JP2013193440A - Light-transmissive conductive film, and method for manufacturing and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart a desirable surface resistance value to a light-transmissive conductive film including (A) a light-transmissive support layer and (B) a light-transmissive conductive layer of 100 nm or larger in thickness including indium tin oxide.SOLUTION: A light-transmissive conductive film is characterized in that a peak of X-ray diffraction of a light-transmissive conductive flayer (B) meets requirements (i) to (iii). Namely, (i) a peak of a (222) plane is strongest; (ii) a half-value width of the peak of the (222) plane is 0.5 or less; and (iii) peak intensities of a (332) plane and a (134) plane are both 3% or larger of a peak intensity of the (222) plane.

Description

  The present invention relates to a light-transmitting conductive film, a manufacturing method thereof, and an application thereof.

  Many light transmissive conductive films are used in which a light transmissive conductive layer made of indium tin oxide (ITO) is disposed on at least one surface of a light transmissive support layer made of plastic or the like directly or via another layer. ing. These applications include solar cells that convert light energy into electrical energy, and on the contrary, displays that convert electrical energy into light energy (including organic EL), lighting, electronic paper (or electronic ink), etc. In addition, a transistor, a printable circuit, and the like are also included.

  As a light-transmitting conductive film used for the above-mentioned applications, since a high surface resistance value causes a decrease in output, it is generally desirable that the surface resistance value (sheet resistance) is relatively low. . For this reason, the thickness of the light-transmitting conductive layer is relatively thick and is approximately 100 nm or more (Patent Document 1).

JP 2006-269338 A

  In a conventional light-transmitting conductive film containing an ITO-containing light-transmitting conductive layer, a sufficiently low surface resistance value cannot be achieved simply by setting the thickness of the ITO-containing light-transmitting conductive layer to 100 nm or more. . This invention makes it a subject to provide the surface resistance value suitable for uses, such as a solar cell, to the light transmissive conductive film containing the ITO containing light transmissive conductive layer of thickness 100nm or more.

The inventors of the present invention have made extensive studies to solve the above problems, and in X-ray diffraction, the peak of the (222) plane is the strongest, the half width of the peak of the (222) plane is 0.5 or less, and The above problem can be solved by forming the light-transmitting conductive layer so that the peak intensity of the (332) plane and the (134) plane are both 3% or more of the peak intensity of the (222) plane. I found it. The present invention has been completed by further various studies based on this new knowledge, and is as follows.
Item 1
(A) a light-transmitting support layer; and (B) a light-transmitting conductive film containing a light-transmitting conductive layer containing indium tin oxide,
The light transmissive conductive layer (B) is disposed on at least one surface of the light transmissive support layer (A) directly or via one or more other layers,
The thickness of the light transmissive conductive layer (B) is 100 nm or more, and the peak in the X-ray diffraction of the light transmissive conductive layer (B) satisfies the following requirements (i) to (iii): Light transmissive conductive film characterized by:
(I) The peak at (222) plane is strongest;
(Ii) The peak half width of the (222) plane is 0.5 or less; and (iii) the peak intensity of the (332) plane and the (134) plane are each 3% or more of the peak intensity of the (222) plane It is.
Item 2
Item 2. The light transmissive conductive film according to Item 1, wherein the surface resistance is 60Ω / □ or less.
Item 3
The light-transmissive conductive layer (B) is
(1) Obtained by a method comprising a step of forming a layer containing indium tin oxide by an ion plating method on a layer held at 90 ° C. or more adjacent to the light transmissive conductive layer (B). Item 3. The light transmissive conductive film according to Item 1 or 2.
Item 4
Item 3. The light transmissive conductive layer (B) can be obtained by a method further comprising (2) a step of maintaining the layer containing indium tin oxide obtained in the step (1) at 90 ° C. or higher. The light-transmitting conductive film described.
Item 5
Item 5. A solar cell, a display, illumination, electronic paper, a transistor, a printable circuit, or a transparent sheet heating element, containing the light transmissive conductive film according to any one of Items 1 to 4.
Item 6
(A) a light-transmitting support layer; and (B) a light-transmitting conductive film containing a light-transmitting conductive layer containing indium tin oxide,
The light transmissive conductive layer (B) is disposed on at least one surface of the light transmissive support layer (A) directly or via one or more other layers,
The thickness of the light transmissive conductive layer (B) is 100 nm or more, and the peak in the X-ray diffraction of the light transmissive conductive layer (B) satisfies the following requirements (i) to (iii): A method for producing a light transmissive conductive film, characterized in that
A method comprising a step of forming a layer containing indium tin oxide by an ion plating method on a layer held at 90 ° C. or more adjacent to the light transmissive conductive layer (B):
(I) The peak on the (222) plane is strongest;
(Ii) The peak half width of the (222) plane is 0.5 or less; and (iii) the peak intensity of the (332) plane and the (134) plane are each 3% or more of the peak intensity of the (222) plane It is.

  According to the present invention, a light transmissive conductive film having a preferable surface resistance value can be provided.

It is sectional drawing which shows the light transmissive conductive film of this invention by which the light transmissive conductive layer (B) is arrange | positioned at the single side | surface of a light transmissive support layer (A). It is sectional drawing which shows the light transmissive conductive film of this invention by which a light transmissive conductive layer (B) is arrange | positioned on both surfaces of a light transmissive support layer (A). It is sectional drawing which shows the light transmissive conductive film of this invention in which the light transmissive conductive layer (B) and the undercoat layer (C) are arrange | positioned at the single side | surface of a light transmissive support layer (A). It is sectional drawing which shows the light transmissive conductive film of this invention in which the light transmissive conductive layer (B) and the undercoat layer (C) are each arrange | positioned on both surfaces of a light transmissive support layer (A). 1 shows a light transmissive conductive film of the present invention in which a light transmissive conductive layer (B), an undercoat layer (C) and a hard coat layer (D) are arranged on one side of a light transmissive support layer (A). It is sectional drawing. The light transmissive conductive film of the present invention, in which a light transmissive conductive layer (B), an undercoat layer (C), and a hard coat layer (D) are disposed on both surfaces of the light transmissive support layer (A), respectively. It is sectional drawing shown. It is sectional drawing which shows the dye-sensitized solar cell using the translucent conductive film of this invention. It is sectional drawing which shows the organic EL element using the transparent electroconductive film of this invention. 2 is a measurement result of X-ray diffraction of Example 1. 4 is a measurement result of X-ray diffraction of Example 2. 4 is a measurement result of X-ray diffraction of Comparative Example 1. 10 is a measurement result of X-ray diffraction of Comparative Example 2. It is a measurement result of the X-ray diffraction of the comparative example 3.

1 Light-transmissive conductive film 11 Light-transmissive support layer (A)
12 Light transmissive conductive layer (B)
13 Undercoat layer (C)
14 Hard coat layer (D)
21 Semiconductor particle 22 Dye 23 Electrolyte layer 24 Counter electrode layer 31 Organic EL layer 32 Cathode electrode layer

1. Light transmissive conductive film The light transmissive conductive film of the present invention comprises:
(A) a light-transmitting support layer; and (B) a light-transmitting conductive film containing a light-transmitting conductive layer containing indium tin oxide,
The light transmissive conductive layer (B) is disposed on at least one surface of the light transmissive support layer (A) directly or via one or more other layers,
The thickness of the light transmissive conductive layer (B) is 100 nm or more, and the peak in the X-ray diffraction of the light transmissive conductive layer (B) satisfies the following requirements (i) to (iii): Light transmissive conductive film characterized by:
(I) The peak on the (222) plane is strongest;
(Ii) The peak half width of the (222) plane is 0.5 or less; and (iii) the peak intensity of the (332) plane and the (134) plane are each 3% or more of the peak intensity of the (222) plane It is.

  In the present invention, “light-transmitting” means having a property of transmitting light (translucent). “Light transmissivity” includes transparency. “Light transmissivity” means, for example, the property that the total light transmittance is 80% or more, preferably 85% or more, more preferably 87% or more. In the present invention, the total light transmittance is measured based on JIS-K-7105 using a haze meter (trade name: NDH-2000 manufactured by Nippon Denshoku Co., Ltd. or equivalent).

  In this specification, when mentioning the relative positional relationship between two layers among a plurality of layers arranged on one surface of the light transmissive support layer (A), the light transmissive support layer (A) is used as a reference. One layer having a large distance from the light transmissive support layer (A) is referred to as “upper layer” or “located above”, and the other layer having a small distance from the light transmissive support layer (A). May be referred to as “lower layer” or “located below”.

  In FIG. 1, the one aspect | mode of the transparent electroconductive film of this invention is shown. In this embodiment, the light transmissive conductive layer (B) is directly disposed on one surface of the light transmissive support layer (A). Such a light-transmitting conductive film is sometimes referred to as a “light-transmitting single-sided conductive film”.

  FIG. 2 shows another embodiment of the light transmissive conductive film of the present invention. In this embodiment, the light transmissive conductive layer (B) is directly disposed on both surfaces of the light transmissive support layer (A). Such a light transmissive conductive film is sometimes referred to as a “light transmissive double-sided conductive film”.

1.1 Light transmissive support layer (A)
In the present invention, the light transmissive support layer refers to a light transmissive conductive film containing a light transmissive conductive layer, which plays a role of supporting the layer containing the light transmissive conductive layer. Although it does not specifically limit as a light-transmissive support layer (A), For example, the light used for the use of a solar cell, a display, illumination, electronic paper (electronic ink), a transistor, a printable circuit, or a transparent planar heating element In a transparent conductive film, what is normally used as a light-transmissive support layer can be used.

  Although the raw material of a light-transmissive support layer (A) is not specifically limited, For example, various organic polymers etc. can be mentioned. The organic polymer is not particularly limited. For example, polyester resin, acetate resin, polyether resin, polycarbonate resin, polyacrylic resin, polymethacrylic resin, polystyrene resin, polyolefin resin, polyimide resin, etc. Examples include resins, polyamide resins, polyvinyl chloride resins, polyacetal resins, polyvinylidene chloride resins, and polyphenylene sulfide resins. Although it does not specifically limit as polyester-type resin, For example, a polyethylene terephthalate (PET), a polyethylene naphthalate (PEN), etc. are mentioned. The material of the light transmissive support layer (A) is preferably a polyester resin, and particularly preferably PET. The light transmissive support layer (A) may be composed of any one of these, or may be composed of a plurality of types.

  Although the thickness of a light-transmissive support layer (A) is not specifically limited, For example, the range of 2-300 micrometers is mentioned.

1.2 Light transmissive conductive layer (B)
The light transmissive conductive layer (B) is disposed on at least one surface of the light transmissive support layer (A) directly or via one or more other layers.

  In the present invention, the light-transmitting conductive layer means a layer that conducts electricity and transmits visible light. Although it does not specifically limit as a light transmissive conductive layer (B), For example, the light used for the use of a solar cell, a display, illumination, electronic paper (electronic ink), a transistor, a printable circuit, or a transparent planar heating element In the transmissive conductive film, those usually used as the light transmissive conductive layer can be used.

  The light transmissive conductive layer (B) contains indium tin oxide (ITO) doped with tin, and may further contain other components. Examples of other components include, but are not limited to, aluminum oxide, zirconium oxide, germanium oxide, zinc oxide, and titanium oxide. In addition to indium tin oxide, the light-transmitting conductive layer (B) may further contain any one of these, or may contain a plurality of types.

The light transmissive conductive layer (B) is preferably indium tin oxide which is an inorganic compound obtained using indium (III) oxide (In ₂ O ₃ ) and tin oxide (IV) (SnO ₂ ). In this case, the addition amount of SnO ₂ is not particularly limited, and examples thereof include 1 to 15% by weight, preferably 2 to 10% by weight, and more preferably 3 to 8% by weight.

  The thickness of the light transmissive conductive layer (B) is 100 nm or more, preferably 100 to 500 nm, more preferably 100 to 300 nm, and still more preferably 100 to 200 nm.

  In the present invention, the thickness of the light-transmitting conductive layer (B) is measured using a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, product surface: RIX1000 or equivalent).

  In the X-ray diffraction of the light transmissive conductive layer (B), the peak on the (222) plane is the strongest.

The half width of the peak of the (222) plane in the X-ray diffraction of the light-transmitting conductive layer (B) is 0.5 or less, preferably 0.4 or less.
In the X-ray diffraction of the light transmissive conductive layer (B), the peak intensity of the (332) plane and the (134) plane are both 3% or more of the peak intensity of the (222) plane, preferably 4% or more. .

  In the present invention, the X-ray diffraction method is performed under the following conditions. The X-ray diffractometer is measured by a thin film method using a Rigaku thin film evaluation sample horizontal X-ray diffractometer SmartLab or equivalent. A parallel beam optical arrangement is used, and CuKα rays (wavelength: 1.54186Å) are used as a light source at a power of 40 kV and 30 mA. The incident side slit system uses a solar slit of 5.0 °, a height control slit of 10 mm, and an incident slit of 0.1 mm, and the light receiving side slit has a parallel slit analyzer (PSA) of 0.114 deg. Is used. The detector uses a scintillation counter. The sample stage uses a porous adsorption sample holder, and a sample is adsorbed and fixed by a pump. The incident side is fixed at 0.35 °, the step interval is 0.01 °, the measurement speed is 3.0 ° / min, and the measurement range is 5 ° to 80 °.

  The peak of the (222) plane in the X-ray diffraction of the light transmissive conductive layer (B) is derived from ITO. That the half width of this peak is smaller indicates that ITO has a more uniform crystal state, in other words, higher crystallinity.

The light transmissive conductive film of the present invention has a surface resistance value due to the feature that the half width of the peak of the (222) plane in the X-ray diffraction of the light transmissive conductive layer (B) is 0.5 or less. Indicates 60Ω / □ or less. The unit of the surface resistance value may be expressed as “Ω / cm ² ”, “Ω / sq.” Or simply “Ω” in addition to “Ω / □”.

  The method for forming the light transmissive conductive layer (B) may be either wet or dry.

  The method for forming the light transmissive conductive layer (B) is not particularly limited, and examples thereof include an ion plating method, a sputtering method, a vacuum deposition method, a CVD method, and a pulse laser deposition method. As a method for forming the light transmissive conductive layer (B), an ion plating method is preferable.

As a method of forming the light transmissive conductive layer (B),
(1) A method comprising a step of forming a layer containing indium tin oxide on a layer held at 90 ° C. or more adjacent to the light transmissive conductive layer (B) is preferable. Note that the layer adjacent to the light transmissive conductive layer (B) may be referred to as a substrate in this specification. In this case, the substrate is preferably maintained at 90 to 250 ° C, more preferably 90 to 150 ° C.
In the present invention, the method for maintaining the substrate at a desired temperature is not particularly limited. For example, it comprises a substrate transport step having a support roll that contacts the back side of the substrate and supports and transports the substrate, and the support roll has an inflow port for flowing liquid into the support roll and an outflow port for flowing out. And a method of controlling the temperature of the support roll by circulating the liquid in the support roll. For example, when this method is used, in the present invention, “holding the substrate at a specific temperature” means that the average value of the temperature of the liquid inlet and outlet is the temperature. Thus, not only in the case of using the above method, in the present invention, “holding the substrate at a specific temperature” generally means that the environment (liquid or atmosphere) in which the substrate is placed is the temperature. means.

As a method of forming the light transmissive conductive layer (B), in addition to the step (1),
(2) A method comprising a step of maintaining the layer containing indium tin oxide obtained in the step (1) at 90 ° C. or higher is preferable. In this case, as said temperature, 90-250 degreeC is preferable and 90-150 degreeC is more preferable. Moreover, as time to hold | maintain at the said temperature, 10 minutes-3 hours are preferable, and 10 minutes-1 hour are more preferable. Examples of the processing atmosphere include vacuum, air, nitrogen, oxygen, hydrogenated nitrogen, and the like, or a combination of two or more of these.

1.3 Undercoat layer (C)
The light-transmitting conductive film of the present invention has an undercoat layer on the surface of the light-transmitting support layer (A) on which the light-transmitting conductive layer (B) is disposed, either directly or via one or more other layers. (C) may be arranged. When the undercoat layer (C) is disposed, at least one of the light transmissive conductive layers (B) is disposed on the surface of the light transmissive support layer (A) via at least the undercoat layer (C). Is arranged. In this case, at least one of the light transmissive conductive layers (B) may be disposed adjacent to the undercoat layer (C).

  In FIG. 3, the one aspect | mode of the transparent electroconductive film of this invention is shown. In this embodiment, the undercoat layer (C) is disposed adjacent to one surface of the light transmissive support layer (A), and the light transmissive conductive layer (B) is adjacent to the undercoat layer (C). Are arranged.

  In FIG. 4, the one aspect | mode of the transparent electroconductive film of this invention is shown. In this embodiment, the undercoat layer (C) is disposed adjacent to both surfaces of the light transmissive support layer (A), and the light transmissive conductive layer (B) is formed on both of the undercoat layers (C). ).

  Although the material of an undercoat layer (C) is not specifically limited, For example, you may have a dielectric property. The material for the undercoat layer (C) is not particularly limited. For example, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon alkoxide, alkylsiloxane and its condensate, polysiloxane, silsesquioxane, Examples include polysilazane. The undercoat layer (C) may be composed of any one of them, or may be composed of a plurality of types. A light-transmitting underlayer containing silicon oxide is preferable, and a light-transmitting underlayer made of silicon oxide is more preferable.

  One layer of the undercoat layer (C) may be disposed. Alternatively, two or more layers may be arranged adjacent to each other or separated from each other via other layers.

  As for the thickness per layer of an undercoat layer (C), 15-40 nm etc. are mentioned. When two or more layers are disposed adjacent to each other, the total thickness of all the undercoat layers (C) adjacent to each other may be within the above range. In the example list shown on the left, the following are more preferable than the above.

  The method for disposing the undercoat layer (C) may be either wet or dry, and is not particularly limited. Examples of the wet include a sol-gel method, a fine particle dispersion, and a method of applying a colloid solution. . Examples of a method for disposing the undercoat layer (C) include a method of laminating on an adjacent layer by a sputtering method, an ion plating method, a vacuum deposition method, a pulse laser deposition method, or the like.

1.4 Hard coat layer (D)
The light transmissive conductive film of the present invention is hard on the surface of the light transmissive support layer (A) on the side where the light transmissive conductive layer (C) is disposed, directly or via one or more other layers. A coat layer (D) may be disposed. The hard coat layer (D) is preferably disposed directly on the surface of the light transmissive support layer (A) on the side where the light transmissive conductive layer (C) is disposed.

  The undercoat layer (C) is disposed on the surface of the hard coat layer (D) directly or via another layer. The undercoat layer (C) is preferably disposed directly on the surface of the hard coat layer (D).

  One layer of the hard coat layer (D) may be disposed. Alternatively, two or more layers may be arranged adjacent to each other or separated from each other via other layers.

  When two or more layers of the hard coat layer (D) are arranged adjacent to each other, the hard coat positioned below may have a higher refractive index than the hard coat positioned above. . By adopting such a configuration, an optical interference action is generated between two layers having different refractive indexes, which is preferable because the transmittance of the light-transmitting conductive film is improved.

  In FIG. 5, the one aspect | mode of the transparent electroconductive film of this invention is shown. In this embodiment, the hard coat layer (D) is disposed directly on one surface of the light transmissive support layer (A), and the undercoat layer (C) is disposed directly on the hard coat layer (D). Furthermore, the light-transmitting conductive layer (B) is directly disposed on the undercoat layer (C).

  In FIG. 6, the one aspect | mode of the transparent electroconductive film of this invention is shown. In this embodiment, the hard coat layer (D) is directly disposed on both sides of the light transmissive support layer (A), and the undercoat layer (C) is directly on the hard coat layer (D). Further, the light-transmitting conductive layer (B) is directly disposed on the undercoat layer (C).

  In the present invention, the hard coat layer means a layer that prevents the plastic surface from being damaged. Although it does not specifically limit as a hard-coat layer (D), For example, the light transmittance used for the use of a solar cell, a display, illumination, electronic paper (electronic ink), a transistor, a printable circuit, or a transparent planar heating element What is normally used as a hard-coat layer in an electroconductive film can be used.

  The material of the hard coat layer (D) is not particularly limited, and examples thereof include colloidal particles such as acrylic resin, silicone resin, urethane resin, melamine resin, alkyd resin, silica, zirconia, titania, and alumina. Can be mentioned. The hard coat layer (D) may be composed of any one of them, or may be composed of a plurality of types. An acrylic resin in which zirconia particles are dispersed is more preferable.

  Although the thickness per layer of a hard-coat layer (D) is not specifically limited, For example, 0.1-10 micrometers, 1-7 micrometers, 2-6 micrometers, etc. are mentioned. When two or more layers are disposed adjacent to each other, the total thickness of all the hard coat layers (D) adjacent to each other may be within the above range. In the example list shown on the left, the following are more preferable than the above.

  The method of disposing the hard coat layer (D) is not particularly limited, and examples thereof include a method of applying to a film and curing with heat, a method of curing with active energy rays such as ultraviolet rays and electron beams, and the like. From the viewpoint of productivity, a method of curing with ultraviolet rays is preferable.

1.5 Other layers The light-transmitting conductive film of the present invention has an undercoat on the surface of the light-transmitting support layer (A) where the light-transmitting conductive layer (B) is disposed. At least one layer selected from the group consisting of the layer (B), the hard coat layer (D), and at least one other layer (E) may be further disposed.

  Although it does not specifically limit as another layer (E), For example, an adhesive layer etc. are mentioned.

  The adhesive layer is a layer that is disposed between two layers so as to be adjacent to each other and to adhere the two layers to each other. Although it does not specifically limit as an adhesive layer, For example, in the transparent electroconductive film used for the use of a solar cell, a display, illumination, electronic paper (electronic ink), a transistor, a printable circuit, or a transparent planar heating element As the adhesive layer, those usually used can be used.

1.6 Use of the light-transmitting conductive film of the present invention The light-transmitting conductive film of the present invention has a surface resistance value (sheet resistance) of 60 Ω / □ or less, so that high output can be expected. For this reason, it can be used in general applications that require high output. Although not particularly limited, such applications include, for example, solar cells that convert light energy into electrical energy, and on the contrary, displays that convert electrical energy into light energy (including organic EL, etc.), lighting, and electronic paper ( Or an electronic ink), a transistor, a printable circuit, or the like, or a transparent sheet-like heating element (hereinafter sometimes collectively referred to as a “solar cell or the like”). Details of the solar cell and the like are as described in 2.

2. Solar cell and the like of the present invention The solar cell and the like of the present invention includes the light-transmitting conductive film of the present invention, and further includes other members as necessary.

2.1 Solar Cell of the Present Invention A specific configuration example of the solar cell of the present invention includes a dye-sensitized solar cell. The dye-sensitized solar cell has a structure in which an electrolyte layer is sandwiched between a negative electrode and a positive electrode. In FIG. 7, the one aspect | mode of the dye-sensitized solar cell using the translucent conductive film of this invention is shown.

  For the positive electrode, a metal such as tungsten, titanium, platinum, or a light-transmitting conductive film can be used. For the electrolyte layer, an iodine-based electrolyte is used because of its low diffusion rate and low oxidation-reduction potential. A negative electrode is comprised from the semiconductor particle which adsorb | sucked the light-transmitting conductive film and the pigment | dye formed on it. Examples of the material of the dye include a metal complex such as a ruthenium dye and a phthalocyanine dye having a COOH group, and an organic dye such as a cyanine dye. Examples of the semiconductor particles include titanium oxide, zinc oxide, and tin oxide.

  When light enters the negative electrode of such a dye-sensitized solar cell, electrons are excited in the dye and injected into the semiconductor particles. These electrons diffuse through the semiconductor particles and reach the electrodes. At the positive electrode, electrons are injected into the electrolyte and iodine is reduced. The reduced iodine diffuses through the electrolytic solution and gives electrons to the dye to be oxidized. Power generation is performed by repeating such a cycle.

  Since the light-transmitting conductive film of the present invention has a low surface resistance, it is difficult to prevent the movement of electrons, the power generation efficiency is increased, and a high output can be expected.

2.2 Display of the Present Invention As a specific configuration example of the display of the present invention, an organic EL display can be mentioned. The organic EL display includes an organic EL element having a structure in which an organic EL layer containing an organic compound is sandwiched between an anode electrode and a cathode electrode. In FIG. 8, the one aspect | mode of the organic EL element using the transparent electroconductive film of this invention is shown.

  If the cathode electrode is a conventionally well-known thing, the raw material will not be limited. A conductive material having a small work function that is easy to inject electrons is preferable, and examples thereof include aluminum and silver. The organic EL layer includes at least a light emitting layer made of an organic light emitting material that causes electroluminescence, a hole transport layer that transports holes to the light emitting layer, a hole injection layer that injects holes into the hole transport layer, and a light emitting layer. An electron transport layer that transports electrons, an electron injection layer that injects electrons into the electron transport layer, and the like may be stacked. A light transmissive conductive film can be used for the anode electrode.

  By applying a voltage to the organic EL element having such a configuration, electrons and holes are injected from the cathode and the anode, respectively, and are combined in the light emitting layer. The light-emitting material of the light-emitting layer is excited by the energy of the bond, and light is generated when the excited state returns to the ground state again. By using this as one pixel, a display is formed.

  Since the light-transmitting conductive film of the present invention has a low surface resistance, the light emission efficiency is increased and high output can be expected.

3. Production method of light transmissive conductive film of the present invention Production method of light transmissive conductive film of the present invention comprises:
(A) a light-transmitting support layer; and (B) a light-transmitting conductive film containing a light-transmitting conductive layer containing indium tin oxide,
The light transmissive conductive layer (B) is disposed on at least one surface of the light transmissive support layer (A) directly or via one or more other layers,
The thickness of the light transmissive conductive layer (B) is 100 nm or more, and the peak in the X-ray diffraction of the light transmissive conductive layer (B) satisfies the following requirements (i) to (iii): A method for producing a light transmissive conductive film, characterized in that
A method comprising a step of forming a layer containing indium tin oxide by an ion plating method on a layer held at 90 ° C. or more adjacent to the light transmissive conductive layer (B):
(I) The peak on the (222) plane is strongest;
(Ii) The peak half width of the (222) plane is 0.5 or less; and (iii) the peak intensity of the (332) plane and the (134) plane are each 3% or more of the peak intensity of the (222) plane It is a method.

  In the method for producing a light transmissive conductive film of the present invention, an undercoat layer (C), a hard coat, in addition to the light transmissive conductive layer (B), on at least one surface of the light transmissive support layer (A) A step of arranging at least one layer selected from the group consisting of the layer (D) and at least one other layer (E) different from the layer (D) may be included. The step of arranging each layer is as described for each layer. In the case of arranging at least one other layer in addition to the light transmissive conductive layer (B), for example, the side of the light transmissive support layer (A) on which the light transmissive conductive layer (B) is disposed. However, the order of arrangement is not particularly limited. For example, you may arrange | position another layer to one side of the layer (for example, light transmissive conductive layer (B)) which is not a light transmissive support layer (A) first. Alternatively, one composite layer is obtained by arranging two or more layers adjacent to each other on the one hand, or at the same time, two or more layers are similarly disposed adjacent to each other on the other side. Thus, one type of composite layer may be obtained, and these two types of composite layers may be further arranged adjacent to each other.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
The film thicknesses in the examples and comparative examples were measured using a fluorescent X-ray analyzer (trade name: RIX1000, manufactured by Rigaku Corporation). Further, the surface resistance was measured by a 4-terminal method using a surface resistance meter (trade name: Loresta-EP) manufactured by MITSUBISHI CHEMICAL ANALYTECH. The total light transmittance was measured based on JIS-K-7105 using a haze meter (manufactured by Nippon Denshoku Co., Ltd., trade name: NDH-2000).

Light transmissive conductive films were obtained by the following production methods.
Example 1
A roll-shaped polyethylene terephthalate film (PET film) having a hard coat layer on both sides is placed in a vacuum apparatus and evacuated to 5 × 10 ⁻⁴ Pa or less, and then argon gas (concentration: 99.9). The following is the same:) 350 sccm and oxygen gas 15 sccm, and undercoat layer made of SiO _x (due to incomplete oxidation, x can take a value between 1 and 2) by DC magnetron sputtering. Was formed to a thickness of about 30 nm. The undercoat layer was formed on both sides of the PET film.

This roll-like PET film is placed in a vacuum apparatus and evacuated to 2 × 10 ⁻⁴ Pa or less, and then subjected to a reactive ion plating method using a pressure gradient type plasma gun to form a film forming pressure of 0.1 Pa. Then, ITO (SnO ₂ was 5% by weight) was formed to have a film thickness of 130 nm. At this time, in order to control the substrate temperature, the heated liquid was circulated inside the roll supporting the substrate during film formation by the reactive ion plating method. The temperature of the liquid was controlled so that the average value of the temperature at the inlet and outlet of the liquid was 110 ° C.

  The film was cut to an appropriate size and placed in an oven controlled at 150 ° C. for 1 hour. The atmosphere of the furnace was air.

  The light-transmitting conductive film thus obtained had a very low surface resistance of 25.6 Ω / □. Further, the total light transmittance was as high as 87% and was transparent.

  This light-transmitting conductive film was measured by a thin film method using a Rigaku thin film evaluation sample horizontal X-ray diffractometer SmartLab. For the measurement, a parallel beam optical arrangement was used, and a CuKα ray (wavelength: 1.54186 mm) was used as a light source at a power of 40 kV and 30 mA. The incident side slit system uses a solar slit of 5.0 °, a height control slit of 10 mm, and an incident slit of 0.1 mm, and the light receiving side slit has a parallel slit analyzer (PSA) of 0.114 deg. Was used. The detector used was a scintillation counter. The sample stage used a porous adsorption sample holder, and the sample was adsorbed and fixed by a pump. The incident side was fixed at 0.35 °, the step interval was 0.01 °, the measurement speed was 3.0 ° / min, and the measurement range was 5 ° to 80 °. The results are shown in FIG.

  The strongest peak was the (222) plane peak near 30 °, and the half width of this peak was 0.36. In the vicinity of 42 °, a peak on the (332) plane was observed at an intensity of 4.11% with respect to the peak intensity on the (222) plane. In the vicinity of 46 °, a peak on the (134) plane was observed at a strength of 6.41% with respect to the peak intensity on the (222) plane.

Example 2
In order to control the substrate temperature, the heated liquid was circulated inside a roll that supports the substrate during film formation by the reactive ion plating method. A light-transmitting conductive film was obtained in the same manner as in Example 1 except that the average temperature at the liquid inlet and outlet was 90 ° C.

  The surface resistance of the light-transmitting conductive film thus obtained was as very low as 51.5Ω / □. Further, the total light transmittance was as high as 87% and was transparent.

  When measured by the thin film method in the same manner as in Example 1, as shown in FIG. 10, the strongest peak was the (222) plane peak near 30 °, and the half width of this peak was 0.31. In the vicinity of 42 °, a peak on the (332) plane was observed at a strength of 4.62% relative to the peak intensity on the (222) plane. In the vicinity of 46 °, a peak on the (134) plane was observed at a strength of 4.95% with respect to the peak intensity on the (222) plane.

Comparative Example 1
In order to control the substrate temperature, the heated liquid was circulated inside a roll that supports the substrate during film formation by the reactive ion plating method. A light-transmitting conductive film was obtained in the same manner as in Example 1 except that the average temperature at the liquid inlet and outlet was 80 ° C.

  The surface resistance of the light transmissive conductive film thus obtained was as high as 69.0Ω / □. Further, the total light transmittance was as high as 86% and was transparent.

  When measured by the thin film method in the same manner as in Example 1, no clear (222) plane peak was observed as shown in FIG. Further, neither the (332) plane peak nor the (134) plane peak was observed.

Comparative Example 2
A light-transmitting conductive film was obtained in the same manner as in Example 1 except that the operation for 1 hour in a furnace controlled at 150 ° C. was not performed.

  The surface resistance of the light-transmitting conductive film thus obtained was as high as 62.0Ω / □. Further, the total light transmittance was as high as 86% and was transparent.

  When measured by the thin film method in the same manner as in Example 1, no clear (222) plane peak was observed as shown in FIG. Further, neither the (332) plane peak nor the (134) plane peak was observed.

Comparative Example 3
A light-transmitting conductive film was obtained in the same manner as in Example 1 except that ITO (SnO ₂ was 5% by weight) was formed so that the film thickness was 42 nm.

  The surface resistance of the light transmissive conductive film thus obtained was as high as 77.1 Ω / □. Further, the total light transmittance was as high as 88% and was transparent.

  When measured by the thin film method in the same manner as in Example 1, as shown in FIG. 13, the strongest peak was the (222) plane peak near 30 °, and the half width of this peak was 0.36. Moreover, the peak of (332) plane and the peak of (134) plane were not observed.

  The light-transmitting conductive films of Examples 1 and 2 that satisfy the requirements of the present invention have low surface resistance, but in Comparative Examples 1 to 3 that do not satisfy the requirements of the present invention, the surface resistance is high. It was recognized that

Claims (6)

(A) a light-transmitting support layer; and (B) a light-transmitting conductive film containing a light-transmitting conductive layer containing indium tin oxide,
The light transmissive conductive layer (B) is disposed on at least one surface of the light transmissive support layer (A) directly or via one or more other layers,
The thickness of the light transmissive conductive layer (B) is 100 nm or more, and the peak in the X-ray diffraction of the light transmissive conductive layer (B) satisfies the following requirements (i) to (iii): Light transmissive conductive film characterized by:
(I) The peak on the (222) plane is strongest;
(Ii) The peak half width of the (222) plane is 0.5 or less; and (iii) the peak intensity of the (332) plane and the (134) plane are each 3% or more of the peak intensity of the (222) plane It is. The light-transmitting conductive film according to claim 1, wherein the surface resistance is 60Ω / □ or less. The light-transmissive conductive layer (B) is
(1) Obtained by a method comprising a step of forming a layer containing indium tin oxide by an ion plating method on a layer held at 90 ° C. or more adjacent to the light transmissive conductive layer (B). The light-transmitting conductive film according to claim 1 or 2. The light transmissive conductive layer (B) can be obtained by a method further comprising (2) a step of maintaining the layer containing indium tin oxide obtained in the step (1) at 90 ° C. or higher. The light-transmitting conductive film described in 1. A solar cell, a display, illumination, electronic paper, a transistor, a printable circuit, or a transparent sheet heating element containing the light transmissive conductive film according to claim 1. (A) a light-transmitting support layer; and (B) a light-transmitting conductive film containing a light-transmitting conductive layer containing indium tin oxide,
The light transmissive conductive layer (B) is disposed on at least one surface of the light transmissive support layer (A) directly or via one or more other layers,
The thickness of the light transmissive conductive layer (B) is 100 nm or more, and the peak in the X-ray diffraction of the light transmissive conductive layer (B) satisfies the following requirements (i) to (iii): A method for producing a light transmissive conductive film, characterized in that
A method comprising a step of forming a layer containing indium tin oxide by an ion plating method on a layer held at 90 ° C. or more adjacent to the light transmissive conductive layer (B):
(I) The peak on the (222) plane is strongest;
(Ii) The peak half width of the (222) plane is 0.5 or less; and (iii) the peak intensity of the (332) plane and the (134) plane are each 3% or more of the peak intensity of the (222) plane It is.

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