for forming the transparent electrode layer. After the body layer and the transparent electrode layer were sequentially formed, patterning and heat treatment of the transparent electrode layer were performed. The transmittance of the electrode layer forming portion of the substrate with a transparent electrode of Comparative Example 4 was 87.2%.
- Example 13 and Comparative Examples 5 to 8 By adjusting the amounts of argon and oxygen introduced during film formation, the pressures in the apparatus during film formation of the first dielectric layer and the third dielectric layer were changed as shown in Table 1. Otherwise, the first dielectric layer, the second dielectric layer, the third dielectric layer, and the transparent electrode layer were sequentially formed in the same manner as in Example 10, followed by patterning and heat treatment of the transparent electrode layer. It was.
- Example 10 film formation pressure of the first dielectric layer and the third dielectric layer: 0.2 Pa
- Example 13 film formation pressure of the first dielectric layer and the third dielectric layer: 0.3 Pa
- Comparative Example 5 film formation pressure of the first dielectric layer and the third dielectric layer: 0.5 Pa
- Comparative Example 6 film formation pressure of the first dielectric layer and the third dielectric layer: 0.8 Pa
- the arithmetic average roughness of the third dielectric layer was 0.5 nm, 0.7 nm, 1.3 nm, and 4.5 nm, respectively. From the comparison of Example 10, Example 13, Comparative Example 5 and Comparative Example 6, it can be seen that the lower the deposition pressure of the third dielectric layer, the smoother the surface.
- Example 14 Sputtering was performed while reducing the relative proportion of oxygen in the introduced gas during the formation of the first dielectric layer.
- the obtained SiO x layer had a thickness of 5 nm and a refractive index of 1.75. Otherwise, the first dielectric layer, the second dielectric layer, the third dielectric layer, and the transparent electrode layer were sequentially formed in the same manner as in Example 10, followed by patterning and heat treatment of the transparent electrode layer. It was.
- a first dielectric layer, a second dielectric layer, a third dielectric layer, and a transparent electrode layer are sequentially formed in the same manner as in Example 14 except that the first dielectric layer is formed with a thickness of 30 nm. Then, patterning and heat treatment of the transparent electrode layer were performed.
- Example 15 By changing the permanent magnet attached to the sputtering apparatus, the magnetic flux density when forming the transparent electrode layer was adjusted to 76 mT. The voltage of the MF power source during sputtering film formation was 306V. Otherwise, in the same manner as in Example 8, the first dielectric layer, the second dielectric layer, the third dielectric layer, and the transparent electrode layer were sequentially formed, and then the transparent electrode layer was patterned and heat-treated. . The transmittance of the electrode layer forming portion of the substrate with a transparent electrode in Example 15 was 89.4%.
- Table 1 shows the refractive index, film thickness and film-forming conditions of each layer in the above Examples and Comparative Examples, the resistivity and sheet resistance of the transparent electrode layer, and the visual evaluation results of the substrate with the transparent electrode.
- the refractive index of the second dielectric layer was 2.18
- the refractive index of the third dielectric layer was 1.47.
- the transparent electrode-equipped substrate of the example of the present invention is transparent because the generation of pattern wrinkles is suppressed and the color difference between transmitted light and reflected light between the electrode layer forming part and the non-formed part is small. It turns out that the pattern of an electrode layer is hard to be visually recognized.
- Example 8 in which the film thickness of the third dielectric layer is 60 nm and Example 9 in which the film thickness of the third dielectric layer is 65 nm, the generation of wrinkles is further suppressed, and the pattern is difficult to visually recognize. An attached substrate is obtained. From these results, it can be said that the pattern wrinkle tends to be suppressed by increasing the film thickness of the third dielectric layer present immediately below the transparent electrode layer.
- Comparative Example 5 and Comparative Example 7 both differ only in the film formation pressure of the first dielectric layer, and the film formation conditions of the third dielectric layer and the film formation conditions of the transparent electrode layer are Are the same.
- the transparent electrode layer of Comparative Example 5 has a lower resistance and a lower refractive index than the transparent electrode layer of Comparative Example 7, and the occurrence of pattern wrinkles is suppressed.
- the same tendency is seen from the comparison between Example 13 and Comparative Example 8. From these results, it is considered that not only the third dielectric layer but also the first dielectric layer contributes to lowering the resistance of the transparent electrode layer and suppressing pattern wrinkles.
- Comparative Example 9 in which the film thickness of the first dielectric layer was 30 nm, the generation of wrinkles was suppressed, but the color difference between transmitted light and reflected light between the electrode layer forming portion and the non-forming portion was large, and the pattern was visually recognized. It was done.
- Example 10 According to the comparison between Example 1 and Example 10, by increasing the magnetic flux density during film formation of the transparent electrode layer, the resistance of the transparent electrode layer is lowered, and the occurrence of pattern defects tends to be suppressed. It was.
- Reference Examples 1 to 8 In order to further examine the relationship between magnetic flux density and film characteristics during film formation of the transparent electrode layer, in Reference Examples 1 to 8 below, the configuration of the dielectric layer and the magnetic flux density during film formation of the transparent electrode layer were changed to be transparent. A substrate with electrodes was manufactured.
- a high refractive index transparent dielectric layer (second dielectric layer) made of niobium oxide is directly formed on one surface of a biaxially stretched PET film, and a transparent electrode layer is formed thereon. It was.
- a low refractive index transparent dielectric layer (third dielectric layer) made of SiO 2 is directly formed on one surface of a biaxially stretched PET film, and a transparent electrode layer is formed thereon. Been formed.
- a target having a tin oxide content of 10% by weight was used when forming the transparent electrode layer.
- the dielectric layer was not formed on one surface of the biaxially stretched PET film, and the transparent electrode layer was formed directly.
- the transparent electrode layer was patterned and heat-treated in the same manner as in the above Examples and Comparative Examples.
- the transparent electrode layer was not crystallized even after the heat treatment.
- Example 8 and Example 15 According to the comparison between Example 8 and Example 15 and the comparison between Reference Examples 2 to 4, by increasing the magnetic flux density when the ITO transparent electrode layer is formed on the dielectric layer made of silicon oxide, In addition, the generation of pattern wrinkles is suppressed, and a transparent electrode layer having a high transmittance and a low b * is obtained.
- Example 8 and Example 15 in which the film thickness of the third dielectric layer is 60 nm, by increasing the magnetic flux density at the time of forming the transparent electrode layer, the electrode layer forming portion is formed in both transmitted light and reflected light. And the electrode layer non-formed part is reduced, and a substrate with a transparent electrode is obtained in which the pattern of the transparent electrode layer is hardly visible.
- the average particle diameter of the crystal in the transparent electrode layer increases and the coefficient of variation of the average particle diameter increases.
- Such crystal characteristics are considered to contribute to lowering the resistance of the transparent electrode layer.
- the average crystal grain size is increased as compared with Reference Example 3 by increasing the magnetic flux density to 76 mT.
- the resistivity was almost the same in Reference Example 3 and Reference Example 4. From this, it is considered that not only the average grain size of crystal grains but also the coefficient of variation contributes to the reduction in resistivity.
- the ITO film is formed with a predetermined magnetic flux density on the dielectric layer of the transparent film substrate, the particle diameter of the ITO film after heat crystallization and the coefficient of variation of the particle diameter increase, There is a tendency that the resistance of the transparent electrode layer is lowered and the generation of pattern wrinkles is suppressed. That is, it is not limited to the case where the dielectric layer has a three-layer configuration, and an ITO film is formed with a predetermined magnetic flux density on a transparent film substrate including a transparent dielectric layer mainly composed of an oxide. While the resistance of the transparent electrode layer is lowered, the pattern wrinkles of the transparent electrode layer tend to be reduced.
- the transparent dielectric layer has a silicon oxide middle refractive index layer (first dielectric layer) having a predetermined thickness, and a metal oxide high refractive index layer (first dielectric layer). (2 dielectric layer) and silicon oxide low refractive index layer (third dielectric layer), the transparent electrode layer is formed on the transparent electrode layer with a predetermined magnetic flux density.
- the transmittance of the electrode layer forming part is increased, and the reflected light color difference and transmitted light color difference between the electrode layer forming part and the electrode layer non-forming part are reduced. There is a tendency that visual recognition is more suppressed. In particular, when the film thickness of the third dielectric layer exceeds 55 nm, the effect of suppressing pattern visual recognition is significant.
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Abstract
Description
以下、本発明の好ましい実施の形態について図面を参照しつつ説明する。図1は、本発明の一実施形態にかかる透明電極付き基板を模式的に表す断面図である。図1において、透明電極付き基板100は、透明フィルム1上に、屈折率n1の第一誘電体層21、屈折率n2の第二誘電体層22および屈折率n3の第三誘電体層23の3層からなる透明誘電体層2と、屈折率n4の透明電極層4とをこの順に有する。図1において、透明電極層4は、電極層形成部4aと電極層非形成部4bとにパターニングされている。このような透明電極付き基板は、例えば、透明フィルム1上に第一誘電体層21、第二誘電体層22、第三誘電体層23および透明電極層4が製膜された後、エッチング等によって透明電極層4がパターニングされることにより形成される。
透明フィルム1は、少なくとも可視光領域で無色透明であり、透明電極層形成温度における耐熱性を有していれば、その材料は特に限定されない。透明フィルムの材料としては、ポリエチレンテレフタレート(PET)やポリブチレンテレフテレート(PBT)やポリエチレンナフタレート(PEN)等のポリエステル樹脂やシクロオレフィン系樹脂、ポリカーボネート樹脂、ポリイミド樹脂、セルロース系樹脂等が挙げられる。中でも、ポリエチレンテレフタレートやシクロオレフィン系樹脂が好ましく用いられる。
透明フィルム1上には、酸化物を主成分とする透明誘電体層2が形成される。透明誘電体層2は、その上に透明電極層4が形成される際に、透明フィルム1から水分や有機物質が揮発することを抑制するガスバリア層として作用し得るとともに、膜成長の下地層としても作用し得る。本発明においては、透明誘電体層上に透明電極層が製膜されることで、透明電極層を低抵抗化することができる。透明誘電体層にこれらの機能を持たせるとともに、透明電極層がパターニングされた際のシワを低減する観点から、透明誘電体層2の膜厚は、5nm以上が好ましく、30nm以上がより好ましく、55nm以上が更に好ましい。一方、透明性の観点からは、誘電体層2の膜厚は、100nm以下が好ましく、85nm以下がより好ましく、70nm以下がさらに好ましい。
透明電極層4としては、インジウム・スズ複合酸化物(ITO)を主成分とする導電性酸化物層が形成される。透明電極層4の膜厚d4は、15~110nmが好ましい。透明電極付き基板100が静電容量方式タッチパネルに用いられる場合、透明電極層4の膜厚d4は、15nm~40nmであることが好ましく、21nm~35nmであることがより好ましく、23nm~30nmであることがさらに好ましい。透明電極層の膜厚を前記範囲とすることで、低抵抗かつ高透過率の透明電極層が得られる。また、透明電極層のパターンの視認を効果的に抑止するためには、d4は32nm以下がさらに好ましく、26nm以下が特に好ましい。
透明電極付き基板100は、透明フィルム1上に、透明誘電体層2および透明電極層4を形成することにより得られる。
△E={(△L*)2+(△a*)2+△b*)2}1/2
各透明誘電体層および透明電極層の屈折率は、分光エリプソメトリー測定を行い、cauchyモデルおよびtauc‐lorentzモデルでフィッティングすることにより、波長550nmの光に対する値を求めた。なお、測定に際しては、ハードコート層による干渉の影響を排除するために、透明導電層非形成面側表面が研磨処理された試料が用いられた。フィッティングに際して、各透明誘電体層および透明電極層の膜厚は、透明電極付き基板の断面の透過型電子顕微鏡(TEM)観察により求めた値を使用した。各透明誘電体層および透明導電層の屈折率、消衰係数および膜厚の測定値を用いたシミュレーションにより算出された透過率および反射率が、分光光度計による測定値と一致することを確認して、上記フィッティングの確度を確認した。
ウレタン系樹脂からなるハードコート層(屈折率1.53)が両面に形成された厚み188μmの二軸延伸PETフィルムの一方の面上に、ロール・トゥ・ロール方式の巻取り式スパッタリング装置を用いて、シリコン酸化物(SiOx層)からなる中屈折率透明誘電体層(第一誘電体層)、酸化ニオブからなる高屈折率透明誘電体層(第二誘電体層)、およびシリコン酸化物(SiO2)からなる低屈折率誘電体層(第三誘電体層)が順次形成された。
第二誘電体層の膜厚d2、および第三誘電体層の膜厚d3および透明電極層の膜厚が表1に示すように変更された。それ以外は、実施例1と同様にして、第一誘電体層、第二誘電体層、第三誘電体層および透明電極層が順次形成された後、透明電極層のパターニングおよび熱処理が行われた。
スパッタリング装置に装着する永久磁石を変更することにより、透明電極層を製膜する際の磁束密度が16mTに調整された。スパッタ製膜時のMF電源の電圧は、511Vであった。それ以外は上記実施例1と同様にして、第一誘電体層、第二誘電体層、第三誘電体層および透明電極層が順次形成された後、透明電極層のパターニングおよび熱処理が行われた。
透明電極層製膜時のターゲットとして、スズ酸化物含量10重量%のターゲットが用いられたこと以外は、実施例10と同様にして、第一誘電体層、第二誘電体層、第三誘電体層および透明電極層が順次形成された後、透明電極層のパターニングおよび熱処理が行われた。
透明電極層が30nmの膜厚で形成されたこと以外は、実施例10と同様にして、第一誘電体層、第二誘電体層、第三誘電体層および透明電極層が順次形成された後、透明電極層のパターニングおよび熱処理が行われた。
透明電極層製膜時のターゲットとして、スズ酸化物含量3重量%のターゲットが用いられたこと以外は、実施例10と同様にして、第一誘電体層、第二誘電体層、第三誘電体層および透明電極層が順次形成された後、透明電極層のパターニングおよび熱処理が行われた。比較例4の透明電極付き基板の電極層形成部の透過率は、87.2%であった。
製膜時のアルゴンおよび酸素の導入量を調整することにより、第一誘電体層および第三誘電体層製膜時の装置内圧力が表1に示すように変更された。それ以外は、実施例10と同様にして、第一誘電体層、第二誘電体層、第三誘電体層および透明電極層が順次形成された後、透明電極層のパターニングおよび熱処理が行われた。
第一誘電体層製膜時の導入ガス中の酸素の相対比率を減少させてスパッタリングが行われた。得られたSiOx層は、膜厚が5nm、屈折率が1.75であった。それ以外は、実施例10と同様にして、第一誘電体層、第二誘電体層、第三誘電体層および透明電極層が順次形成された後、透明電極層のパターニングおよび熱処理が行われた。
第一誘電体層が30nmの膜厚で形成されたこと以外は、実施例14と同様にして、第一誘電体層、第二誘電体層、第三誘電体層および透明電極層が順次形成された後、透明電極層のパターニングおよび熱処理が行われた。
スパッタリング装置に装着する永久磁石を変更することにより、透明電極層を製膜する際の磁束密度が76mTに調整された。スパッタ製膜時のMF電源の電圧は、306Vであった。それ以外は実施例8と同様にして、第一誘電体層、第二誘電体層、第三誘電体層および透明電極層が順次形成された後、透明電極層のパターニングおよび熱処理が行われた。実施例15の透明電極付き基板の電極層形成部の透過率は、89.4%であった。
二軸延伸PETフィルムの一方の面上に、中屈折率透明誘電体層(第一誘電体層)を形成せずに、酸化ニオブからなる高屈折率透明誘電体層(第二誘電体層)が直接形成され、その上に、実施例10と同様にして、シリコン酸化物(SiO2)からなる低屈折率誘電体層(第三誘電体層)および透明電極層が順次形成された後、透明電極層のパターニングおよび熱処理が行われた。
透明電極層製膜時の磁束密度と膜特性の関係についてさらに検討するため、以下の参考例1~8では、誘電体層の構成および透明電極層製膜時の磁束密度を変更して、透明電極付き基板が製造された。
2 透明誘電体層
21 第一誘電体層
22 第二誘電体層
23 第三誘電体層
10 透明フィルム基材
4 透明電極層
4a 電極層形成部(非エッチング部)
4b 電極層非形成部(エッチング部)
100 透明電極付き基板
Claims (16)
- 透明フィルムの少なくとも一方の面に、第一誘電体層;第二誘電体層;第三誘電体層;および電極層形成部と電極層非形成部とにパターニングされた透明電極層、をこの順に有する透明電極付き基板であって、
前記第一誘電体層は、SiOx(x≧1.5)を主成分とする膜厚が1nm~25nmのシリコン酸化物層であり、
前記第二誘電体層は、Nb,Ta,Ti,Zr,Zn,およびHfからなる群より選択される1以上の金属の酸化物を主成分とする、膜厚が5nm以上、10nm未満の金属酸化物層であり、
前記第三誘電体層は、SiOy(y>x)を主成分とする、膜厚が35nm~80nmのシリコン酸化物層であり、
前記透明電極層は、インジウム・スズ複合酸化物を主成分とする、膜厚が20nm~35nmの導電性金属酸化物層であり、
前記第一誘電体層の屈折率n1、前記第二誘電体層の屈折率n2、および前記第三誘電体層の屈折率n3が、n3<n1<n2の関係を満たし、
前記透明電極層は、抵抗率が5.0×10-4Ω・cm以下であり、
透明電極層付き基板の電極層形成部における透過率が87%以上である、透明電極付き基板。 - 前記透明電極層は、屈折率n4が1.88以下である、請求項1に記載の透明電極付き基板。
- 前記透明電極層の屈折率n4が、前記第一誘電体層の屈折率n1より大きく、かつ前記第二誘電体層の屈折率n2より小さい、請求項1または2に記載の透明電極付き基板。
- 前記透明電極層は、抵抗率が3.7×10-4Ω・cm以下である、請求項1~3のいずれか1項に記載の透明電極付き基板。
- 前記透明電極層におけるインジウム・スズ複合酸化物の平均結晶粒径が110nm~700nmである、請求項1~4のいずれか1項に記載の透明電極付き基板。
- 前記透明電極層におけるインジウム・スズ複合酸化物の結晶粒径の変動係数が0.35以上である、請求項5に記載の透明電極付き基板。
- 前記第三誘電体層の透明電極層側界面の算術平均粗さが1nm以下である、請求項1~6のいずれか1項に記載の透明電極付き基板。
- 前記第二誘電体層が、Nb2O5を主成分とする金属酸化物層である、請求項1~7のいずれか1項に記載の透明電極付き基板。
- 前記透明電極層のキャリア密度が、6.1×1020/cm3以上である、請求項1~8のいずれか1項に記載の透明電極付き基板。
- 前記透明電極層は、酸化インジウムと酸化スズの合計100重量部に対して、酸化スズを4重量部~14重量部含有する、請求項1~9のいずれか1項に記載の透明電極付き基板。
- 前記第三誘電体層の膜厚が、膜厚が55nmを超え80nm以下である、請求項1~10のいずれか1項に記載の透明電極付き基板。
- 請求項1~11のいずれか1項に記載の透明電極付き基板を製造する方法であって、
透明フィルム上に、第一誘電体層、第二誘電体層、第三誘電体層および透明電極層がこの順に形成され、
前記透明電極層は、スパッタリング法により非晶質のインジウム・スズ複合酸化物を主成分とする非晶質透明電極層を形成する非晶質層形成工程;および前記非晶質透明電極層を結晶化して結晶質透明電極層を得る結晶化工程、により形成され、
前記非晶質層形成工程におけるスパッタリング時のターゲット表面の磁束密度が30mT以上である、透明電極付き基板の製造方法。 - 前記第三誘電体層が、0.4Pa未満の圧力下でスパッタリング法により製膜される、請求項12に記載の透明電極付き基板の製造方法。
- 前記第一誘電体層が、0.4Pa未満の圧力下でスパッタリング法により製膜される、請求項13に記載の透明電極付き基板の製造方法。
- 透明フィルム基材の少なくとも一方の面に、酸化物を主成分とする誘電体層;および電極層形成部と電極層非形成部とにパターニングされた透明電極層、をこの順に有する透明電極付き基板であって、
前記透明電極層は、インジウム・スズ複合酸化物を主成分とする、膜厚が20nm~35nmの導電性金属酸化物層であり、前記透明電極層の抵抗率が5.0×10-4Ω・cm以下であり、
前記透明電極層における前記インジウム・スズ複合酸化物は、平均結晶粒径が110nm~700nmであり、かつ結晶粒径の変動係数が0.35以上である、透明電極付き基板。 - 請求項1~11のいずれか1項に記載の透明電極付き基板を備える、静電容量方式タッチパネル。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008275737A (ja) * | 2007-04-26 | 2008-11-13 | Toppan Printing Co Ltd | 光学薄膜積層体 |
JP2010021048A (ja) * | 2008-07-11 | 2010-01-28 | Kaneka Corp | 透明導電膜 |
JP2010069675A (ja) * | 2008-09-17 | 2010-04-02 | Toppan Printing Co Ltd | 機能性フィルム、その製造方法、積層体および電子デバイス |
JP2010184477A (ja) * | 2009-02-13 | 2010-08-26 | Toppan Printing Co Ltd | 積層フィルム及びその製造方法 |
WO2011048648A1 (ja) * | 2009-10-19 | 2011-04-28 | 東洋紡績株式会社 | 透明導電性積層フィルム |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11195487A (ja) * | 1997-12-27 | 1999-07-21 | Tdk Corp | 有機el素子 |
JP2004123403A (ja) * | 2002-09-30 | 2004-04-22 | Fuji Photo Film Co Ltd | 結晶性ito分散液の製造方法 |
US7133032B2 (en) * | 2003-04-24 | 2006-11-07 | Eastman Kodak Company | OLED display and touch screen |
JP3819927B2 (ja) * | 2004-06-03 | 2006-09-13 | 日東電工株式会社 | 透明導電性フィルム |
JP4984204B2 (ja) * | 2005-03-22 | 2012-07-25 | Dowaエレクトロニクス株式会社 | 酸化インジウム粉末およびその製造方法 |
KR100954309B1 (ko) * | 2005-09-12 | 2010-04-21 | 닛토덴코 가부시키가이샤 | 투명 도전성 필름, 터치 패널용 전극판 및 터치 패널 |
US7622865B2 (en) * | 2006-06-19 | 2009-11-24 | Seiko Epson Corporation | Light-emitting device, image forming apparatus, display device, and electronic apparatus |
JP5116004B2 (ja) * | 2006-08-03 | 2013-01-09 | 日東電工株式会社 | 透明導電性積層体及びそれを備えたタッチパネル |
US20100127611A1 (en) * | 2007-05-22 | 2010-05-27 | Masaaki Imura | Transparent electrode |
US7713758B2 (en) * | 2007-06-13 | 2010-05-11 | Tokyo Electon Limited | Method and apparatus for optimizing a gate channel |
JP5216501B2 (ja) * | 2007-09-28 | 2013-06-19 | 富士フイルム株式会社 | 光学フィルム、偏光板、及び画像表示装置 |
CN101566903B (zh) * | 2008-04-25 | 2012-01-18 | 联享光电股份有限公司 | 透明导电膜及应用其的具耐写性高穿透度电阻式触控面板 |
TWI361998B (en) * | 2008-05-08 | 2012-04-11 | Wintek Corp | Touch panel |
JP2010015861A (ja) | 2008-07-04 | 2010-01-21 | Toyobo Co Ltd | 透明導電性積層フィルム |
JP4966924B2 (ja) * | 2008-07-16 | 2012-07-04 | 日東電工株式会社 | 透明導電性フィルム、透明導電性積層体及びタッチパネル、並びに透明導電性フィルムの製造方法 |
JP5556436B2 (ja) * | 2009-10-13 | 2014-07-23 | 東洋紡株式会社 | 透明導電性積層フィルム及び透明導電性積層シート並びにタッチパネル |
EP2402481A1 (en) * | 2010-06-29 | 2012-01-04 | Applied Materials, Inc. | Method and system for manufacturing a transparent body for use in a touch panel |
JP5739742B2 (ja) * | 2010-11-04 | 2015-06-24 | 日東電工株式会社 | 透明導電性フィルムおよびタッチパネル |
US9563315B2 (en) * | 2010-11-09 | 2017-02-07 | Tpk Touch Solutions Inc. | Capacitive touch panel and method for producing the same |
JP6023402B2 (ja) * | 2010-12-27 | 2016-11-09 | 日東電工株式会社 | 透明導電性フィルムおよびその製造方法 |
US8747959B2 (en) * | 2011-06-30 | 2014-06-10 | Guardian Industries Corp. | Planar patterned transparent contact, devices with planar patterned transparent contacts, and/or methods of making the same |
US20130005139A1 (en) * | 2011-06-30 | 2013-01-03 | Guardian Industries Corp. | Techniques for manufacturing planar patterned transparent contact and/or electronic devices including same |
KR101407681B1 (ko) * | 2011-11-11 | 2014-06-17 | 가부시키가이샤 가네카 | 투명 전극 부착 기판 및 그 제조 방법, 및 터치 패널 |
-
2013
- 2013-01-29 CN CN201380025510.8A patent/CN104303240B/zh active Active
- 2013-01-29 JP JP2014515511A patent/JP6014128B2/ja active Active
- 2013-01-29 US US14/401,495 patent/US9696751B2/en active Active
- 2013-01-29 KR KR1020147033452A patent/KR101964945B1/ko active IP Right Grant
- 2013-01-29 WO PCT/JP2013/051831 patent/WO2013172055A1/ja active Application Filing
- 2013-02-07 TW TW102104772A patent/TWI569191B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008275737A (ja) * | 2007-04-26 | 2008-11-13 | Toppan Printing Co Ltd | 光学薄膜積層体 |
JP2010021048A (ja) * | 2008-07-11 | 2010-01-28 | Kaneka Corp | 透明導電膜 |
JP2010069675A (ja) * | 2008-09-17 | 2010-04-02 | Toppan Printing Co Ltd | 機能性フィルム、その製造方法、積層体および電子デバイス |
JP2010184477A (ja) * | 2009-02-13 | 2010-08-26 | Toppan Printing Co Ltd | 積層フィルム及びその製造方法 |
WO2011048648A1 (ja) * | 2009-10-19 | 2011-04-28 | 東洋紡績株式会社 | 透明導電性積層フィルム |
Cited By (21)
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CN105473756A (zh) * | 2014-05-20 | 2016-04-06 | 日东电工株式会社 | 透明导电性薄膜 |
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JP2016091183A (ja) * | 2014-10-31 | 2016-05-23 | 大日本印刷株式会社 | 中間基材フィルム、導電性フィルムおよびタッチパネルセンサ |
WO2016072441A1 (ja) * | 2014-11-07 | 2016-05-12 | Jx金属株式会社 | Itoスパッタリングターゲット及びその製造方法並びにito透明導電膜及びito透明導電膜の製造方法 |
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WO2017010249A1 (ja) * | 2015-07-13 | 2017-01-19 | コニカミノルタ株式会社 | ガスバリア性フィルム |
JP6159490B1 (ja) * | 2015-09-30 | 2017-07-05 | 積水化学工業株式会社 | 光透過性導電フィルム、及び、アニール処理された光透過性導電フィルムの製造方法 |
WO2017057556A1 (ja) * | 2015-09-30 | 2017-04-06 | 積水化学工業株式会社 | 光透過性導電フィルム、及び、アニール処理された光透過性導電フィルムの製造方法 |
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US9696751B2 (en) | 2017-07-04 |
CN104303240B (zh) | 2017-03-01 |
US20150145816A1 (en) | 2015-05-28 |
TW201349074A (zh) | 2013-12-01 |
CN104303240A (zh) | 2015-01-21 |
KR20150013638A (ko) | 2015-02-05 |
JP6014128B2 (ja) | 2016-10-25 |
TWI569191B (zh) | 2017-02-01 |
JPWO2013172055A1 (ja) | 2016-01-12 |
KR101964945B1 (ko) | 2019-04-02 |
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