JPH1120075A - Transparent conductive laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To raise adhesiveness with binder resin, and restrain the deterioration of distributed EL elements during the luminous continuity by forming a transparent conductive layer consisting mainly of indium oxide and an oxide layer consisting mainly of zinc oxide and having a specific resistance on one major surface of a transparent polymeric base body. SOLUTION: The one major surface of a transparent polymeric base body 10 includes a transparent conductive layer 20 consisting mainly of indium oxide and oxide layer 30 consisting mainly of zinc oxide formed successively thereon, and the oxide layer 30 consisting mainly of zinc oxide is 5 Ω.cm or more in its specific resistance. Providing the oxide layer 30 permits the improvement of adherence with the resin binder. Besides, the transparent conductive layer 20 having 5 Ω.cm or more resistivity and consisting of zinc oxide being the higher range than the transparent conductive layer 20 by 3 figures or more, thus restraining the deterioration of the transparent conductive layer 20. The control of the oxide layer 30 in its resistivity can be done by varying a temperature of film formation, a speed of film making operation, and a quantity of oxygen gas in the sputtering gas.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive laminate, and more particularly, to electroluminescence (EL).
The present invention relates to a transparent conductive laminate that can be suitably used as a transparent electrode of a surface light emitter and that suppresses deterioration with time of emission luminance.

[0002]

2. Description of the Related Art Conventionally, transparent conductive laminates have conventionally been used for electrodes of display elements such as liquid crystal displays, EL surface light emitters, electrochromic displays, window electrodes of photoelectric conversion elements such as solar cells, electromagnetic wave shielding films of electromagnetic wave shields, or It is used as an electrode of an input device such as a transparent touch panel. Conventionally known transparent conductive layers include gold, silver, platinum,
A noble metal thin film such as palladium and an oxide semiconductor thin film such as indium oxide, stannic oxide, and zinc oxide are known. The former noble metal thin film having a low resistance value can be easily obtained, but is inferior in transparency. The latter oxide semiconductor thin film has a slightly lower resistance value than a noble metal thin film, but is widely used because of its excellent transparency. Among them, an indium oxide thin film containing tin oxide (hereinafter referred to as ITO (Indium T
in oxide) film is widely used because of its low resistance and excellent transparency. The resistivity of the ITO film is usually about 5 × 10 ⁻⁵ to 1 × 10 ⁻³ Ω · cm, and the transmittance is generally 80 to 90%.

A dispersion type EL device has a structure in which a luminescent layer, an insulating layer and a back electrode are sequentially formed on the transparent conductive layer based on a transparent conductive substrate having a transparent conductive layer formed on a transparent substrate. Are known. For the transparent conductive layer, tin oxide,
Indium oxide, etc., in which a powder of zinc sulfide or the like is dispersed in a resin binder for the light emitting layer, the same resin binder used for the light emitting layer for the insulating layer, and carbon, silver, etc. for the back electrode Is often used. A feature of the dispersion-type EL element is that the material of the light-emitting layer, the insulating layer, and the back electrode can be formed by a printing method since the materials are all liquid. Can be

[0004] As a substrate of the transparent conductive laminate, glass and a polymer molded body are used. When glass is used as the substrate, the substrate temperature can be heated to about 400 ° C., so that a chemically stable crystalline transparent conductive layer can be formed, and a transparent conductive laminate excellent in transparency and environmental resistance can be obtained. Obtained easily. On the other hand, when the polymer molded body is used as the substrate, a transparent conductive laminate that is lighter, does not break, and can be bent as compared with glass is obtained. In particular, bendability is notable even with glass, no matter how thin it is. However, since the substrate temperature is limited to the heat-resistant temperature of the polymer material, it is necessary to form the transparent conductive layer at a low temperature.

[0005]

The following characteristics are required for the transparent electrode of the dispersion type EL device. (1) The surface resistance is low. Specifically, it is 500 Ω / □ or less, depending on the size of the light emitting surface. (2) High transmittance. Specifically, the visible light transmittance is 7
It is desirable that it be 5% or more. (3) No deterioration occurs to the binder resin. (4) Excellent adhesiveness with the binder resin. (5) The heat resistance temperature is higher than the drying temperature of the binder resin. (6) No change occurs in the electrical characteristics and the light transmission characteristics when light emission is continued.

Even when a polymer is used for the substrate, a transparent conductive laminate having a surface resistance of 500 Ω / □ or less and a visible light transmittance of 75% or more can be obtained by using an ITO film as a transparent conductive layer. Have been.

However, the conventional transparent conductive laminate does not always satisfy the above requirements (3) to (6). The requirements of (3) to (5) depend on the material of the binder resin. However, when a fluorine-based resin that has recently been used as a binder resin is used,
In particular, the adhesion may be low. In particular, (6) presents a major problem at present.
Some non-lighting occurs such that the film deteriorates and the deteriorated portion stops emitting light. This is a problem that occurs remarkably when the power supply voltage and frequency for emitting light are increased, and occurs when the ITO film is energized with the back electrode via the binder resin and the current continuously flows. It is a phenomenon. In view of the above circumstances, an object of the present invention is to improve the adhesion of a transparent conductive laminate using a transparent polymer molded body to a binder resin to a binder resin and to suppress the deterioration of a dispersion-type EL element when light emission is continued. It is assumed that.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that an oxide composed of zinc oxide having a resistivity of 5 Ω · cm or more is formed on a transparent conductive layer. The present inventors have found that by forming a layer, it is possible to improve the adhesion to the binder resin and to suppress the deterioration of the transparent conductive layer that occurs when the light emission is continued, and have reached the present invention.

That is, the present invention provides (1) at least one transparent conductive layer (B) mainly composed of indium oxide and an oxide layer (primarily zinc oxide) on one main surface of a transparent polymer substrate (A). (2) a transparent conductive laminate, wherein the oxide layer (C) has a resistivity of 5 Ω · cm or more; The thickness of the layer (B) is from 20 to 200
(1) wherein the thickness of the oxide layer (C) is 1 to 100 nm.
The present invention relates to the transparent conductive laminate according to (1) or (2), which can be suitably used as a transparent electrode of a dispersion-type electroluminescence (EL) element.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A transparent conductive laminate of the present invention will be described with reference to FIG. 1. A transparent conductive layer (B) mainly composed of indium oxide is formed on one main surface of a transparent polymer substrate (A) 10. ) 20 and an oxide layer (C) 30 mainly composed of zinc oxide, which are sequentially formed in a configuration of ABC, wherein the oxide layer (C) has a resistivity of 5 Ω · cm or more.

The polymer substrate (A) used in the present invention
A plastic molded article having transparency can be used. Specific examples include polyethylene terephthalate, polyethersulfone, polyetheretherketone, polycarbonate, polypropylene, and polyimide. These polymer substrates may be plate-shaped or film-shaped as long as the main surface on which the transparent conductive layer is formed is smooth. A plate-shaped polymer substrate is excellent in dimensional stability and mechanical strength, and can be suitably used particularly when such a substrate is required. In addition, since the polymer film has flexibility and the transparent conductive layer can be formed continuously by a roll-to-roll method, when this is used, the transparent conductive laminate can be efficiently formed. It can also be suitably used because it can be produced. In this case, a film having a thickness of usually 10 to 250 μm is used. When the thickness of the film is less than 10 μm, the mechanical strength as a substrate is insufficient, and when it exceeds 250 μm, the film lacks flexibility and is not suitable for use by winding the film around a roll.

[0012] Among the transparent polymer substrates, polyethylene terephthalate is more preferably used because of its excellent transparency and processability. Further, since polyether sulfone has excellent heat resistance, when heat treatment is required after preparing a transparent conductive laminate, and when assembling a dispersion type EL element using the transparent conductive laminate, It can be more suitably used when high-temperature heat treatment is required.

The transparent polymer substrate is subjected to etching treatment such as sputtering, corona treatment, flame treatment, ultraviolet irradiation, electron beam irradiation, etc., or undercoating on its surface, and a transparent coating mainly composed of indium oxide is formed thereon. A treatment for improving the adhesion of the conductive layer to the substrate may be performed. Before forming the transparent conductive layer mainly composed of indium oxide, dust-proofing treatment such as solvent cleaning or ultrasonic cleaning may be performed as necessary.

In the present invention, a transparent conductive layer (B) mainly composed of indium oxide is formed on one main surface of the transparent polymer substrate. The transparent conductive layer may be mixed with tin to lower the resistivity. Usually 3-20% by weight
By containing tin in a certain degree, the resistivity can be reduced, and a transparent conductive layer having a required sheet resistance value with a smaller film thickness can be formed.

The thickness of the transparent conductive layer mainly composed of indium oxide is usually preferably from 20 nm to 200 nm. The thickness of the transparent conductive layer affects its surface resistance and visible light transmittance. In order to lower the surface resistance value, the thickness of the transparent conductive layer may be increased, but if it is increased, the visible light transmittance is reduced. Therefore, the thickness of the transparent conductive layer is determined by the required surface resistance and visible light transmittance. When the thickness of the transparent conductive layer is less than 20 nm, the surface resistance increases and exceeds 500 Ω / □.
It cannot be suitably used as a transparent electrode of a dispersion type EL element.
In order to lower the surface resistance value, it is sufficient to increase the film thickness.
If it exceeds 200 nm, the visible light transmittance decreases, and
Since it is 5% or less, it cannot be suitably used as a transparent electrode of a dispersion-type EL element.

As a method for forming a transparent conductive layer mainly composed of indium oxide, there are a vacuum deposition method, a sputtering method,
Any of conventionally known physical vapor deposition methods such as an ion plating method can be adopted. A transparent conductive layer having a low surface resistance and mainly made of indium oxide is generally formed by a sputtering method. In the sputtering method, indium oxide containing indium oxide or tin is used as a target, and an inert gas such as argon is used as a sputtering gas.
Under the conditions of mTorr and polymer substrate temperature: 20 to 150 ° C., a direct current (DC) or high frequency (RF) magnetron sputtering method or the like can be used. Further, in order to increase the transparency and conductivity of the transparent conductive layer, 0.1
Oxygen gas at a flow rate of up to 20% may be mixed. In addition, indium or indium tin alloy is used as the target,
A direct current or high frequency reactive sputtering method using an inert gas such as argon as a sputtering gas and an oxygen gas as a reactive gas can also be suitably used. In this method, the transmittance and conductivity of the transparent conductive layer very sensitively affect the partial pressure of oxygen gas, which is a reactive gas, so that it is necessary to strictly control the partial pressure. All of the above sputtering methods,
Since a transparent conductive layer excellent in transparency and conductivity is easily obtained, it can be suitably used.

As described above, by forming a transparent conductive layer mainly composed of indium oxide having a thickness of 20 to 200 nm on one main surface of the transparent polymer substrate, a transparent electrode of a dispersion type EL element is required. Although a transparent conductive laminate having a surface resistance value and visible light transmittance can be obtained, the adhesion to the binder resin and the durability at the time of continuation of light emission are insufficient with this alone, so that it is used as it is for a transparent electrode. Even if a dispersion-type EL element is manufactured, it is easily peeled off, resulting in poor quality in which light emission failure appears early after use.

Therefore, in the present invention, after forming the transparent conductive layer mainly composed of indium oxide as described above, an oxide layer (C) mainly composed of zinc oxide is further provided thereon. The purpose of providing the oxide layer is, in part, to improve the adhesion to the resin binder. By using the oxide layer as a surface layer in contact with the binder resin, the adhesion to the binder resin can be improved.

Another reason for providing the oxide layer is to prevent the transparent conductive layer from deteriorating when energization is continued. Since the dispersion type EL element emits light by applying an AC electric field mainly through a light emitting layer containing a binder resin as a component and an insulating layer, the electrical structure is the same as that of a capacitor, and a transparent conductive layer is used as an electrode. in use. The deterioration of the transparent conductive layer is caused by an increase in the surface resistance value of the transparent conductive layer when light emission is continued, that is, when energization is continued. Although the cause of the increase in the surface resistance is not clear, it is presumed that the transparent conductive layer is degraded due to the movement of electric charges generated through the light emitting layer. The present inventors formed an oxide layer of zinc oxide on the transparent conductive layer, the zinc oxide having a resistivity of 5 Ω · cm or more and a range of at least three orders of magnitude higher than the transparent conductive layer. It has been found that the deterioration of can be suppressed. The relationship between the deterioration of the transparent conductive layer during continuous light emission and the resistivity of the oxide layer suggests that the movement of charges has some influence on the deterioration of the transparent conductive layer.

A technique for improving corrosion resistance by forming a zinc oxide thin film on a transparent conductive layer is disclosed in Japanese Patent Application Laid-Open No. 63-8965.
No. 7 discloses this. However, the zinc oxide used in the publication is conductive zinc oxide, and uses a zinc oxide film having a resistivity of 2.5 to 3.0 × 10 ⁻⁴ Ω · cm. Need something low. It is intended to be used as a transparent electrode of a solar cell that needs to conduct current through a low resistivity zinc oxide film,
Surprisingly, when used as a transparent electrode of a dispersion-type EL element, a laminate of such a low-resistance zinc oxide film cannot be used. This is because, as described above, the deterioration of the transparent conductive layer is presumed to be caused by the movement of charges through the zinc oxide film, and it is necessary to suppress the movement of charges by using a zinc oxide film having as high a resistivity as possible. It is. That is, the oxide layer mainly composed of zinc oxide used in the present invention is more preferable as it becomes an insulator.

The thickness of the oxide layer mainly composed of zinc oxide is preferably 1 to 100 nm. More preferably, 1 to 5
0 nm. If the thickness is smaller than 1 nm, the effect of suppressing the occurrence of deterioration when light emission is continued cannot be obtained.
In other words, in order to provide the transparent electrode of the dispersion-type EL element with the effect of suppressing deterioration when light emission is continued, the oxide layer mainly composed of zinc oxide needs to have a thickness of at least 1 nm. If the thickness is greater than 100 nm, the transparency is impaired. In addition, since the thickness of the oxide layer is less than 100 nm to suppress the deterioration during the light emission continuation, the deposition time is unnecessarily long. To form a thick layer is not preferable. Economically, the thickness of the oxide layer is preferably as thin as possible within a range that does not impair the effect of lowering luminance when light emission is continued. Since the effect is sufficiently obtained with a thickness of 50 nm, the thickness of the oxide layer is reduced. Is more preferably 1 to 50 nm.

As for the method of forming the oxide layer mainly composed of zinc oxide, similarly to the transparent conductive layer, any of the conventionally known physical vapor deposition methods such as a vacuum deposition method, a sputtering method and an ion plating method can be adopted. Whichever method is used, a transparent conductive laminate can be efficiently obtained by adopting the same method as the transparent conductive layer and continuously manufacturing a two-layer structure in the same vacuum apparatus. In the case of forming by a sputtering method, zinc oxide is used as a target, an inert gas such as argon is used as a sputtering gas, and a normal sputtering gas pressure is 1 to 10 mTorr, and a polymer substrate temperature is 20 to 1.
Under the condition of 50 ° C., direct current or radio frequency (RF) sputtering can be used. For the purpose of improving the transparency of the oxide layer, an argon gas containing an appropriate amount of oxygen may be used as a sputtering gas. Also, an appropriate amount of aluminum or the like may be mixed as long as the resistivity of the obtained oxide layer is 5 Ω · cm or more.

The control of the resistivity of the oxide layer mainly composed of zinc oxide can be changed by changing the film forming conditions, and mainly the film forming temperature, the film forming rate, and the amount of oxygen gas in the sputtering gas are controlled. Can be changed. In order to form an oxide layer with high resistivity, it is desired that the film formation temperature be as low as possible, the film formation rate be as high as possible, and the amount of oxygen gas be as large as possible. Although it depends on the target, it is desired that the amount of oxygen gas is, for example, such that the ratio of argon to oxygen is larger than 100: 10 in the flow rate ratio of the sputtering gas.

In order to improve the adhesion between the transparent polymer substrate and the transparent conductive layer mainly composed of indium oxide, an appropriate intermediate layer may be inserted between these layers as long as the performance is not impaired. Further, in order to improve the scratch resistance and the water vapor barrier property, an appropriate hard surface is provided on the surface of the transparent polymer substrate opposite to the main surface on which the laminated structure is formed as long as the performance is not impaired. A coat layer or the like may be formed.

The transparent conductive laminate obtained by the above method may be subjected to a heat treatment in order to improve environmental resistance. The heat treatment temperature is usually about 100 to 250 ° C. When thin film layers made of different kinds of elements are stacked as in the present invention, their interfaces are not clearly distinguished, and usually cause interdiffusion. However, even if mutual diffusion occurs near the interface between the transparent conductive layer and the thin film layer made of zinc oxide, it does not matter as long as the performance is not affected. The layer constitution referred to in the present invention has such significance, and can be confirmed by the following analysis method.

The atomic composition of the transparent conductive layer and the oxide layer formed by the above method is determined by Auger electron spectroscopy (AE
S), inductively coupled plasma method (ICP), Rutherford backscattering method (RBS) and the like. These film thicknesses can be measured by Auger electron spectroscopy observation in the depth direction, cross-sectional observation by a transmission electron microscope, or the like.

The surface resistance can be measured by a four-terminal method or a Hall measurement method. The resistivity (ρ) is the surface resistance value (R)
And its film thickness (t) can be calculated by the following equation (1). ρ (Ω · cm) = R (Ω / □) × t (cm) (1)

It should be noted here that when the resistivity of the transparent conductive laminate having a two-layer structure is obtained by the four-terminal method or the Hall measurement method, the value is a combined value of the two layers. However, the resistivity is not the oxide layer alone. Resistivity is 5Ω
In order to form an oxide layer having a resistivity of at least 5 Ω · cm, an oxide layer having a resistivity of 5 Ω · cm or more must be obtained. May be investigated in advance, and a film may be formed under the conditions.

[0029]

Next, the present invention will be described in detail with reference to examples. Prior to manufacturing the transparent conductive laminate, an oxide layer mainly composed of zinc oxide was formed to have a thickness of 100 nm by the same substrate, material, and film forming conditions, and the surface resistance was measured by a four-terminal method. And the resistivity was calculated from the equation (1).

The thicknesses of the transparent conductive layer and the oxide layer are controlled in advance by the same substrate, material, and film forming conditions for a certain period of time: T (min). The height of the step of the film: h (nm) is obtained by measuring the height of the film with a thickness meter, and the film forming speed DR (nm / min) is calculated by the following equation (2) to change the film forming time. This changed the film thickness. DR (nm) = h (nm) / T (min) (2)

Example 1 A polyethylene terephthalate film having a thickness of 125 μm (manufactured by Teijin Limited: Tetron H)
5% by weight of tin oxide on one side of SA)
The indium oxide contained was sputtered to a thickness of 50 nm by DC magnetron reactive sputtering under an atmosphere of 2 mTorr using an argon / oxygen mixed gas having a flow ratio of argon: oxygen = 100: 1.
A transparent conductive layer made of an ITO film was formed. Further, on the upper surface thereof, a DC magnetron sputtering was performed in a 2 mTorr atmosphere using a zinc oxide containing 1 wt% of aluminum as a target and an argon / oxygen mixed gas having a flow ratio of argon: oxygen = 100: 20 as a sputtering gas. An oxide layer having a thickness of 10 nm was formed by a method, and a transparent conductive laminate having a two-layer structure was manufactured.

[Examples 2 and 3] In order to change the resistivity of the oxide layer, the flow rate of the sputtering gas when forming the oxide layer was changed to argon: oxygen = 100: 10.
(Example 2) A transparent conductive laminate having a two-layer structure was produced in the same manner as in Example 1 except that argon: oxygen = 100: 50 (Example 3).

Comparative Example 1 Same as Example 1 except that the flow rate of the sputtering gas when forming the oxide layer was changed to argon: oxygen = 100: 5 in order to change the resistivity of the oxide layer. By the method, a transparent conductive laminate having a two-layer structure was produced.

[Examples 4 and 5] A two-layer transparent conductive film was formed in the same manner as in Example 1 except that the thickness of the oxide layer was changed to 1 nm (Example 4) and 100 nm (Example 5). A laminate was prepared.

Comparative Example 2 A transparent conductive laminate having a single-layer structure was produced in the same manner as in Example 1 except that no oxide layer was formed. Comparative Example 3 A transparent conductive laminate having a two-layer structure was produced in the same manner as in Example 1 except that the thickness of the oxide layer was changed to 200 nm.

[Examples 6 and 7] A two-layer transparent conductive film was formed in the same manner as in Example 1 except that the thickness of the transparent conductive layer was changed to 20 nm (Example 6) and 200 nm (Example 7). A laminate was prepared.

[Comparative Examples 4 and 5] A two-layer transparent conductive film was formed in the same manner as in Example 1 except that the thickness of the transparent conductive layer was changed to 10 nm (Comparative Example 4) and 500 nm (Comparative Example 5). A laminate was prepared. Table 1 shows the surface resistance value and the visible light transmittance of the above transparent conductive laminate.

[0038]

[Table 1]

Using the transparent conductive laminate produced as described above, a dispersion type EL device was produced by the following method. <Materials> Light emitting layer Per 100 cc of methyl ethyl ketone, 20 g of a fluoroelastomer (trade name: Daiel, manufactured by Daikin Industries, Ltd.) was dissolved and used as a binder resin. For 1 g of the binder resin, a phosphor powder (a zinc sulfide powder manufactured by OSRAM Sylvania, product number: capsule type #)
30) was dispersed in an amount of 2 g to obtain a light emitting layer material. -Dielectric layer The binder resin used for the light emitting layer was used. -Backside electrode Aluminum having a purity of 99.9% was used.

<Manufacturing Method> After forming a transparent conductive layer and an oxide layer, a light emitting layer material is applied by a bar coater, and this is heated at 120 ° C. for 2 hours in the air to be dried. Was also applied with a bar coater and dried under the same conditions. At that time, the portion where the ITO film electrode was taken out was left uncoated. The bar coater was adjusted so that the thickness was 30 μm and 40 μm, respectively. Next, a back electrode material was formed by a resistance heating type vacuum evaporation method. 0.3 thickness
μm.

A sine wave of 100 Vrms and 400 Hz was applied between the transparent electrode (ITO film) and the back electrode (aluminum vapor-deposited film) of the dispersion type EL device produced as described above to emit light. The light emission was at a temperature of 50 ° C. and a relative humidity of 90.
% In a constant temperature bath. The light was allowed to stand while emitting light, and the emission time up to the point where a non-light emitting portion having a diameter of 1 mm or more was generated was defined as the lifetime.

Further, in order to measure the adhesion between the light emitting layer and the transparent conductive laminate, the dispersion type EL element was cut into a strip having a width of 1 cm, and the light emitting layer and the transparent conductive laminate were separated by 90 mm.
At the angle of °, the force required at that time was measured. Table 2 shows the above results.

[0043]

[Table 2]

As is clear from Table 2, when used as a transparent electrode of a dispersion type EL device, the transparent conductive laminate of the present invention has excellent adhesion to the light emitting layer and can have a long life. I understand. On the other hand, Comparative Example 2 in which the oxide layer was not formed had a small adhesion and a short life time.
In Comparative Example 1 in which the resistivity of the oxide layer was low, the life time was short.

The emission luminance of the dispersion-type EL element was 50 to 70 cd / m ² in the example, whereas each layer was thick in the comparative example 3 and the comparative example 5.
It was 15 cd / m ² . In order to make the display section clearly visible even at night, about ²⁰ cd / m ² or more is required, so that the comparative example cannot be suitably used.

[0046]

As described above, in the present invention, a transparent conductive layer mainly composed of indium oxide is formed on one main surface of a polymer transparent substrate, and an oxide layer mainly composed of zinc oxide is formed thereon. By stacking, the dispersion type E
The life of the L element can be extended.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a transparent conductive laminate of the present invention.

[Explanation of symbols]

Reference Signs List 10 transparent polymer substrate (A) 20 transparent conductive layer (B) mainly composed of indium oxide 30 oxide layer (C) mainly composed of zinc oxide

Claims (3)

[Claims] At least one transparent conductive layer (B) mainly composed of indium oxide and an oxide layer (C) mainly composed of zinc oxide are formed on one main surface of a transparent polymer substrate (A). Wherein the oxide layer (C) has a resistivity of 5 Ω · cm or more. 2. The thickness of the transparent conductive layer (B) is from 20 to 200.
The transparent conductive laminate according to claim 1, wherein the thickness of the oxide layer (C) is 1 to 100 nm. 3. A dispersion-type electroluminescence (E)
L) The transparent conductive laminate according to claim 1 or 2, which can be suitably used as a transparent electrode of an element.