WO2015159804A1 - Stratifié, stratifié conducteur et dispositif électronique - Google Patents

Stratifié, stratifié conducteur et dispositif électronique Download PDF

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Publication number
WO2015159804A1
WO2015159804A1 PCT/JP2015/061144 JP2015061144W WO2015159804A1 WO 2015159804 A1 WO2015159804 A1 WO 2015159804A1 JP 2015061144 W JP2015061144 W JP 2015061144W WO 2015159804 A1 WO2015159804 A1 WO 2015159804A1
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Prior art keywords
tin oxide
indium tin
oxide layer
layer
less
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PCT/JP2015/061144
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English (en)
Japanese (ja)
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尚洋 眞下
和久 吉岡
富田　倫央
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旭硝子株式会社
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Priority to JP2016513749A priority Critical patent/JPWO2015159804A1/ja
Publication of WO2015159804A1 publication Critical patent/WO2015159804A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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

Definitions

  • the present invention relates to a laminate, a conductive laminate, and an electronic device.
  • the transparent conductive film Since the transparent conductive film has conductivity and optical transparency, it is used as a transparent electrode, a dustproof film, and an electromagnetic wave shielding film. In recent years, a transparent conductive film has attracted attention as a capacitive touch panel electrode. An indium tin oxide film is preferably used as the transparent conductive film.
  • an indium tin oxide film pattern is formed by etching. For this reason, the indium tin oxide film is required to have good etching properties. In addition, the indium tin oxide film is required to have low etching pattern visibility so that the appearance of a touch panel or the like is improved. Furthermore, the indium tin oxide film is required to have optical transparency, electrical conductivity, durability against mechanical contact, and the like.
  • an indium tin oxide film As a method for producing an indium tin oxide film, a method of performing sputtering while heating a substrate is known. According to the above method, an indium tin oxide film that is crystalline and has good conductivity and durability can be produced. However, since it is crystalline, the etching property is not good.
  • an indium tin oxide film As a method for producing an indium tin oxide film, a method of performing sputtering at room temperature and a method of performing sputtering by introducing moisture are known. According to the above method, an indium tin oxide film that is amorphous and has good etching properties can be produced. However, since it is amorphous, conductivity and durability are not good.
  • a method in which an amorphous indium tin oxide film is formed, then etched and further heat-treated to form a crystalline indium tin oxide film.
  • etching property, electroconductivity, and durability become favorable.
  • such a method is referred to as a crystallization method.
  • the transmittance increases, so the visibility of the etching pattern decreases.
  • the crystallization method when the thickness is reduced, crystallization by heat treatment becomes difficult, so that conductivity and durability are not improved.
  • electroconductivity it can improve by making the content rate of the tin oxide in indium tin oxide high.
  • crystallization by heat treatment becomes difficult, and thus conductivity is not necessarily improved.
  • Patent Document 1 Conventionally, various manufacturing methods have been proposed as a method for manufacturing a transparent conductive film (for example, see Patent Document 1). Moreover, in order to suppress peeling between the base material and the transparent conductive film, it is known to provide a base layer between the base material and the transparent conductive film (see, for example, Patent Documents 2 and 3).
  • the present invention has been made to solve the above-mentioned problems, and a crystalline indium tin oxide layer can be obtained by heat treatment, and the visibility of an etching pattern formed on the indium tin oxide layer is also improved. It aims at providing the laminated body which can be reduced. Another object of the present invention is to provide a conductive laminate having a crystalline indium tin oxide layer and having low visibility of an etching pattern formed in the indium tin oxide layer. Furthermore, this invention aims at provision of the electronic device which has such an electroconductive laminated body.
  • the laminate of the present invention has a transparent substrate, an underlayer, and an indium tin oxide layer.
  • the underlayer is laminated on the transparent substrate and contains silicon, oxygen, and nitrogen.
  • the indium tin oxide layer is laminated on the base layer and is mainly made of amorphous indium tin oxide.
  • the laminated body of the present invention has the following reflectance difference ⁇ R of 1% or less by heat treatment at a heat treatment temperature of 150 ° C. and a heat treatment time of 30 minutes.
  • the reflectance difference ⁇ R is the average reflectance R 1 [%] at a wavelength of 480 nm or more and 650 nm or less at a position where the indium tin oxide layer exists, with the transparent substrate side being the light incident surface, and the indium tin oxide layer is It is the absolute value of the difference from the average reflectance R 2 [%] at a wavelength of 480 nm or more and 650 nm or less at a position where it does not exist.
  • the conductive laminate of the present invention has a transparent substrate, an underlayer, and an indium tin oxide layer.
  • the underlayer is laminated on the transparent substrate and contains silicon, oxygen, and nitrogen.
  • the indium tin oxide layer is laminated on the underlayer and is mainly made of crystalline indium tin oxide.
  • the following reflectance difference ⁇ R is 1% or less.
  • the reflectance difference ⁇ R is the average reflectance R 1 [%] at a wavelength of 480 nm or more and 650 nm or less at a position where the indium tin oxide layer exists, with the transparent substrate side being the light incident surface, and the indium tin oxide layer is It is the absolute value of the difference from the average reflectance R 2 [%] at a wavelength of 480 nm or more and 650 nm or less at a position where it does not exist.
  • the electronic device of the present invention has the conductive laminate of the present invention.
  • an underlayer containing silicon, oxygen, and nitrogen is disposed between the transparent substrate and the amorphous indium tin oxide layer.
  • This underlayer improves the crystallization of the indium tin oxide layer by heat treatment. Moreover, the visibility of the etching pattern formed in the indium tin oxide layer is also reduced by this base layer.
  • Sectional drawing which shows an example of the laminated body of this invention.
  • Sectional drawing which shows an example of the electroconductive laminated body of this invention.
  • FIG. 1 is a cross-sectional view showing an example of the laminate of the present invention.
  • the stacked body 10 includes, for example, a transparent base material 11, an underlayer 12, and an amorphous indium tin oxide layer 13 in this order.
  • the indium tin oxide layer 13 becomes a crystalline indium tin oxide layer by heat treatment.
  • the transparent substrate 11 is, for example, polyolefin such as polyethylene or polypropylene, polyester such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate, polyamide such as nylon 6 or nylon 66, polyimide, polyarylate, polycarbonate, polyacrylate or polyether. Sulphone, polysulfone, and unstretched or stretched plastic films of these copolymers are preferred.
  • the transparent base material 11 can also use another highly transparent plastic film and glass base material.
  • the transparent base material 11 may have a single layer structure or a laminated structure having two or more layers having different compositions.
  • a polyethylene terephthalate film is particularly preferable.
  • a hard coat layer, a primer layer, an undercoat layer, or the like may be provided on one or both surfaces of the transparent substrate 11.
  • the hard coat layer makes the transparent substrate 11 difficult to be damaged.
  • the primer layer improves the adhesion between the organic material and the inorganic material.
  • the undercoat layer is a refractive index adjusting layer or the like that reduces the visibility of the etching pattern formed on the indium tin oxide layer 13.
  • the transparent substrate 11 may be subjected to surface treatment such as easy adhesion treatment, plasma treatment, corona treatment and the like.
  • the thickness of the transparent substrate 11 is preferably 10 ⁇ m or more and 200 ⁇ m or less, and more preferably 25 ⁇ m or more and 180 ⁇ m or less from the viewpoints of flexibility, durability, and the like.
  • the underlayer 12 is provided to promote crystallization of the indium tin oxide layer 13.
  • the underlayer 12 compared to a silicon oxide layer (SiO 2 layer), a silicon nitride layer (Si 3 N 4 layer), a magnesium fluoride layer (MgF 2 layer), an aluminum oxide layer (Al 2 O 3 layer), etc.
  • SiO 2 layer silicon oxide layer
  • Si 3 N 4 layer silicon nitride layer
  • MgF 2 layer magnesium fluoride layer
  • Al 2 O 3 layer aluminum oxide layer
  • crystallization can be greatly promoted.
  • the underlayer 12 contains silicon, oxygen, and nitrogen as essential components.
  • the ratio of each element can be appropriately selected according to the effect of promoting crystallization, the required refractive index, and the like.
  • another element may be included, for example, aluminum (Al) or carbon (C) may be included.
  • the underlayer 12 contains nitrogen, for example, resistance to alkalinity (hereinafter, also referred to as alkali resistance) is significantly increased as compared with an underlayer made of silicon oxide. Thereby, when passing through the process exposed to alkaline chemicals, such as an etching process, damage, such as film
  • the ratio of the number of molecules of N 2 / O 2 contained in the underlayer 12 is preferably 0.03 or more and 15 or less, and 0.05 or more and 10 The following is more preferable, and 0.07 to 5 is particularly preferable.
  • the ratio of the number of molecules can be measured by electron beam spectroscopic analysis or secondary ion mass spectrometry.
  • the refractive index of the underlayer 12 at a wavelength of 500 nm is preferably 1.48 or more, more preferably 1.49 or more.
  • the refractive index of the underlayer 12 at a wavelength of 500 nm is preferably 2.00 or less, more preferably 1.95 or less, and even more preferably 1.9 or less.
  • An arbitrary refractive index in the above range can be obtained by adjusting the ratio of silicon, oxygen, and nitrogen in the underlayer 12.
  • the refractive index of the entire constituent layer can be adjusted regardless of the refractive index of each layer (hereinafter also simply referred to as a constituent layer) constituting the laminate 10 excluding the base layer 12. Adjustment is easy.
  • the refractive index of the underlayer 12 is within the above range, the effect of reducing the visibility of the etching pattern formed on the indium tin oxide layer 13 is great.
  • the thickness of the underlayer 12 is preferably 1 nm or more. When the thickness is 1 nm or more, the effect of promoting crystallization of the indium tin oxide layer 13 is large. Moreover, when thickness is 1 nm or more, the effect of reducing the visibility of the etching pattern formed in the indium tin oxide layer 13 is large. From the viewpoint of promoting crystallization and reducing the visibility of the etching pattern, the thickness of the underlayer 12 is more preferably 3 nm or more, further preferably 5 nm or more, and particularly preferably 7 nm or more.
  • the thickness of the underlayer 12 is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 70 nm or less from the viewpoint of productivity.
  • the underlayer 12 may have a single layer structure or a laminated structure having two or more layers having different compositions.
  • the refractive index of the foundation layer 12 may be read as the refractive index of the foundation film layer 12 in contact with the indium oxide layer 13, and the thickness may be read as the entire film thickness of the foundation layer 12 of the lamination structure.
  • the indium tin oxide layer 13 is amorphous and becomes crystalline by heat treatment. Since it is amorphous, the etching property is improved. Moreover, durability becomes favorable by becoming crystalline by heat processing.
  • the indium tin oxide layer 13 may be patterned by etching to provide a portion 13a where the indium tin oxide layer 13 is present and a portion 13b where the indium tin oxide layer 13 is not present.
  • the indium tin oxide layer 13 may have a single layer structure, or may have a laminated structure having two or more layers having different compositions.
  • the indium tin oxide layer 13 is preferably in contact with the underlayer 12 because crystallization by heat treatment is good.
  • amorphous and crystalline materials can be distinguished by the resistance change rate.
  • the evaluation object is immersed in an HCl solution (concentration: 1.5 mol / L) for 5 minutes. From the sheet resistance before and after immersion, the rate of change in resistance (sheet resistance after immersion / sheet resistance before immersion) is determined. Those having a resistance change rate of 200% or less are crystalline, and those having a resistance change rate exceeding 200% are amorphous. When the resistance change rate is 200% or less, the crystalline portion and the amorphous portion are mixed, and when the resistance change rate is about 100%, the whole is almost crystallized.
  • the indium tin oxide layer 13 is mainly composed of indium tin oxide, which is an oxide of indium and tin.
  • examples of the oxide constituting the indium tin oxide include indium oxide, tin oxide, and a composite oxide of indium oxide and tin oxide.
  • the indium tin oxide preferably contains 5% by mass to 17% by mass of tin in terms of oxide (SnO 2 , the same applies hereinafter).
  • tin is contained in an amount of 5% by mass or more in terms of oxide, the sheet resistance when crystallized is lowered.
  • tin is contained in an amount of 17% by mass or less in terms of oxide, crystallization becomes easy.
  • the indium tin oxide preferably contains 6% by mass or more of tin in terms of oxide, more preferably 7% by mass or more, and particularly preferably 8% by mass or more. Further, the indium tin oxide preferably contains 15% by mass or less of tin in terms of oxide.
  • the indium tin oxide layer 13 is preferably made of only indium tin oxide, but can contain components other than indium tin oxide as necessary and within the limits not departing from the spirit of the present invention.
  • components other than indium tin oxide include oxides such as aluminum, zirconium, gallium, silicon, tungsten, zinc, titanium, magnesium, cerium, and germanium.
  • Content of components other than indium tin oxide layer 13 in indium tin oxide layer 13 is 10 mass% or less in the whole indium tin oxide layer 13, 5 mass% or less is preferable, and 3 mass% or less is more preferable. 1% by mass or less is particularly preferable.
  • the thickness of the indium tin oxide layer 13 is preferably 10 nm or more. When the thickness is 10 nm or more, crystallization is good and sheet resistance after crystallization is also low. From the viewpoint of crystallization and sheet resistance, the thickness is more preferably 15 nm or more. On the other hand, the thickness is preferably 40 nm or less because the film formation time is shortened and the transmittance is increased. From the viewpoint of film formation time, transmittance, and reflectance difference ⁇ R, the thickness is more preferably 35 nm or less, and further preferably 30 nm or less.
  • the indium tin oxide layer 13 is crystallized by heat treatment.
  • the heat treatment can usually be performed in the atmosphere.
  • the heat treatment temperature is preferably 100 ° C. or higher, and the heat treatment time is preferably 3 minutes or longer.
  • the heat treatment temperature is preferably 170 ° C. or less, and the heat treatment time is preferably 180 minutes or less.
  • the laminate 10 preferably has a reflectance difference ⁇ R of 1% or less when the indium oxide layer 13 is crystallized by heat treatment.
  • the heat treatment temperature is 150 ° C. and the heat treatment time is 30 minutes.
  • the reflectance difference ⁇ R after the heat treatment is 1% or less, the visibility of the etching pattern formed on the indium tin oxide layer 13 is sufficiently lowered.
  • the reflectance difference ⁇ R after the heat treatment is more preferably 0.7% or less.
  • the adjustment of the reflectance difference ⁇ R can be performed by adjusting the thickness and refractive index of each layer after the heat treatment, and in particular by adjusting the thickness and refractive index of the underlayer 12.
  • the refractive index of the underlayer 12 varies greatly depending on the proportion of the constituent elements. Thereby, the refractive index of the entire constituent layer can be easily adjusted regardless of the refractive index of the constituent layer excluding the base layer 12.
  • FIG. 2 is a cross-sectional view showing an example of the conductive laminate 20.
  • the conductive laminate 20 is obtained by heat-treating the laminate 10.
  • the conductive laminate 20 includes, for example, a transparent substrate 11, an underlayer 12, and a crystalline indium tin oxide layer 21 in this order.
  • the transparent substrate 11 and the foundation layer 12 are the same as the transparent substrate 11 and the foundation layer 12 in the laminate 10.
  • the indium tin oxide layer 21 is crystalline, durability is improved.
  • the indium tin oxide layer 21 may be provided with a portion 21a where the indium tin oxide layer 21 exists and a portion 21b where the indium tin oxide layer 21 does not exist by pattern formation by etching. Examples of the etching pattern include a large number of transparent electrodes.
  • the indium tin oxide layer 21 is preferably in contact with the underlayer 12 because crystallization is good.
  • the indium tin oxide layer 21 is mainly composed of indium tin oxide, which is an oxide of indium and tin.
  • the oxide constituting the indium tin oxide include indium oxide, tin oxide, and a composite oxide of indium oxide and tin oxide.
  • the indium tin oxide layer 21 may have a single layer structure or a laminated structure having two or more layers having different compositions.
  • the specific resistance of the indium tin oxide layer 21 is preferably 2.8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less. In the case of the said specific resistance, it becomes a thing suitable for an electronic device.
  • the specific resistance is preferably 2.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, and more preferably 2.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less.
  • the indium tin oxide preferably contains 5% by mass to 17% by mass of tin in terms of oxide. When tin is contained in an amount of 5% by mass or more in terms of oxide, the specific resistance is lowered. On the other hand, when tin is contained in an amount of 17% by mass or less in terms of oxide, crystallization is good.
  • the indium tin oxide preferably contains 6% by mass or more of tin in terms of oxide, more preferably 7% by mass or more, and particularly preferably 8% by mass or more. Further, the indium tin oxide preferably contains 15% by mass or less of tin in terms of oxide.
  • the indium tin oxide layer 21 is preferably composed only of indium tin oxide, but can contain components other than indium tin oxide as necessary and within the limits not departing from the spirit of the present invention.
  • components other than indium tin oxide include oxides such as aluminum, zirconium, gallium, silicon, tungsten, zinc, titanium, magnesium, cerium, and germanium.
  • Content of components other than indium tin oxide 21 in indium tin oxide layer 21 is 10 mass% or less in the whole indium tin oxide layer 21, 5 mass% or less is preferable, and 3 mass% or less is more preferable. 1% by mass or less is particularly preferable.
  • the thickness of the indium tin oxide layer 21 is preferably 10 nm or more. When the thickness is 10 nm or more, crystallization is improved and sheet resistance is reduced. From the viewpoint of crystallization and sheet resistance, the thickness is more preferably 15 nm or more. On the other hand, the thickness is preferably 40 nm or less because the film formation time is shortened and the transmittance is increased. From the viewpoint of film formation time, transmittance, and reflectance difference ⁇ R, the thickness is more preferably 35 nm or less, and further preferably 30 nm or less.
  • the conductive laminate 20 preferably has the following reflectance difference ⁇ R of 1% or less.
  • the reflectance difference ⁇ R is 1% or less, the visibility of the etching pattern formed on the indium tin oxide layer 21 is sufficiently low.
  • the reflectance difference ⁇ R is preferably 0.7% or less.
  • the reflectance difference ⁇ R is the average reflectance R 1 [%] at a wavelength of 480 nm or more and 650 nm or less at the position where the indium tin oxide layer 21 exists with the transparent substrate 11 side as the light incident surface, and indium tin oxide.
  • the underlayer 12 is preferably present from the viewpoint of the visibility of the etching pattern, alkali resistance, and scratch resistance.
  • the adjustment of the reflectance difference ⁇ R can be performed by adjusting the thickness, refractive index and the like of each layer, and particularly by adjusting the thickness and refractive index of the underlayer 12.
  • the refractive index of the underlayer 12 varies greatly depending on the proportion of the constituent elements. Thereby, the refractive index of the entire constituent layer can be easily adjusted regardless of the refractive index of the constituent layer excluding the base layer 12.
  • the conductive laminate 20 is preferably used for an electronic device, for example, an electronic device having a display unit and a touch panel arranged on the front surface of the display unit.
  • the conductive laminate 20 is used as a substrate having a transparent electrode in a touch panel.
  • the touch panel include a resistive film type that specifies a touch position by contacting upper and lower electrodes, and a capacitive coupling method that senses a change in capacitance.
  • the laminated body 10 can be manufactured by forming an indium tin oxide layer 13 after forming the base layer 12 on the transparent substrate 11.
  • the film forming method is not necessarily limited, and a sputtering method, an ion plating method, and a vacuum evaporation method can be applied, and the sputtering method is particularly preferable.
  • the underlayer 12 is formed by sputtering using, for example, a sputtering target mainly made of silicon. At this time, it is preferable to adjust the ratio of the introduced gas as follows.
  • the metal mode and the transition mode are states in which a film having absorption in visible light due to lack of oxygen is to be formed.
  • the proportion of oxygen gas is preferably 0.1% by volume or more, more preferably 0.3% by volume or more, and further preferably 0.5% by volume or more with respect to the total amount of argon gas and oxygen gas.
  • the proportion of oxygen gas is preferably 30% by volume or less, more preferably 20% by volume or less, and still more preferably 10% by volume or less with respect to the total amount of argon gas and oxygen gas.
  • the reaction mode is a state in which silicon, oxygen, and nitrogen react to form a film having transparency to visible light.
  • the proportion of nitrogen gas is preferably 30% by volume or more, more preferably 40% by volume or more, and still more preferably 45% by volume or more with respect to the total amount of argon gas and nitrogen gas.
  • the ratio of nitrogen gas is preferably less than 50% by volume, more preferably 49.7% by volume or less, and further preferably 49.5% by volume or less with respect to the total amount of argon gas and nitrogen gas.
  • the ratio of argon gas and oxygen gas is adjusted so as to be in the metal mode or transition mode, and further, argon gas, oxygen gas, and nitrogen gas are introduced. It is preferable to adjust the ratio of argon gas and nitrogen gas so that the reaction mode is achieved. According to such a method, it is possible to form the underlayer 12 having a large effect of promoting crystallization of the indium tin oxide layer 13.
  • the indium tin oxide layer 13 is formed by sputtering using a sputtering target made of indium tin oxide, for example. It is preferable that a sputtering target contains 5 mass% or more and 17 mass% or less of tin in oxide conversion in indium tin oxide.
  • the indium tin oxide in the sputtering target is preferably composed of a sintered body obtained by mixing and sintering tin oxide (SnO 2 ) and indium oxide (In 2 O 3 ).
  • the indium tin oxide layer 13 is formed, for example, by introducing a mixed gas in which oxygen gas is mixed in an amount of 0.5% by volume to 10% by volume, preferably 0.8% by volume to 6% by volume in argon gas. Sputtering is preferably performed. By performing sputtering while introducing such a mixed gas, it is possible to form a film that is amorphous, can be easily crystallized by heat treatment, and has low specific resistance after crystallization.
  • the conductive laminate 20 is obtained by heat-treating the laminate 10.
  • the heat treatment can usually be performed in the atmosphere.
  • the heat treatment temperature is preferably 100 ° C. or higher, and the heat treatment time is preferably 3 minutes or longer.
  • the heat treatment temperature is preferably 170 ° C. or less, and the heat treatment time is preferably 180 minutes or less.
  • Examples 1 to 5 are examples of the present invention, and examples 6 to 9 are comparative examples of the present invention. Note that the present invention is not limited to these examples. Moreover, the thickness of each layer is calculated
  • Example 1 As a transparent substrate, a polyethylene terephthalate film having a thickness of 100 ⁇ m was prepared by subjecting the surface to an easy adhesion treatment. On this transparent substrate, a silicon oxynitride film (SiO x N y film) was formed as a base layer. The thickness of the underlayer is 10 nm. The refractive index of the underlayer is 1.49. The refractive index is a value at a wavelength of 500 nm and was measured by ellipsometry.
  • the underlayer was formed as follows. First, using a boron-doped silicon target, argon gas and oxygen gas were introduced, and pre-sputtering was performed with a DC pulse power source. The ratio of oxygen gas to the total amount of argon gas and oxygen gas is 5% by volume. The sputtering state at this time is a metal mode or a transition mode.
  • Sputtering was continued while introducing argon gas, oxygen gas, and nitrogen gas under the above conditions to form an underlayer on the transparent substrate.
  • the thickness of the underlayer was adjusted by the sputtering rate and the conveyance speed of the transparent substrate.
  • an amorphous indium tin oxide layer having a thickness of 25 nm was formed on the underlayer to obtain a test piece.
  • the ITO layer is formed by using a target (10% by mass of tin oxide (SnO 2 )) and 90% by mass of indium oxide (In 2 O 3 ) made of indium tin oxide containing 10% by mass of tin in terms of oxide.
  • a target 10% by mass of tin oxide (SnO 2 )
  • indium oxide In 2 O 3
  • argon gas and oxygen gas were introduced, and sputtering was performed by a DC power source.
  • the ratio of oxygen gas to the total amount of argon gas and oxygen gas is 1% by volume.
  • the thickness of the ITO layer was adjusted by the sputtering rate and the conveyance speed of the transparent substrate and the like.
  • Example 2 A base layer and an ITO layer were formed in the same manner as in Example 1 except that the base layer formation conditions were changed and the refractive index of the base layer was changed to 1.59.
  • the formation conditions of the underlayer are as follows. In the introduction of argon gas and oxygen gas during pre-sputtering, the ratio of oxygen gas to the total amount of argon gas and oxygen gas was set to 2% by volume. The sputtering state at this time is a metal mode or a transition mode. In the subsequent introduction of argon gas, oxygen gas, and nitrogen gas during sputtering, the ratio of nitrogen gas to the total amount of argon gas and nitrogen gas was 48% by volume. Note that the ratio of oxygen gas to the total amount of argon gas and oxygen gas was the same as in pre-sputtering. The state of sputtering at this time is a reaction mode.
  • Example 3 A base layer and an ITO layer were formed in the same manner as in Example 1 except that the base layer formation conditions were changed and the refractive index of the base layer was changed to 1.80.
  • the formation conditions of the underlayer are as follows. In the introduction of argon gas and oxygen gas during pre-sputtering, the ratio of oxygen gas to the total amount of argon gas and oxygen gas was set to 1% by volume. The sputtering state at this time is a metal mode or a transition mode. In the subsequent introduction of argon gas, oxygen gas, and nitrogen gas during sputtering, the ratio of nitrogen gas to the total amount of argon gas and nitrogen gas was 49 vol%. Note that the ratio of oxygen gas to the total amount of argon gas and oxygen gas was the same as in pre-sputtering. The state of sputtering at this time is a reaction mode.
  • Example 4 A base layer and an ITO layer were formed in the same manner as in Example 1 except that the base layer formation conditions were changed and the refractive index of the base layer was changed to 1.95.
  • the formation conditions of the underlayer are as follows. In the introduction of argon gas and oxygen gas at the time of pre-sputtering, the ratio of oxygen gas to the total amount of argon gas and oxygen gas was set to 0.5% by volume. The sputtering state at this time is a metal mode or a transition mode. In the subsequent introduction of argon gas, oxygen gas, and nitrogen gas at the time of sputtering, the ratio of nitrogen gas to the total amount of argon gas and nitrogen gas was 49.5% by volume. Note that the ratio of oxygen gas to the total amount of argon gas and oxygen gas was the same as in pre-sputtering. The state of sputtering at this time is a reaction mode.
  • Example 5 A base layer and an ITO layer were formed in the same manner as in Example 1 except that the thickness of the ITO layer was changed to 20 nm to obtain a test piece.
  • Example 6 A base layer and an ITO layer were formed in the same manner as in Example 1 except that the base layer was changed to a silicon oxide film (SiO 2 film) to obtain a test piece.
  • the SiO 2 film was formed by sputtering with a DC pulse power source using a boron-doped silicon target, introducing argon gas and oxygen gas. The ratio of oxygen gas to the total amount of argon gas and oxygen gas was 50% by volume. The state of sputtering at this time is a reaction mode.
  • the refractive index of the underlayer is 1.47.
  • Example 7 A base layer and an ITO layer were formed in the same manner as in Example 1 except that the base layer was changed to a silicon oxide film (Si 3 N 4 film) to obtain a test piece.
  • Si 3 N 4 film was formed by sputtering with a DC pulse power supply using a boron-doped silicon target and introducing argon gas and nitrogen gas. The ratio of nitrogen gas to the total amount of argon gas and nitrogen gas was 50% by volume. The state of sputtering at this time is a reaction mode.
  • the refractive index of the underlayer is 2.04.
  • Example 8 A base layer and an ITO layer were formed in the same manner as in Example 1 except that the base layer was changed to an aluminum oxide film (Al 2 O 3 film) to obtain a test piece.
  • the Al 2 O 3 film was formed by sputtering with a DC pulse power source using a pure aluminum target, introducing argon gas and nitrogen gas. The ratio of nitrogen gas to the total amount of argon gas and nitrogen gas was 50% by volume. The state of sputtering at this time is a reaction mode.
  • the refractive index of the underlayer is 2.04.
  • Example 9 A test piece was produced by forming an underlayer and an ITO layer in the same manner as in Example 6 except that the thickness of the ITO layer was changed to 20 nm.
  • the test piece of each example was heat-treated in air at 150 ° C. for 30 minutes.
  • the following evaluation was performed about the test piece after heat processing.
  • the results are shown in Table 1.
  • the flow ratio (oxygen) of Examples 1 to 5 is the ratio of oxygen gas to the total amount of argon gas and oxygen gas when introducing argon gas and oxygen gas during pre-sputtering.
  • the flow ratio (nitrogen) of Examples 1 to 5 is the ratio of nitrogen gas to the total amount of argon gas and nitrogen gas when argon gas, oxygen gas, and nitrogen gas are introduced during subsequent sputtering. is there.
  • composition analysis was performed by photoelectron spectroscopy for the underlayer 12 of Examples 1 to 5 in which the effect of reducing the sheet resistance was recognized.
  • the ratio of the number of molecules of N 2 / O 2 in the underlayer 12 of Examples 1 to 5 was 0.05 or more and 3.6 or less.
  • the molecular number ratio of N 2 / O 2 in Example 1 is 0.06
  • the molecular number ratio of N 2 / O 2 in Example 2 is 0.07
  • the molecular number ratio of N 2 / O 2 in Example 3 is 1
  • the ratio of N 2 / O 2 molecules in Example 4 and Example 4 was 3.6.
  • Example 10 is an example of the present invention
  • Example 11 is a comparative example of the present invention.
  • the transparent substrate was a polyethylene terephthalate film having a refractive index of 1.53 with respect to light having a wavelength of 500 nm and a thickness of 100 ⁇ m.
  • urethane acrylate containing a titanium oxide filler was laminated to a thickness of 1 ⁇ m as an undercoat layer.
  • the undercoat layer has a refractive index of 1.55 with respect to light having a wavelength of 500 nm.
  • a first silicon oxynitride layer having a refractive index of 1.70 with respect to light having a wavelength of 500 nm was laminated so as to have a thickness of 47 nm.
  • a second silicon oxynitride layer having a refractive index of 1.50 with respect to light having a wavelength of 500 nm was laminated on the first silicon oxynitride layer so as to have a thickness of 20 nm.
  • the base layer includes a first silicon oxynitride layer and a second silicon oxynitride layer.
  • An ITO layer having a refractive index of 1.83 with respect to light having a wavelength of 500 nm was laminated on the underlayer so as to have a thickness of 25 nm.
  • the reflectance difference ⁇ R was calculated for such a test piece.
  • the vacuum between the light source and the test piece and between the test piece and the measuring instrument is assumed to be a vacuum (refractive index is 1), and the angle between the normal of the surface of the test piece and the light traveling direction is zero. It was assumed that light was incident on the test piece from the transparent substrate side.
  • the portion of ITO layer for obtaining an average reflectivity R 2 is not present, it consisted of the transparent substrate and the underlayer. As a result, the reflectance difference ⁇ R was 0.02%.
  • Example 11 The test piece was the same as that of Example 10 except that the configuration of the underlayer was changed.
  • the underlayer was a silicon oxide layer having a refractive index of 1.47 with respect to light having a wavelength of 500 nm and a thickness of 30 nm.
  • the reflectance difference ⁇ R was calculated in the same manner as in Example 11, the reflectance difference ⁇ R was 1.35%.
  • SYMBOLS 10 Laminated body, 11 ... Transparent base material, 12 ... Underlayer, 13 ... Amorphous indium tin oxide layer, 20 ... Conductive laminated body, 21 ... Crystalline indium tin oxide layer.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne un stratifié qui permet d'obtenir une couche d'oxyde d'indium-étain cristalline par traitement thermique, et qui peut réduire la visibilité d'un motif de gravure qui est formé sur la couche d'oxyde d'indium-étain. Ce stratifié comprend une base transparente, une couche de fondation et une couche d'oxyde d'indium-étain. La couche de fondation est stratifiée sur la base transparente, et contient du silicium, de l'oxygène et de l'azote. La couche d'oxyde d'indium-étain est stratifiée sur la couche de fondation, et est principalement composée d'un oxyde d'indium-étain amorphe. Ce stratifié présente une différence de réflectance (∆R) de 1 % ou moins après traitement thermique à une température de traitement thermique de 150 °C pendant une durée de traitement thermique de 30 minutes. La différence de réflectance (∆R) est la valeur absolue de la différence entre la réflectance moyenne (R1) [%] de positions où la couche d'oxyde d'indium-étain est présente et la réflectance moyenne (R2) [%] de positions où la couche d'oxyde d'indium-étain est absente.
PCT/JP2015/061144 2014-04-15 2015-04-09 Stratifié, stratifié conducteur et dispositif électronique WO2015159804A1 (fr)

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JPH1148388A (ja) * 1997-07-31 1999-02-23 Mitsui Chem Inc 透明導電性フィルム
JPH11110110A (ja) * 1997-09-29 1999-04-23 Mitsui Chem Inc タッチパネル用透明導電性フィルム
JP2005183007A (ja) * 2003-12-16 2005-07-07 Dainippon Printing Co Ltd 透明導電性シート
JP2008310550A (ja) * 2007-06-14 2008-12-25 Epson Imaging Devices Corp 静電容量型入力装置
JP2010027294A (ja) * 2008-07-16 2010-02-04 Nitto Denko Corp 透明導電性フィルム及びタッチパネル
JP2010137447A (ja) * 2008-12-12 2010-06-24 Toyobo Co Ltd 透明導電性積層フィルム
JP2012134085A (ja) * 2010-12-24 2012-07-12 Nitto Denko Corp 透明導電性フィルムおよびその製造方法
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JPH1034798A (ja) * 1996-07-29 1998-02-10 Mitsui Petrochem Ind Ltd 透明導電性フィルム
JPH1148388A (ja) * 1997-07-31 1999-02-23 Mitsui Chem Inc 透明導電性フィルム
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JP2010137447A (ja) * 2008-12-12 2010-06-24 Toyobo Co Ltd 透明導電性積層フィルム
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