KR101143289B1 - Substrate with film, substrate with transparent conductive film, and light-emitting device - Google Patents

Abstract

Provided is a light emitting device having good extraction efficiency, a substrate with a film and a substrate with a transparent conductive film that can be used for the light emitting device. A substrate with a film formed by forming a scattering layer containing inorganic fine particles on at least one side of the substrate, wherein the inorganic fine particles contain hollow fine particles, and the hollow fine particles have SiO ₂ as a main component, and further other metals. contained and the other content of the metal (oxide basis) is, based on 100 parts by mass of the SiO ₂ of the hollow fine particles, 0.1 to 15 parts by mass, the substrate film is attached.

Light emitting element, substrate with film, transparent conductive film, inorganic fine particle, scattering layer, hollow fine particle

Description

SUBSTRATE WITH FILM, SUBSTRATE WITH TRANSPARENT CONDUCTIVE FILM, AND LIGHT-EMITTING DEVICE}

Technical Field

 The present invention relates to a substrate with a film, a substrate with a transparent conductive film, and a light emitting element having these substrates used in various displays, display elements, liquid crystal backlights, and the like.

Background

In recent years, various displays have been developed according to the progress of the information society. As one of the typical examples of the thin film type light emitting element used for such a display, there is an organic electroluminescent (hereinafter referred to as "organic EL") light emitting body.

Conventionally, such a thin film type light emitting element has a problem that the extraction efficiency of emitted light is difficult to improve.

In the thin film type light emitting element, as shown in FIG. 3, the light emitted from the electroluminescent element 10 passes through the glass substrate 1 and is emitted to the outside by being emitted from the exposed surface of the glass substrate 1. . However, as indicated by the arrow in FIG. 3, a part of light incident on the surface of the glass substrate 1 and the interface between the air at a small angle of incidence is emitted from the exposed surface of the glass substrate 1 and taken out to the outside, Much of the light is reflected at the interface between the exposed surface of the glass substrate 1 and the air, which is guided in the direction toward the edge of the substrate in the glass substrate 1, so that only about 20% of the emitted light is extracted. there was. 3 is a schematic sectional drawing explaining the structure of the organic EL light-emitting body which forms the electroluminescent element 10 on the glass substrate 1, and is formed.

Regarding such a problem, Patent Document 1 discloses, "As a composite thin film holding substrate having a substrate and a composite thin film disposed on the surface thereof, the composite thin film contains a filler and a binder, and the refractive index (Nf) of the filler is A composite thin film holding substrate, which is smaller than the refractive index (Nb) of the binder and smaller than the refractive index (Ns) of the substrate. '', "A transparent conductive film holding in which a transparent conductive film is formed on the composite thin film of the composite thin film holding substrate." Board | substrate. "And" a surface light-emitting body in which a light emitting layer and a metal electrode are laminated | stacked in this order on the transparent conductive film of this transparent conductive film holding substrate, and a transparent conductive film, a light emitting layer, and a metal electrode comprise an electroluminescent element. " Proposed.

Patent Document 1: Japanese Unexamined Patent Publication No. 2003-216061

DISCLOSURE OF INVENTION

Problems to be Solved by the Invention

However, it has become clear that the surface light-emitting body described in Patent Document 1 may deteriorate the extraction efficiency due to the presence of temperature or resistance value problems for forming the light-emitting body.

Moreover, in order to solve the said problem, the applicant of "the board | substrate with a film | membrane formed by forming a scattering layer and a low resistance layer in this order in one side of a board | substrate in this order, and the surface roughness on the low resistance layer is 5-20 nm. (Japanese Patent Application No. 2006-59760: filing date March 6, 2006 (Japanese Laid-open Patent Publication No. 2007-242286: publication date September 20, 2007)), hereinafter referred to as "Season 1" ).

An object of the present invention is to provide a light emitting device having better extraction efficiency than the film-bearing substrate of the source 1, a substrate with a film and a substrate with a transparent conductive film that can be used for the light emitting device.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present invention has a substrate with a film having a scattering layer formed using inorganic fine particles containing specific hollow fine particles containing SiO ₂ and other metals, and a transparent conductive material on the substrate. When the board | substrate with a transparent conductive film in which the film was formed was used, it discovered that the light emitting element with favorable extraction efficiency was obtained, maintaining the resistance value of a transparent conductive film, and completed this invention.

This invention is based on said knowledge and has the following summary.

(1) A substrate with a film formed by forming a scattering layer containing inorganic fine particles on at least one side of the substrate,

The inorganic fine particles contain hollow fine particles,

The hollow fine particles contain SiO ₂ as a main component, and further contain other metals,

The other content of the metal (oxide basis) is, based on 100 parts by mass of the SiO ₂ of the hollow fine particles, 0.1 to 15 parts by mass the film substrate is attached.

(2) A substrate with a film formed by forming a scattering layer containing inorganic fine particles on at least one side of the substrate,

The inorganic fine particles contain hollow fine particles and chain fine particles connecting the hollow fine particles,

The hollow fine particles contain SiO ₂ as a main component, and further contain other metals,

The chain fine particles contain SiO ₂ as a main component, and further contain other metals,

The hollow fiber content of the other metal in the fine particles (oxide basis) and the total of the content (an oxide basis) of the other metal in a chain-like particles, the hollow fine particles of SiO _2, and the total 100 parts by mass of SiO ₂ of the chain-like particles The board | substrate with a film which is 0.1-15 mass parts with respect to a part.

(3) The board | substrate with a film as described in said (1) or (2) whose surface roughness on the said scattering layer is 10-20 nm.

(4) The board | substrate with a film in any one of said (1)-(3) which the said inorganic fine particle is prepared in an inorganic fine particle dispersion liquid by the method of providing the following (a) and (b) process at least.

(a) To the dispersion medium in which the core fine particles exist, a curing catalyst containing a precursor of SiO ₂ and another metal is added, and the surface of the core fine particles contains Si0 ₂ as a main component and further contains another metal. Process of obtaining core-shell particle | grains by depositing a shell.

(b) A step of dissolving or decomposing the core fine particles of the core-shell particles obtained in the step (a).

(5) Furthermore, the board | substrate with a film in any one of said (1)-(4) which forms a scattering layer in the surface on the opposite side to the surface on which the said scattering layer was formed.

(6) The film according to any one of (1) to (4), wherein the scattering layer does not contain a matrix or contains a matrix of 5% by mass or less based on the mass (solid content conversion) of the scattering layer. Attached substrate.

(7) Furthermore, the board | substrate with a film in any one of said (1)-(4) formed by forming a low resistance layer on the said scattering layer.

(8) A transparent conductive film is formed on the scattering layer of the substrate with a film according to any one of the above (1) to (6), and the specific resistance of the transparent conductive film is 3 × 10 ⁻⁴ Ω · cm or less. Substrate with film deposition.

(9) The board | substrate with a transparent conductive film formed by forming a transparent conductive film on the low resistance layer of the board | substrate with a film as described in said (7), and whose specific resistance is 3 * 10 <^{-4> (} ohm) * cm or less.

The light emitting element formed by forming a light emitting layer and a metal electrode in this order on the transparent conductive film of the board | substrate with a transparent conductive film as described in said (8) or (9).

Effects of the Invention

According to the present invention, it is possible to provide a light emitting device having good extraction efficiency, a substrate with a film and a substrate with a transparent conductive film which can be used for the light emitting device.

Moreover, the composite thin film holding | substrate used for the surface light-emitting body of patent document 1 contains the binder (henceforth "matrix") which connects fillers (for example, hollow silica fine particles, etc.) to a composite thin film. Although manufacturing cost is high, according to this invention, since it is no longer necessary to use the matrix which connects the inorganic fine particles which form a scattering layer, cost reduction can be attained.

In addition, although it is preferable to use a matrix from a viewpoint of connecting fillers, it is preferable not to use it from a viewpoint of improving luminous efficiency on the contrary. In the present invention, it is not necessary to contain the matrix and, as a substitute, the content of the inorganic fine particles in the scattering layer can be increased, so that the extraction efficiency can be further improved.

Brief description of the drawings

BRIEF DESCRIPTION OF THE DRAWINGS It is partial cutaway sectional drawing which shows the shape and structure of the board | substrate with a transparent conductive film of this invention.

2 is a partially cutaway cross-sectional view showing the shape and configuration of the light emitting device of the present invention.

3 is a schematic cross-sectional view for explaining the structure of an organic EL light-emitting body formed by providing an electroluminescent element 10 on a glass substrate 1.

Explanation of the sign

1 glass substrate

2 scattering layer

3 substrate with film

4 transparent conductive film

5 Board with transparent conductive film

6 hole transport floor

7 emitting layer

8 electron transport layer

9 metal electrode

10 Electroluminescent Devices

11 light emitting element

Invention  Conduct  Best form for

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

The substrate with a film (hereinafter also referred to as "the substrate with a film of the present invention") according to the first aspect of the present invention is a substrate with a film formed by forming a scattering layer containing inorganic fine particles on at least one side of the substrate. The inorganic fine particles contain hollow fine particles, the hollow fine particles have SiO ₂ as a main component, and further contain other metals, and the content (oxide conversion) of the other metals is different from that of the SiO ₂ in the hollow fine particles. It is 0.1-15 mass parts with respect to 100 mass parts, Preferably it is a board | substrate with a film which is 0.2-8 mass parts.

Moreover, it is preferable that the said board | substrate with a film of this invention contains the chain fine particles which connect the hollow microparticles other than the said hollow microparticles. Here, the chain fine particles contain SiO ₂ as a main component and further contain other metals. In the case of containing the chain fine particles, the sum of the content (oxide conversion) of the other metal in the hollow fine particles and the content (oxide conversion) of the other metal in the chain fine particles is SiO in the hollow fine particles. ₂ and the chain-like as to the total 100 parts by weight of SiO ₂ of the microparticles, 0.1 to 15 parts by weight, preferably from 0.2 to 8 parts by mass.

In addition, the substrate with a film of the present invention may further form a low resistance layer on the scattering layer.

Next, the board | substrate used for the board | substrate with a film of this invention, the scattering layer formed on a board | substrate, and the low resistance layer formed as needed are explained in full detail.

[Board]

The substrate used for the substrate with a film of the present invention is not particularly limited as long as it is a transparent material having heat resistance and strength capable of forming an organic EL element thereon. Specific examples thereof include a glass substrate, a ceramic substrate, a plastic substrate, a metal substrate, and the like, or an alkali barrier layer such as a silicon oxide film, an aluminum oxide film, a zirconium oxide film, a titanium oxide film, or the like attached to the surface of these substrates. Can be.

Among these, a glass substrate, especially a glass substrate with an alkali barrier layer, is preferable because it has heat resistance of 300 ° C. or more, has resistance to sintering described later, and also has excellent strength.

Specific examples of the glass substrate include colorless transparent soda-lime silicate glass substrates, aluminosilicate glass substrates, borate glass substrates, lithium aluminosilicate glass substrates, quartz glass substrates, borosilicate glass substrates, and alkali-free glass substrates. Can be mentioned.

 Moreover, when using the board | substrate with a film of this invention for a light emitting element, it is preferable that the thickness of a glass substrate is 0.1-6 mm, Preferably it is 0.2-1.2 mm from a viewpoint of intensity | strength and transmittance | permeability.

In the present invention, when using a glass substrate containing sodium such as soda-lime silicate glass or a low alkali-containing glass substrate, in order to minimize diffusion of an alkali component to a scattering layer formed on at least one side of the glass substrate, It is preferable to use the glass substrate with an alkali barrier layer (for example, silicon dioxide film etc.).

Moreover, as an alkali barrier layer formation method, an ion plating method etc. are mentioned specifically ,, for example. In addition, as for the film thickness of an alkali barrier film, 10 nm or more is preferable from a viewpoint of alkali barrier performance, and 500 nm or less is preferable from a cost point of view. Especially preferable film thickness is 20-200 nm.

[Scattering layer]

In order to improve the extraction efficiency, the scattering layer of the present invention is a layer having a suitable surface roughness on the surface after formation, and is a layer formed on at least one side of the substrate, preferably on both sides.

In the present invention, the scattering layer contains inorganic fine particles and is formed using a scattering layer coat liquid containing an inorganic fine particle dispersion.

In addition, in the present invention, the scattering layer can be formed without containing a matrix (binder). As will be described later, the scattering layer contains a matrix of 5 mass% or less with respect to the mass (solid content conversion) of the scattering layer. You may be. In this case, the scattering layer is formed using a scattering layer coat liquid containing an inorganic fine particle dispersion and a matrix-containing liquid. By reducing the content of the matrix, the content of the inorganic fine particles (particularly hollow fine particles) can be increased, thereby contributing to the improvement of luminous efficiency and extraction efficiency.

[Inorganic fine particle and inorganic fine particle dispersion]

An inorganic fine particle is a main component which comprises the film | membrane of the said scattering layer, and the said inorganic fine particle dispersion means the dispersion liquid of the inorganic fine particle which disperse | distributed the said inorganic fine particle in a dispersion medium.

Herein, the inorganic fine particles refer to fine particles of an inorganic substance, and specifically, SiO ₂ fine particles and the like are exemplified.

[Hollow particles]

In this invention, the said inorganic fine particle contains the specific hollow microparticles shown below, and may consist only of the hollow microparticles | fine-particles. Specifically, the inorganic fine particles preferably contain 85% by mass or more of specific hollow microparticles described below, and more preferably 90% by mass or more.

Here, the said hollow fine particle is particle | grains which have a space | gap inside an outer shell. As the above-mentioned hollow microparticles, specifically, for example, spherical hollow microparticles and a fibrous hollow microparticle, a tubular hollow microparticle, and a sheet-shaped hollow microparticle are larger in length than the length in a direction perpendicular to the stretching direction. Etc. can be mentioned. In addition, the fibrous hollow fine particles may be primary particles or large secondary particles as aggregates, as the hollow fine particles having a larger length in the stretching direction than the length in the direction perpendicular to the stretching direction.

The hollow fine particles contain SiO ₂ as a main component and further contain other metals.

Here, the content of the SiO _2, in that it suppresses the low refractive index of the whole of the scattering layer, and preferably at least 85% by weight contained in the hollow fine particles, it is more preferable to be not less than 90% by weight.

In the present invention, the other metal in the hollow fine particles is not particularly limited as long as it is a metal other than silicon (Si) which is a semimetal, but Zr, Al, Cu, Ce, Sn, Ti, Cr, Co, Fe, Mn, Ni And at least one metal selected from the group consisting of Zn. In addition, the other metal may form a composite oxide with Si.

Among other metals, Zr is preferable because of excellent chemical durability. Moreover, Al is preferable for the reason that it is excellent in adhesiveness with a board | substrate.

Here, the amount of the other metal in the hollow fine particles (in terms of oxide) are, with respect to 100 parts by weight of SiO ₂ of the hollow fine particles is 0.1 to 15 parts by weight of 0.2 to 8 wt denied preferably, 0.5 to 5 parts by mass It is more preferable.

If the amount of other metals (oxide equivalent) is 0.1 part by mass or more, the strength of the hollow fine particles is sufficiently high. When the amount of other metals (oxide equivalent) is 15 parts by mass or less, the refractive index of the whole scattering layer is suppressed low.

The amount of other metals (oxide conversion) is the amount converted to ZrO ₂ when the other metal is Zr, the amount converted to Al ₂ O ₃ when Al, and the amount converted to CuO when Cu. In the case of Ce, the amount converted to CeO ₂ , In the case of Sn, the amount converted to SnO ₂ , In the case of Ti, the amount converted to TiO ₂ , and in the case of Cr, the amount converted to Cr ₂ O ₃ In the case of Co, the amount is converted into CoO, in the case of Fe, the amount is converted to Fe ₂ O ₃ , in the case of Mn, the amount is converted to MnO ₂ , and in the case of Ni, it is the amount converted to NiO, In the case of Zn, it is the amount converted into ZnO (it is the same below).

When the hollow fine particles contain such a metal, there is no need to use a matrix connecting the inorganic fine particles containing the hollow fine particles, and as described above, the light emission efficiency and the extraction efficiency are improved. Although the reason is not clear in detail, it is thought that it is because it becomes easy to produce chain-like fine particles mentioned later by using another metal at the time of manufacturing the said inorganic fine particle.

In addition, as one of the reasons that the matrix does not need to be used, the present inventors speculate that this is because a chelate compound is formed by the presence of another metal, and as a result, the polymerization reaction of silanol is promoted.

In this invention, it is preferable that it is 5-300 nm, and, as for the average aggregate particle diameter of the said hollow microparticles, it is more preferable that it is 10-100 nm. When the average aggregated particle diameter of the hollow fine particles is 5 nm or more, sufficient voids are formed between adjacent hollow fine particles, so that the refractive index of the scattering layer is low, and the antireflection effect is high. Since scattering of light is suppressed when the average aggregated particle diameter of the hollow fine particles is 300 nm or less, a highly transparent scattering layer is obtained.

 Here, the average aggregate particle diameter of the said hollow microparticles | fine-particles is an average aggregate particle diameter of the said hollow microparticles | fine-particles in the said inorganic fine particle dispersion, and is measured by the dynamic scattering method.

Moreover, it is preferable that the average primary particle diameter of the said hollow fine particle is 5-100 nm. If the average primary particle diameter of hollow microparticles | fine-particles exists in this range, the reflection prevention effect of a scattering layer will become high, and transparency of a scattering layer can be fully ensured.

Here, the average primary particle diameter of the said hollow microparticles | fine-particles observes the said hollow microparticles with a transmission electron microscope, randomly selects 100 particle | grains, measures the particle diameter of each hollow microparticle, and averages the particle diameter of 100 hollow microparticles | fine-particles. Value. Moreover, in the case of hollow fine particles, such as a fibrous shape, a tube shape, a sheet shape, long axis is made into a particle diameter.

Moreover, it is preferable that it is 1.1-1.4, and, as for the refractive index of the said hollow fine particle, it is more preferable that it is 1.2-1.35. When the refractive index of the hollow fine particles is 1.1 or more, a scattering layer having a refractive index of 1.2 or more can be easily obtained, and a scattering layer having a high antireflection effect can be obtained when the glass is used as a substrate. Moreover, when the refractive index of hollow microparticles | fine-particles is 1.1 or more, the shell of sufficient thickness will be formed and the intensity | strength of the said hollow microparticles | fine-particles becomes high. When the refractive index of the hollow fine particles is 1.4 or less, a scattering layer having a refractive index of 1.4 or less is easily obtained, and a scattering layer having a high antireflection effect can be obtained when the glass is used as a substrate.

Here, the refractive index of the said hollow microparticles | fine-particles is a refractive index in 550 nm, and is calculated by measuring a refractive index with a refractometer in the state disperse | distributed in inorganic fine particle dispersion liquid, and converting from volume ratio. In addition, the refractive index of the said hollow microparticles | fine-particles in a scattering layer is equal to the refractive index of the said hollow microparticles | fine-particles in an inorganic fine particle dispersion.

In the present invention, the inorganic fine particles include hollow fine particles (e.g., airgel fine particles and the like) or solid fine particles (e.g., chain-like fine particles described later) other than the hollow fine particles. You may include in the range which does not impair an effect.

[Chain-shaped fine particles]

The inorganic fine particles preferably contain solid chain fine particles, and the hollow fine particles are preferably connected by the chain fine particles. Since the hollow fine particles are connected with the chain fine particles, there is no need to use a matrix connecting the inorganic fine particles, and a scattering layer containing the inorganic fine particles as a main component forms a network so that it is difficult to peel off from the substrate.

Here, the said chain-shaped microparticles | fine-particles are particle | grains whose length of an extension direction is large compared with the length of the direction perpendicular | vertical to an extension direction. The chain fine particles are usually secondary particles as aggregates, but are not necessarily limited to secondary particles. As a shape of the primary particle which comprises a secondary particle, spherical shape, needle shape, rod shape, etc. are mentioned, for example. As a form in which a plurality of primary particles are aggregated, a form in which chain-shaped or pearl-necked secondary particles are entangled to form a two-dimensional or three-dimensional network as a whole is preferable.

The chain fine particles contain SiO ₂ as a main component and further contain other metals.

Here, the content of the SiO _2, in that it suppresses the low refractive index, with respect to the hollow fine particles and the total mass of the chain-like particles, and preferably less than 85% by mass, more preferably 90% by mass.

In the present invention, the other metal in the chain fine particles is not particularly limited as long as it is a metal other than silicon (Si) which is the same as the metal in the hollow fine particles, and is a semimetal, but Zr, Al, Cu, Ce, Sn, Ti, And at least one metal selected from the group consisting of Cr, Co, Fe, Mn, Ni, and Zn. In addition, the other metal may form a composite oxide with Si.

Among other metals, Zr is preferable because of the fact that the content of the matrix can be further reduced. Moreover, Al is preferable for the reason that it is excellent in chemical durability.

Here, when the said inorganic fine particle contains a chain fine particle, as mentioned above, the sum total of content (oxide conversion) of the other metal in the said hollow fine particle and content (oxide conversion) of the other metal in the said chain fine particle are , the hollow fine particles of SiO _2, and for the total of 100 parts by weight of SiO ₂ of the chain-shaped particles, 0.1 to 15 parts by mass, and preferably 0.2 ~ 8 parts by mass, more preferably 0.5 to 5 mass denied.

In addition, the chain fine particles are by-products when the hollow fine particles are produced, and the composition of the chain fine particles is the same as the hollow fine particle composition.

In this invention, it is preferable that it is 2-10, and, as for the aspect ratio of the said linear fine particle, it is more preferable that it is 5-10. When the aspect ratio of the chain particles is 2 or more, sufficient voids are formed between adjacent chain fine particles, so that the refractive index of the scattering layer is lowered and the antireflection effect is increased. When the aspect ratio of the linear fine particles is 10 or less, the film forming property is excellent, and thus a scattering layer having excellent appearance is obtained.

Here, the aspect ratio of the chain fine particles is a value calculated by dividing the length in the stretching direction by the length in the direction perpendicular to the stretching direction. The length in the stretch direction and the length in the direction perpendicular to the stretch direction are measured by observation with an electron microscope or the like.

Moreover, it is preferable that it is 2-500 nm, and, as for the average length of the extension direction of the said chain-shaped microparticles | fine-particles, it is more preferable that it is 10-100 nm. If the average length of the chain-shaped fine particles in the elongation direction is 2 nm or more, the network is easily formed when the scattering layer is formed, so that the scattering layer does not peel off well from the substrate. When the average length of the chain-shaped fine particles in the elongation direction is 500 nm or less, the film is excellent in film formation, and thus a scattering layer having an excellent appearance is obtained.

Moreover, it is preferable that it is 1-50 nm, and, as for the average length of the direction perpendicular | vertical to the extension direction of the said chain-shaped microparticles | fine-particles, it is more preferable that it is 1-20 nm. If the average length in the direction perpendicular to the elongation direction of the chain fine particles is 1 nm or more, the network is retained when the scattering layer is formed, so that the scattering layer does not peel off well from the substrate. When the average length in the direction perpendicular to the stretching direction of the chain fine particles is 50 nm or less, the adhesiveness can be improved without increasing the refractive index of the scattering layer.

Here, the length of the chain-shaped fine particles in the elongation direction has a certain range of distribution as a whole because each one of the particles is different. The average length in the extending direction of the chain fine particles means the length of the average value of the distribution. The average length in the direction perpendicular to the stretching direction is also the same.

[Method for producing inorganic fine particles]

In this invention, it is preferable that the said inorganic fine particle is prepared in an inorganic fine particle dispersion liquid by the manufacturing method provided with at least the following (a) and (b) process.

(a) A curing catalyst containing a precursor of SiO ₂ and another metal is added to a dispersion medium containing the core fine particles, and SiO ₂ is a main component on the surface of the core fine particles, and further contains another metal. Precipitating the shell to obtain core-shell particles.

(b) A step of dissolving or decomposing the core fine particles of the core-shell particles obtained in the step (a).

(a) process:

In step (a), core-shell-type particles are produced, that is, a curing catalyst containing a precursor of SiO ₂ and another metal is added to a dispersion medium in which the core fine particles are present, and the surface of the core fine particles is SiO _2. It is a process of preparing core-shell type particle | grains in a dispersion liquid as a main component and further depositing the shell containing another metal.

Specific examples of the core fine particles include thermally decomposable organic fine particles such as surfactant micelles, water-soluble organic polymers, styrene resins and acrylic resins; Acid-soluble inorganic fine particles such as ZnO, NaAlO ₂ , CaCO ₃ , and basic ZnCO ₃ ; Photo-soluble inorganic fine particles, such as ZnS, CdS, ZnO, etc. are mentioned.

In the present invention, the dispersion medium in which the core fine particles are dispersed is not particularly limited, and specific examples thereof include water; Alcohols such as methanol, ethanol and isopropanol; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran and 1,4-dioxane; Esters such as ethyl acetate and methyl acetate; Glycol ethers such as ethylene glycol monoalkyl ether; Nitrogen-containing compounds such as N, N-dimethylacetamide and N, N-dimethylformamide; Sulfur containing compounds, such as dimethyl sulfoxide, etc. are mentioned.

Such a dispersion medium, it is containing water, though not required, SiO ₂ when added to the precursor, and to the reaction (hydrolysis and condensation), as for the mass of the dispersion medium from the viewpoint that it can be used, from 5 to 100 It is preferable to contain mass% of water.

The pH of such a dispersion medium is preferably 7 or more, more preferably 8 or more, particularly preferably 9 to 10, since the SiO ₂ precursor is easily polymerized in three dimensions to form a shell. .

When acid-soluble inorganic fine particles are used as the core fine particles, a pH at which the fine particles are not dissolved, that is, 8 or more is preferable.

As the SiO ₂ precursor, specifically, for example, silicic acid; Silicate; Hydrolyzable silanes, such as tetramethoxysilane and tetraethoxysilane, etc. are mentioned.

The curing catalyst (hereinafter, also simply referred to as "curing catalyst") containing the other metal is a curing catalyst for polymerizing a compound having a silanol group.

Specifically as a curing catalyst, a metal chelate compound, an organic tin compound, a metal alcoholate, a metal fatty acid salt, etc. are mentioned, for example.

Among them, from the viewpoint of the strength of the hollow fine particles, a metal chelate compound and an organic tin compound are preferable, and a metal chelate compound is particularly preferable.

 When a metal chelate compound is added, solid chain fine particles are by-produced, and the hollow fine particles are easily formed in a structure in which the chain fine particles are connected.

Specific examples of the metal chelate compound include aluminum acetylacetonate, aluminum bisethyl acetoacetate monoacetyl acetonate, aluminum di-n-butoxide-monoethyl acetoacetate, and aluminum di-isopropoxide-. Aluminum chelate compounds such as monomethyl acetoacetate and diisopropoxy aluminum ethyl acetate; Titanium chelate compounds such as titanium acetylacetonate and titanium tetraacetyl acetonate; Copper chelate compounds such as copper acetylacetonate; Cerium chelate compounds such as cerium acetylacetonate; Chromium chelate compounds such as chromium acetylacetonate; Cobalt chelate compounds such as cobalt acetylacetonate; Tin chelate compounds such as tin acetylacetonate; Iron chelating compounds such as iron (III) acetylacetonate; Manganese chelate compounds such as manganese acetylacetonate; Nickel chelate compounds such as nickel acetylacetonate; Zinc chelate compounds, such as zinc acetylacetonate, etc. are mentioned.

Among them, metal acetylacetonate is preferable in view of the strength of the hollow fine particles.

Specific examples of the organic tin compound include dibutyltin dilaurate, dioctyl tin dilaurate, dibutyltin diacetate, dioctyl tin diacetate, dibutyltin diacetylacetonate, and dibutyl tin bis. Liethoxy silicate etc. are mentioned.

Specific examples of the metal alcoholate include tetraisopropyl titanate, tetra-n-butyl titanate, tetra-2-ethylhexyl titanate, triethoxyaluminum, triisopropoxyaluminum, and the like. .

Specific examples of the metal fatty acid salts include zinc naphthenate, cobalt octylate, and cobalt naphthenate.

Amount (an oxide basis) of the curing catalysts containing other metals, based on 100 parts by mass of SiO ₂ amount of precursor (SiO ₂ basis), and preferably 0.1 to 15 parts by mass is, more preferably denied 0.2 ~ 8 wt It is more preferable that it is 0.5-5 mass parts. If the curing catalyst (oxide equivalent) containing another metal is 0.1 mass part or more, the intensity | strength of hollow microparticles | fine-particles becomes high enough. When the curing catalyst (oxide conversion) containing another metal is 15 mass parts or less, the refractive index of hollow microparticles | fine-particles is suppressed low.

(b) process:

The step (b) is a step of preparing the inorganic fine particles in the inorganic fine particle dispersion by dissolving or decomposing the core fine particles of the core-shell particles obtained in the step (a).

For example, when the core fine particles are acid-soluble fine particles, the core fine particles can be dissolved and removed by adding an acid.

As such an acid, Inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid; Organic acids such as formic acid and acetic acid; Acidic cation exchange resin etc. are mentioned.

In this invention, it is preferable that the density | concentration (solid content concentration) of the said inorganic fine particle in the said inorganic fine particle dispersion is 0.1-50 mass%, It is more preferable that it is 0.5-30 mass%, It is more preferable that it is 1-25 mass% desirable. If solid content concentration is this range, since inorganic particle dispersion liquid is stabilized, it is preferable.

(Matrix and matrix solution)

A matrix is a binder mix | blended in order to connect the said hollow fine particles, and to make it easy to contain an said inorganic fine particle in a scattering layer, and a matrix containing liquid means the solution which contained the said matrix in the solvent.

In the present invention, as described above, since the inorganic fine particles contain the hollow fine particles and the chain fine particles as desired, there is no need to use a matrix, but the scattering layer is the mass (solid content conversion) of the scattering layer. May contain 5% by mass or less of the matrix.

Although such a matrix is not particularly limited, it is preferable to be cured by heat or ultraviolet rays, for example, a precursor of an oxide of a metal or semimetal (hereinafter, these are all referred to as “primary metals”), an organic resin, and the like. Can be mentioned.

As the precursor of the primary metal oxides, _{e.g., Al 2 O 3, SiO 2} , SnO 2, TiO 2, there can be a precursor, such as ZrO _2, specifically, aluminum, silicon, tin, titanium, zirconium, etc. And main metal alkoxides.

As said main metal alkoxide, alkoxide silicate is inexpensive, it is easy to control reaction, and it is preferable from the reason that the adhesiveness of a scattering layer and a board | substrate becomes favorable. Specifically, for example, (1) tetraethyl silicate and tetramethyl silicate; (2) silicic acid alkoxides having perfluoropolyether groups such as perfluoropolyethertriethoxysilane; (3) alkoxides of silicates having a perfluoroalkyl group such as perfluoroethyltriethoxysilane; (4) Alkoxy silicates having vinyl groups such as vinyltrimethoxysilane and vinyltriethoxysilane; (5) 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrie Alkoxy silicate which has epoxy groups, such as oxysilane; (6) alkoxide silicic acid etc. which have acrylic groups, such as 3-acryloxypropyl trimethoxysilane, etc. are mentioned.

Specific examples of the organic resin include silicone resins, acrylic resins, urethane acrylate resins, epoxy acrylate resins, polyester acrylates, polyether acrylates, epoxy resins, and the like.

In this invention, such a matrix may be used independently and may use multiple types together.

Moreover, in this invention, it is preferable to contain a coupling agent in a part of matrix for hardening. For example, by using a matrix containing 3-acryloxypropyltrimethoxysilane as a coupling agent for tetraethyl silicate, the inorganic fine particles can be easily contained in the scattering layer, and the scattering layer can be prevented while preventing the occurrence of cracks. It is preferable because the film thickness can be easily thickened.

In this invention, it is preferable that it is 0.1-5 mass%, and, as for the density | concentration (solid content concentration of a matrix containing liquid) of the said matrix containing liquid, it is more preferable that it is 0.3-3 mass%. If solid content concentration is this range, it is necessary to repeat a coating process several times, but since it becomes easy to prevent the crack generation at the time of baking, it is preferable.

In this invention, since the said scattering layer contains the said inorganic fine particle and the said matrix as desired, the crystallinity of the transparent conductive film formed on the said scattering layer is improved, and it is related with the 2nd aspect of this invention. The specific resistance of the board | substrate with a transparent conductive film (henceforth "the board | substrate with a transparent conductive film of this invention") can be kept low (3x10 <^{-4> (} ohm) * cm or less).

Although the detail is not clear about the reason, this inventor guesses because the gas mixed in the said hollow microparticles | fine-particles is very few or does not exist at all.

(Formation method of scattering layer)

The scattering layer can be formed using the scattering layer coat liquid containing the inorganic fine particle dispersion and the matrix-containing liquid as desired, as described above.

In this invention, when using the scattering layer coat liquid containing any of the inorganic fine particle dispersion liquid and matrix containing liquid which were mentioned above, the scattering layer coat liquid prepares the above-mentioned inorganic fine particle dispersion liquid and matrix containing liquid separately. Although it is preferable to mix and prepare each, it may be what prepared the inorganic fine particle dispersion and the matrix containing liquid simultaneously in the same system.

In addition, when using the scattering layer coat liquid containing any of the above-mentioned inorganic fine particle dispersion liquid and matrix containing liquid, the scattering layer coat liquid is in the above-mentioned inorganic fine particle dispersion liquid from a viewpoint of tolerance as a scattering layer, etc. It is preferable that an inorganic fine particle composition and the matrix composition in the matrix containing liquid mentioned above are the same. Specifically, the composition is preferably a component containing Si.

In addition, when using the scattering layer coat liquid containing any of the above-mentioned inorganic fine particle dispersion and matrix containing liquid, the matrix solid content conversion amount in the scattering layer coat liquid forms a scattering layer as mentioned above. It is preferable that it is 5 mass% or less with respect to solid content, ie, the total mass of the said inorganic fine particle and the said matrix, and it is more preferable that it is 3 mass% or less.

In this invention, it is preferable that solid content concentration of the said scattering layer coat liquid is 0.1-5 mass%, It is more preferable that it is 0.3-3 mass%, It is further more preferable that it is 0.5-2 mass%. If solid content concentration is this range, it is necessary to repeat a coating process several times, but since it becomes easy to prevent the crack generation at the time of baking, it is preferable.

In this invention, as a formation method of the said scattering layer, the method of apply | coating a scattering layer coat liquid to the surface of the said board | substrate specifically, for example, etc. are mentioned, for example.

Specific examples of the coating method include roller coating, manual coating, brush coating, dipping, rotary coating, dip coating, coating by various printing methods, curtain flow, bar coat, die coat, gravure coat, and microgravure coat. , Reverse coat, roll coat, flow coat, spray coat, dip coat, etc. Among them, the dip coat can form scattering layers on both sides of the substrate at once, and also thick layers can be formed without cracking. It is preferable because there is.

Moreover, baking at the time of formation of the said scattering layer is a thing with the transparent conductive film of this invention WHEREIN: It is preferable to perform a transparent conductive film at the temperature higher than the temperature at the time of film-forming, specifically 300-650 degreeC in air | atmosphere, It is more preferable to carry out at 300-550 degreeC. When the firing temperature is within this range, even when a small amount of gas is mixed in the hollow fine particles, the transparent conductive film can be formed without being adversely affected by the gas or the like, and the crystallinity of the transparent conductive film is improved. It is preferable because the specific resistance of the substrate with a transparent conductive film of the invention can be kept low.

This point is described in patent document 1 as 10 minutes at 200 degreeC in Example 1 as a condition of heat processing. In order to reliably simply solidify as a film, it is enough at this temperature, but as mentioned above, when using it as a light emitting element, the transparent conductive film formed after that by the gas etc. which exist in a film | membrane is mentioned. This results in lower crystallinity and higher specific resistance. On the other hand, in this invention, even if a small amount of gas mixes in the said hollow microparticles | fine-particles by baking at the temperature of 300-650 degreeC higher than the temperature of the board | substrate with a film at the time of transparent conductive film film-forming, the influence of the gas etc. Can be minimized.

Moreover, it is preferable that the baking time at the time of formation of a scattering layer is about 10 to 60 minutes.

In this invention, although the film thickness of the said scattering layer is not specifically limited, It is preferable that it is 0.7-10 micrometers, and it is more preferable that it is 1-2.5 micrometers.

The surface roughness of the scattering layer is 10 to 10 from the viewpoint of transmitting light (for example, visible light) when the substrate with a film of the present invention is used for a light emitting element, or further improving the extraction efficiency of the light emitting element. It is preferable that it is 20 nm, and it is more preferable that it is 12-18 nm.

Here, in the present invention, the surface roughness refers to the arithmetic mean height Ra defined in JIS BO601 (2001), and is characterized by an atomic force microscope (Nano Scope IIIa; ScanRate 1 Hz, Sample Lines 256, Off-line Modify Flatten). Measurement area of 5 micrometers x 5 micrometers (vertical x horizontal) in each point by order-2, Planefit order-2, Digital Instruments make) (A measuring point is the center of a board | substrate with length x width 100 x 100 mm). Refers to the value obtained by measuring

[Low resistance layer]

The low resistance layer of the present invention is a layer for further improving the crystallinity of the transparent conductive film formed thereon and keeping the specific resistance of the substrate with the transparent conductive film of the present invention lower. Is a layer formed on.

In addition, when the said scattering layer is formed in both surfaces of the said board | substrate, the said low resistance layer may be formed only on the scattering layer of the side which forms a transparent conductive film, but scattering of both surfaces is because the extraction efficiency improves further. It is preferably formed on the layer.

In this invention, it is preferable that the said low resistance layer is formed using the matrix containing liquid containing the matrix mentioned above. Specifically as a matrix, the precursor of a main metal oxide, organic resin, etc. which were illustrated above are mentioned, for example.

Moreover, it is preferable that the density | concentration (solid content concentration of a matrix containing liquid) in a matrix containing liquid is 0.1-5 mass%, It is more preferable that it is 0.3-3 mass%, It is still more preferable that it is 0.5-2 mass%. . If solid content concentration is this range, it is necessary to repeat a coating process several times, but since it becomes easy to prevent the crack generation at the time of baking, it is preferable.

As the formation method of the said low resistance layer, like the formation method of the scattering layer mentioned above, specifically, the method of apply | coating a matrix containing liquid to the surface of the said scattering layer, and baking after that etc. are mentioned, for example. have. Specifically, application by a dip coat is preferable because a low resistance layer can be formed on both surfaces of the substrate at one time.

By this formation method, the low resistance layer is formed as a film containing a matrix.

Among them, it is preferable for the reason that a low resistance hwacheung the can to form an SiO ₂ film, and further improve the crystallinity of the transparent conductive film is formed on the low resistance hwacheung.

In this invention, although the total film thickness of the said scattering layer and the said low resistance layer is not specifically limited, It is preferable that it is 0.01-10 micrometers, and it is more preferable that it is 0.05-2 micrometers. When the low resistance layer is formed, the coating liquid for forming the low resistance layer penetrates into the scattering layer, and as a result, the total film thickness after firing may be about the same as that of only the scattering layer, or vice versa. .

 Moreover, it is preferable that it is 10-20 nm, and, as for the surface roughness of the said low resistance layer, it is more preferable that it is 12-18 nm. If surface roughness is this range, the extraction efficiency of the light emitting element manufactured using the board | substrate with a film of this invention becomes more favorable.

In the present invention, by having the low resistance layer, even when a small amount of gas is mixed in the hollow fine particles, the gas serves to shield the gas without diffusing to the transparent conductive film. It is preferable at the point which can maintain electroconductivity.

In the case where the substrate is glass, the low-resistance layer is a SiO ₂ film, which is similar to each other in terms of expansion coefficient and the like, and therefore is preferable in that cracks due to expansion and the like can be prevented.

Further, the transparent conductive film is determined improvement of, by a low-resistance ITO film by hwacheung and below the transparent conductive film as an Si0 ₂ film, it is exhibited more significantly.

As described above, the substrate with a film of the present invention formed by forming the low-resistance layer as desired with the scattering layer not only improves the extraction efficiency of the light emitting device manufactured using the substrate, but also lowers the specific resistance of the transparent conductive film. It can be very useful.

Here, paragraphs [0125] to [0126] of Patent Document 1 describe forming a smoothing base layer. This base layer literally means "smoothing", that is, a layer for smoothing the layer is necessary. This is also described in Patent Document 1 that by forming a smoothing base layer, it is easy to form on a composite thin film that smoothness between the thin films, high uniformity of thickness, etc. is required, such as an organic EL element. It can be easily guessed.

However, in the present invention, the underlying layer does not need to be smooth, and on the contrary, it has been found that it is desirable to have some surface roughness. This does not have a problem of refractive index difference as described in Patent Document 1, and the larger the surface roughness of the underlying layer is, the more light is scattered when the light proceeds from the transparent conductive film to the underlying layer. This is due to the new knowledge that light is reduced by reflecting at the interface between the exposed surface of the substrate 1 and the air and being directed toward the edge of the substrate, and as a result, the extraction efficiency is improved.

Although the manufacturing method of the board | substrate with a film of this invention is not specifically limited, The method of providing the said scattering layer formation method, specifically, the scattering layer coating liquid containing an inorganic fine particle dispersion liquid is apply | coated to the surface of a board | substrate, The manufacturing method of the board | substrate with a film provided with the process of forming is illustrated preferably. Moreover, when it has the said low resistance layer, the method provided with the formation method of the said low resistance layer and the said low resistance layer, specifically, the scattering layer coating liquid which contains an inorganic fine particle dispersion liquid and a matrix containing liquid on the surface of a board | substrate. The step of forming a scattering layer by applying a coating, the matrix-containing liquid is applied, and fired for 10 to 60 minutes at 300 ~ 650 ℃, to form a low resistance layer on the scattering layer, the scattering layer and the low resistance layer The manufacturing method of the board | substrate with a film provided with the process of obtaining the board | substrate with a film formed in order is preferably illustrated.

The board | substrate with a transparent conductive film which concerns on the 2nd aspect of this invention is a scattering layer of the board | substrate with a film which concerns on the 1st aspect of this invention mentioned above (when a low resistance layer is formed as desired. It is a substrate with a transparent conductive film formed by forming a transparent conductive film on it, and whose specific resistance is 3 * 10 <^{-4> (} ohm) * cm or less.

Next, the transparent conductive film used for the board | substrate with a transparent conductive film of this invention is explained in full detail.

[Transparent Conductive Film]

The transparent conductive film of this invention is a film used as a positive electrode when it uses for the light emitting element (henceforth a "light emitting element of this invention") which concerns on the 3rd aspect of this invention mentioned later, and is formed on the said scattering layer That's it. Further, even when the scattering layer is formed on both surfaces of the substrate, the light emitting layer constituting the light emitting element is formed only on one side of the substrate, so that the transparent conductive film is formed only on one scattering layer.

The transparent conductive film may be a single layer film made of one kind of conductive material, or may be a laminated film having two or more layers made of different types of transparent conductive materials.

Specifically as an electrically-conductive material which forms the said transparent conductive film, For example, indium oxide which doped indium oxide, tin oxide, zinc oxide, and tin oxide (henceforth abbreviated as "ITO"), and zinc oxide doped oxidation are mentioned, for example. Indium (hereinafter abbreviated as "IZO"), zinc oxide doped with aluminum oxide (hereinafter abbreviated as "AZO"), etc. are mentioned.

In this invention, it is preferable that the said transparent conductive film is a film | membrane containing 80-99 mass% and 1-20 mass% of dopant materials of the conductive material which does not contain a dopant material among the said conductive materials.

Moreover, it is preferable that the said transparent conductive film is a film which has indium oxide as a main component, and it is more preferable that it is a film which consists of ITO (henceforth an "ITO film").

Moreover, it is preferable to contain 1-20 mass% of tin oxide in 100 mass% of total of an ITO membrane, indium oxide, and tin oxide.

In the present invention, examples of the method for forming the transparent conductive film include sputtering, chemical vapor deposition (CVD), vapor deposition, ion plating, and the like. Among these, the method of forming by the sputtering method of RF (high frequency) or DC (direct current) using the target of various electroconductive materials is preferable.

In addition, it is preferable to use the argon-oxygen mixed gas as an atmosphere gas at the time of film-forming by the said sputtering method, and to determine the gas ratio of argon and oxygen so that the specific resistance value of a transparent conductive film may be minimum. Specifically, the ratio of the oxygen gas in the argon-oxygen mixed gas is preferably 0.1 to 5% by volume, more preferably 0.5 to 2% by volume.

Moreover, the temperature of the board | substrate with a film at the time of film-forming by the said sputtering method is 100-500 degreeC, Preferably it is 250-450 degreeC. This makes a transparent conductive film hard to become amorphous by making glass substrate temperature 100 degreeC or more, and the specific resistance and chemical-resistance of a transparent conductive film become favorable. Moreover, it is because crystallinity is suppressed by making film-forming temperature into 500 degrees C or less, and the unevenness | corrugation of a film surface hardly becomes large.

In the present invention, the transparent conductive film has a film thickness of 30 to 500 nm and preferably 50 to 200 nm from the viewpoint of specific resistance and transparency.

Moreover, the specific resistance of the said transparent conductive film is 3 * 10 <^-4> ohm * cm or less from a viewpoint of using the board | substrate with a transparent conductive film of this invention for a light emitting element, It is preferable that it is 2.8 * 10 <^-4> ohm * cm or less.

In the present invention, the specific resistance value of the transparent conductive film (Ω? Cm) is, to measure the sheet resistance R _□ of the transparent conductive film with a surface resistance meter (e.g., a reseuta IP MCP-250, manufactured by Mitsubishi Oil Painting Company) The film thickness of a transparent conductive film is measured with the shape measuring instrument (for example, DEKTAK3-ST, Veeco company make), and the value calculated | required by following formula (1) is said.

The sheet resistance R of the resistivity of the transparent conductive film means transparent conductive film _□ × Film thickness of transparent conductive film (1)

Since the substrate with a transparent conductive film of this invention which forms such a transparent conductive film forms the said scattering layer which is a base layer of a transparent conductive film as mentioned above, while taking out low specific resistance, the extraction efficiency is also improved. You can.

Although the shape and structure of the board | substrate with a transparent conductive film of this invention are demonstrated in detail using FIG. 1 below, the board | substrate with a transparent conductive film of this invention is not limited to this figure.

1 is a partially cutaway cross-sectional view showing the shape and configuration of a substrate with a transparent conductive film of the present invention.

As shown in FIG. 1, the board | substrate 5 with a transparent conductive film of this invention is a transparent conductive film (on the board | substrate 3 with a film | membrane 3 in which the scattering layer 2 was formed on the single side | surface of the glass substrate 1). 4) is formed.

The light emitting element which concerns on 3rd aspect of this invention forms a light emitting layer and a metal electrode (negative electrode) in this order on the transparent conductive film (positive electrode) of the board | substrate with a transparent conductive film which concerns on the 2nd aspect of this invention mentioned above. Light emitting element.

Moreover, it is preferable that the light emitting element of this invention laminated | stacked the hole transport layer, the light emitting layer, the electron carrying layer, and a metal electrode in this order on the transparent conductive film of the board | substrate with a transparent conductive film. Moreover, it is preferable that a hole injection layer, a hole transport layer, a light emitting layer, an electron carrying layer, an electron injection layer, and a metal electrode are laminated | stacked in this order on the transparent conductive film of the board | substrate with a transparent conductive film.

In addition, it is preferable that the light emitting layer, the hole injection layer, the hole transport layer, and the electron transport layer formed as desired contain an organic material.

Next, the light emitting layer used for the light emitting element of this invention, the hole injection layer formed as desired, a hole transport layer, an electron carrying layer, and an electron injection layer are explained in full detail.

[Light Emitting Layer]

The light emitting layer of this invention is a layer which excitons generate | occur | produce by recombination of the hole injected from the transparent conductive film which is a positive electrode, and the electron injected from a metal electrode.

The material of the light emitting layer is not particularly limited as long as it is a light emitting molecule that emits light by recombination of holes and electrons, and conventionally known light emitting molecules can be used. Specific examples thereof include fluorescent light emitting materials such as aluminquinolinol complexes (for example, Alq3); Phosphorescent light emitting materials such as iridium complexes (eg, Ir (ppy) ₃ ); Rare earth metal complexes; Anthracenes (eg, anthracene); Π conjugated polymer materials such as polyphenylene vinylenes (for example, polyphenylene vinylene (PPV)), polyfluorenes, polythiophenes, and the like; The light emitting material containing the non-conjugated polymer material which is a pigment | dye containing polymer, etc. are mentioned.

Among these, it is preferable to use the fluorescent light emitting material containing an aluminoquinolinol complex (for example, Alq3) for the reason which has electron transport property and light emission characteristic.

[Hall transport layer]

The hole transport layer of the present invention is a layer for increasing the mobility in the light emitting layer of the holes to be injected.

-NPD), TPD (N,N'-비스(3-메틸페닐)N,N'-7-디페닐-[1,1-비페닐]-4,4'-디아민), 아릴아민류 (예를 들어, 디페닐아민, N-페닐-m-톨루이딘 등), 폴리페닐렌비닐렌 등을 들 수 있다.As a material of the said hole transport layer, specifically, the triphenyl diamine derivative (for example,

-NPD), TPD (N, N'-bis (3-methylphenyl) N, N'-7-diphenyl- [1,1-biphenyl] -4,4'-diamine), arylamines (eg , Diphenylamine, N-phenyl-m-toluidine and the like), polyphenylenevinylene and the like.

[Electron transport layer]

The electron transport layer of the present invention is a layer for increasing the mobility in the light emitting layer of the injected electrons.

As a material of the said electron carrying layer, specifically, the alumininolinol complex (for example, Alq3) mentioned above, oxadiazoles (for example, oxadiazole), triazoles (for example, Triazole), phenanthrosine (for example, phenanthrosine), etc. are mentioned.

[Hole injection layer]

The hole injection layer of this invention is a layer which improves the injection efficiency of the hole injected into a light emitting layer.

Specifically as a material of the said hole injection layer, For example, arylamines (for example, diphenylamine, N-phenyl-m-toluidine, etc.), phthalocyanines (for example, phthalocyanine), Lewis acid dope organic The material, the material containing polyaniline and an organic acid, the material containing polythiophene and a polymeric acid, etc. are mentioned.

[Electron injection layer]

The electron injection layer of this invention is a layer which improves the injection efficiency of the electron injected into a light emitting layer.

As a material of the said electron injection layer, an alkali metal (for example, Li, Na, Ka etc.), lithium fluoride, lithium oxide, a lithium complex, an alkali metal dope organic material, barium, calcium etc. are specifically mentioned, for example. Can be mentioned.

[Metal Electrode]

Conventionally well-known metal electrodes can be used for the metal electrode of this invention, For example, an aluminum (Al) electrode, a magnesium (Mg) electrode, the electrode which consists of these alloys, etc. are mentioned, It is preferable to form using a small metal material for the reason that the injection of electrons into the light emitting layer becomes easy. As a metal material with a small work function, Al, Mg, their alloy, etc. are specifically illustrated preferably.

Here, the light emitting layer, the hole transport layer, the electron transport layer, the hole injection layer, and the electron injection layer provided as desired may be formed by coating the materials of the above-described layers using, for example, vacuum deposition or spin coating. Can be.

Although the shape and structure of the light emitting element of this invention are demonstrated in detail using FIG. 2 below, the light emitting element of this invention is not limited to this figure.

2 is a partially cutaway cross-sectional view showing the shape and configuration of the light emitting device of the present invention.

As shown in FIG. 2, the light emitting element 11 of the present invention includes a transparent conductive film 4, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and the like on a substrate 3 with a film. The electroluminescent element 10 which consists of metal electrodes 9 is formed.

Example

Although an Example demonstrates this invention concretely below, this invention is limited to this and is not interpreted.

[Preparation of hollow silica sol liquid A (inorganic fine particle dispersion)]

First, ethanol 29.82 g, water 39 g, ZnO fine particle water dispersion sol (FZO-50, average primary particle diameter 21 nm, average aggregate particle diameter 50 nm, manufactured by Ishihara Industrial Co., Ltd.) 21 g, tetra after addition of the silane (SiO ₂ solid content of 29% by weight) 10 g, and the aqueous ammonia solution to pH = 10 by the addition, the mixture was stirred at 20 ℃ 4.5 hours.

Next, 0.18 g of zirconium acetylacetonate (manufactured by Kanto Chemical Co., Ltd.) was added, and stirred for 1.5 hours to obtain 100 g of a core-shell fine particle dispersion (solid content concentration of 6% by weight).

Then, 100 g of strongly acidic cation exchange resins (diamond ions, total exchange capacity of 2 (meq / ml) or more, manufactured by Mitsubishi Chemical Corporation) was added to the obtained core-shell fine particle dispersion, which was stirred for 1 hour to reach pH = 4. Thereafter, by removing the strongly acidic cation resin by filtration, 100 g of an inorganic fine particle dispersion containing hollow SiO ₂ fine particles containing Zr was obtained.

The thickness of the outer shell of the obtained hollow SiO ₂ fine particles was 6 nm, and the pore diameter was 30 nm. In addition, hollow SiO ₂ fine particles thus obtained were agglomerate particles, the average aggregated particle diameter of 50 nm, solid content concentration 3% by mass. Further, the obtained hollow fine particles of Si0 Si0 ₂ content of Zr based on 100 parts by weight of ₂ (ZrO ₂ conversion) was 1.68 parts by mass. The refractive index of the hollow SiO ₂ fine particles was 1.33.

The inorganic fine particle dispersion thus obtained was concentrated by ultrafiltration to prepare a hollow silica sol liquid A (inorganic fine particle dispersion) having a solid content of 10% by weight in terms of SiO ₂ .

[Preparation of silica sol liquid B (matrix-containing liquid)]

First, 0.97 mass part of 61 mass% nitric acid was added to 4.71 mass parts of ion-exchange water, and it stirred for 5 minutes. This aqueous nitric acid solution was added to 54.05 parts by mass of ethanol, mixed and stirred for 5 minutes to prepare a mixed solution I.

Next, 6.94 mass parts of tetraethyl silicates were added to this liquid mixture I, and it stirred at room temperature for 60 minutes. After stirring for 60 minutes, 33.33 parts by mass of ethanol was further added and stirred and mixed for 5 minutes to obtain a polymerized silica sol liquid B of ethyl silicate having a solid content of 2 mass% of SiO ₂ .

Further, SiO ₂ in terms of solid content is, when a solid content of all of the ethyl silicate is Si minutes call SiO _2.

[Preparation of Polymeric Sol Solution C (Matrix-Containing Liquid)]

First, 0.082 mass part of 61 mass% nitric acid was added to 3.96 mass parts of ion-exchange water, and it stirred for 5 minutes. This aqueous nitric acid solution was mixed with 88.17 parts by mass of ethanol and stirred for 5 minutes to prepare a liquid mixture II.

Next, 7.80 mass parts of 3-acryloxypropyl trimethoxysilane (Shin-Etsu Silicone Co., Ltd. brand name KBM-5103) which is an acryl-type silane coupling agent is added to this liquid mixture II, after stirring and mixing for 30 minutes in 60 degreeC hot water bath, It cooled to room temperature and obtained the polymerization sol liquid C of a silane coupling agent.

SiO ₂ in terms of solid content of the polymerization sol liquid C is 2% by mass. Further, a solid content at the time the case of SiO ₂ both in terms of solid content is 3-acryloxy propyl trimethoxy silane Si-minute call is SiO _2.

[Preparation of Scattering Layer Coating Liquid D (Dip Liquid)]

10 mass parts of hollow silica sol liquid A was added to 90 mass parts of ethanol, stirring, Finally, 1 mass part of propylene glycol was added, and also it stirred for 30 minutes, and the scattering layer coat liquid D was obtained. In addition, this scattering layer coating liquid D does not contain a matrix component.

The scattering layer coating solution of SiO ₂ in terms of solid content of the D was 1% by mass.

[Preparation of Low Resistance Layer Coating Liquid E (Dip Liquid)]

40 mass parts of silica sol liquid B and 10 mass parts of polymerization sol liquid C were added to 50 mass parts of ethanol in order, stirring, Finally, 1 mass part of propylene glycol was added, and it stirred and mixed for 30 minutes further, and the low-resistance layer Coat liquid E was obtained.

The low resistance in terms of SiO ₂ solids content of the coating solution E hwacheung was 1% by mass.

In addition, each of the SiO ₂ in terms of solid content mass ratio of the silica sol liquid B, and a polymeric sol liquid C is 4: 1.

[Preparation of hollow silica sol liquid F (inorganic fine particle dispersion)]

75.61 parts by mass of isopropyl alcohol was added to 24.39 parts by mass of a hollow silica sol (ELCOM V-8205, manufactured by Catalytic Chemical Industries, Ltd.) to obtain a hollow silica sol liquid F having a solid content of 5% by mass.

In addition, ELCOM V-8205 of a commercial item did not have another metal and was 20.5% of solid content in the hollow silica sol liquid of IPA (isopropyl alcohol) dispersion | distribution, and the average aggregate particle diameter was 65 nm. In addition, the average aggregate particle diameter was measured by the Nikkiso company make, and the microtrack UPA150.

[Preparation of Scattering Layer Coating Liquid G (Dip Liquid)]

18 mass parts of hollow silica sol liquid F, 4 mass parts of silica sol liquids B, 1 mass part of polymerization sol liquids C are added to 77 mass parts of ethanol, stirring, and finally, 1 mass part of propylene glycol is added, and it adds The mixture was stirred for 30 minutes, thereby obtaining a scattering layer coat liquid G.

The scattering layer coating solution of SiO ₂ in terms of solid content of G was 1% by mass.

In addition, the hollow silica sol liquid F, the silica sol liquid B and for each SiO mass ratio of ₂ in terms of solid content of the polymeric sol liquid C was 45: 4: 4 was: 1 (10 SiO ₂ mass ratio in terms of solid content of the fine particle component and a matrix-containing liquid 90).

(Example 1)

A glass substrate (AN 100, alkali-free glass, size 100 x 100 mm, thickness 0.7 mm, manufactured by Asahi Glass Co., Ltd.) was prepared, and the glass substrate surface was wiped with cerium oxide dispersed in water.

Next, the polished glass substrate was placed on a dip coater (CT-1020 type, manufactured by JPC Co., Ltd.) that satisfies the scattering layer coating liquid D in a liquid tank. mm / sec, holding time 20 seconds after pulling up all the samples as 1 cycle, 40 cycles of dipping, and baking for 30 minutes at 500 degreeC in air | atmosphere, and obtained the deep-coat sample in which the scattering layer was formed on both surfaces of the glass substrate. .

The film thickness (layer thickness) of the scattering layer was 2 µm.

The obtained dip coat sample was evaluated by the following method, and the result was shown in Table 1.

(1) surface roughness

As described above, the surface roughness was determined at each point by an atomic force microscope (Nano Scope IIIa manufactured by Digital Instruments; Scan Rate 1 Hz, Sample Lines 256, Off-line Modify Flatten order -2, Planefit -2). The measurement area | region (measurement point was 100 x 100 mm (vertical x horizontal) center part of a board | substrate) of 5 micrometers x 5 micrometers (vertical x horizontal) of was calculated | required.

Subsequently, an ITO film having a film thickness of 180 nm was formed on the obtained dip coat sample by a magnetron sputtering method using an ITO target made of indium oxide containing 10% by mass of tin oxide in a total of 100% by mass of indium oxide and tin oxide. And the glass substrate with an ITO membrane was obtained. In addition, the substrate temperature at the time of film-forming was 300 degreeC.

Subsequently, heating was performed for 30 minutes in a vacuum.

Here, the film-forming pressure at the time of sputtering was 3.5 mmTorr (0.13 Pa).

In addition, using a mixed gas of argon and oxygen as the sputtering gas, the film was formed by changing the oxygen concentration (volume%) in the sputter gas to 0, 1, 2, 3, 4%, and the oxygen having the lowest specific resistance. The specific resistance at the time of film-forming on condition was measured.

The composition of the formed film was equivalent to the target.

The formed glass substrate with an ITO membrane was evaluated by the following method, and the result was shown in Table 1.

(2) Specific resistance value

As described above, the specific resistance (Ω? Cm) of the ITO film is measured by measuring the sheet resistance R _□ of the ITO film with a surface ohmmeter (Lorista IP MCP-250, manufactured by Mitsubishi Emulsion Co., Ltd.), and measuring the film thickness of the ITO film by a shape measuring instrument. It measured by (DEKTAK3-ST, Veeco company) and calculated | required by following formula (1).

Specific resistance value of ITO film = sheet resistance of ITO film R _□ × film thickness of ITO film (1)

(Example 2)

A glass substrate (AN 100, alkali-free glass, size 100 x 100 mm, thickness 0.7 mm, manufactured by Asahi Glass Co., Ltd.) was prepared, and the glass substrate surface was wiped with cerium oxide dispersed in water.

Next, the polished glass substrate was placed on a dip coater (CT-1020 type, manufactured by JPC Co., Ltd.) that satisfies the scattering layer coating liquid D in a liquid tank. 30 cycles of dipping were performed at mm / sec and 20 cycles of holding time after pulling up all samples.

Subsequently, the dip coater (CT-1020 type, manufactured by JP C), which satisfies the low-resistance layer coating liquid E in the liquid tank, had a falling speed of 6 mm / sec, a holding time of 5 seconds after sample dipping, a pulling speed of 1.5 mm / sec, The holding time 20 seconds after pulling up all the samples was made into 1 cycle, 10 cycles of dipping, and it baked at 500 degreeC for 30 minutes in air | atmosphere, and obtained the dip coat sample. The total layer thickness of the scattering layer and the low resistance layer was 1.4 µm.

The obtained dip coat sample was evaluated similarly to Example 1, and the result was shown in Table 1. In addition, the surface roughness measured the surface roughness on the low resistance layer.

Next, the ITO film | membrane was formed in the obtained dip coat sample similarly to Example 1, and the glass substrate with an ITO film | membrane was obtained. The formed glass substrate with an ITO film | membrane was evaluated like Example 1, and the result was shown in Table 1.

(Comparative Example 1)

A glass substrate (AN 100, alkali-free glass, size 100 x 100 mm, thickness 0.7 mm, manufactured by Asahi Glass Co., Ltd.) was prepared, and the glass substrate surface was wiped with cerium oxide dispersed in water.

Next, the polished glass substrate was placed on a dip coater (TD-1500, manufactured by SDI Co., Ltd.) that satisfies the scattering layer coating liquid G in a liquid bath. The falling speed was 6 mm / sec, the holding time was 5 seconds after the sample dipping, and the pulling speed was 1.5. 40 cycles of dipping was carried out by holding | maintaining 20 seconds of holding | maintenance time 20 second after pulling up a sample in mm / sec, and baking for 30 minutes at 500 degreeC in air | atmosphere, and the deep-coat sample in which the scattering layer was formed on both surfaces of the glass substrate was obtained. The layer thickness of the scattering layer was 1.5 µm.

The obtained dip coat sample was evaluated similarly to Example 1, and the result was shown in Table 1.

Next, the ITO film | membrane was formed in the obtained dipcoat sample like Example 1, and the glass substrate with an ITO film | membrane was obtained. The formed glass substrate with an ITO film | membrane was evaluated like Example 1, and the result was shown in Table 1.

(Comparative Example 2)

A glass substrate (AN 100, alkali-free glass, size 100 x 100 mm, thickness 0.7 mm, manufactured by Asahi Glass Co., Ltd.) was prepared, and the glass substrate surface was wiped with cerium oxide dispersed in water.

 Next, the polished glass substrate was subjected to a dip coater TD-1500 (manufactured by SDI Co., Ltd.) satisfying the scattering layer coating liquid G in a liquid tank, and a lowering speed of 6 mm / sec, a holding time of 5 seconds after sample dipping, and a pulling speed of 1.5 mm. 30 cycles of dipping were carried out for 1 second with the holding time of 20 seconds / sec after pulling up all the samples.

Subsequently, in the dip coater (TD-1500 type | mold, the SDI company made) satisfying the low-resistance layer coating liquid E in the liquid tank, descending speed 6 mm / sec, holding time 5 second after sample dipping, pulling speed 1.5 mm / sec, sample The holding time 20 seconds after pulling up all was made into 1 cycle, and 10 cycles of dipping was carried out, and it baked for 30 minutes at 500 degreeC in air | atmosphere, and obtained the dip coat sample. The total layer thickness of the scattering layer and the low resistance layer was 1.6 µm.

The obtained dip coat sample was evaluated similarly to Example 1, and the result was shown in Table 1. In addition, the surface roughness measured the surface roughness on the low resistance layer.

Next, the ITO film | membrane was formed in the obtained dip coat sample similarly to Example 1, and the glass substrate with an ITO film | membrane was obtained. The formed glass substrate with an ITO film | membrane was evaluated like Example 1, and the result was shown in Table 1.

(Comparative Example 3)

A dip coat sample was obtained in the same manner as in Comparative Example 2 except that the number of dipping of the upper layer low resistance layer coating liquid E was changed from 10 cycles to 4 cycles.

The obtained dip coat sample was evaluated similarly to Example 1, and the result was shown in Table 1. In addition, the surface roughness measured the surface roughness on the low resistance layer.

Next, the ITO film | membrane was formed in the obtained dip coat sample similarly to Example 1, and the glass substrate with an ITO film | membrane was obtained. The formed glass substrate with an ITO film | membrane was evaluated like Example 1, and the result was shown in Table 1.

(Comparative Example 4)

A glass substrate (AN 100, alkali-free glass, size 100 x 100 mm, thickness 0.7 mm, manufactured by Asahi Glass Co., Ltd.) was prepared, and the glass substrate surface was wiped with cerium oxide dispersed in water.

Next, the polished glass substrate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Next, the ITO film | membrane was formed in the wiped glass substrate similarly to Example 1, and the glass substrate with an ITO film | membrane was obtained. The formed glass substrate with an ITO film | membrane was evaluated like Example 1, and the result was shown in Table 1.

Scattering layer Low resistance layer Immersion count
(D liquid or G liquid / E liquid) Ra
(nm) Resistivity
(× ^10-4 Ωcm) Example 1 D liquid - 40/0 12.5 2.5 Example 2 D liquid E liquid 30/10 12.4 2.8 Comparative Example 1 G liquid - 40/0 9.7 3.4 Comparative Example 2 G liquid E liquid 30/10 8.1 2.5 Comparative Example 3 G liquid E liquid 30/4 8.5 2.4 Comparative Example 4 - - - 0.2 1.9

In the aspect of Comparative Examples 1-3 which formed the scattering layer formed using the inorganic fine particle containing liquid (hollow silica sol liquid F) containing hollow fine particles which do not contain another metal from the result shown in the said Table 1, it is a low-resistance layer By making it necessary to form a structure, it can be seen that the increase in the ITO film specific resistance can be suppressed. On the contrary, it can be seen that the specific resistance increases unless the low resistance layer is formed.

On the other hand, in the aspect of Examples 1 and 2 in which the scattering layer formed using the inorganic fine particle containing liquid (hollow silica sol liquid A) containing specific hollow microparticles containing other metal (Zr) was formed, With or without it, it turned out that the raise of ITO membrane specific resistance can be suppressed.

In addition, from the result of Examples 1 and 2, even if a matrix containing liquid (silica sol liquid B, polymerization sol liquid C) is not used for a scattering layer coat liquid, the raise of a specific resistance can be suppressed to the extent equivalent to Comparative Examples 2 and 3. It can be seen that.

Moreover, when an organic EL was formed using the glass substrate with ITO film of Examples 1 and 2, compared with the case where organic EL was formed using the glass substrate with ITO film of Comparative Examples 2 and 3, extraction efficiency is taken out. This is improved. This is considered to be because the surface roughness of the substrate-attached substrate surface produced in Examples 1 and 2 is increased to 10 nm or more, and the content of the hollow fine particles is increased as a result of the unnecessary matrix.

Industrial availability

According to the present invention, it is possible to provide a light emitting device having good extraction efficiency, a substrate with a film and a substrate with a transparent conductive film which can be used for the light emitting device.

 In addition, all the content of the JP Patent application 2007-113955, the claim, drawing, and the abstract for which it applied on April 24, 2007 is referred here, and it takes in as an indication of the specification of this invention.

Claims (11)

A substrate with a film formed by forming a scattering layer containing inorganic fine particles on at least one side of the substrate, The inorganic fine particles contain hollow fine particles, The hollow fine particles contain SiO ₂ , and further contain other metals, The content of the other metal (oxide basis) based on 100 parts by weight of said SiO ₂ is in the hollow fine particles, and 0.1 to 15 parts by weight, The said scattering layer does not contain a matrix with respect to the mass (solid content conversion) of the scattering layer, or contains a matrix of 5 mass% or less, The board | substrate with a film characterized by the above-mentioned. A substrate with a film formed by forming a scattering layer containing inorganic fine particles on at least one side of the substrate, The inorganic fine particles contain hollow fine particles and chain fine particles connecting the hollow fine particles, The hollow fine particles contain SiO ₂ , and further contain other metals, The chain-like fine particles contain SiO ₂ , further contain other metals, The hollow fiber content of the other metal in the fine particles (oxide basis) and the total of the content (an oxide basis) of the other metal in a chain-like particles, the hollow fine particles of SiO _2, and the total 100 parts by mass of SiO ₂ of the chain-like particles 0.1-15 mass parts with respect to parts, The said scattering layer does not contain a matrix with respect to the mass (solid content conversion) of the scattering layer, or contains a matrix of 5 mass% or less, The board | substrate with a film characterized by the above-mentioned. The method according to claim 1 or 2, The substrate with a film whose surface roughness on the said scattering layer is 10-20 nm. The method according to claim 1 or 2, The board | substrate with a film | membrane in which the said inorganic fine particle is prepared in an inorganic fine particle dispersion liquid by the method of providing the following (a) and (b) process at least. (a) a shell containing the other metal in the dispersion medium of the core fine particles are present, the addition of a curing catalyst containing the precursor and a different metal of SiO _2, the surface of the core fine particles contain SiO _2, and more The process of obtaining core-shell particle | grains by making it precipitate. (b) A step of dissolving or decomposing the core fine particles of the core-shell particles obtained in the step (a). The method according to claim 1 or 2, Furthermore, the board | substrate with a film formed by forming a scattering layer in the surface on the opposite side to the surface in which the said scattering layer was formed of the said board | substrate. delete The method according to claim 1 or 2, Furthermore, the substrate with a film formed by forming a low resistance layer on the said scattering layer. The board | substrate with a transparent conductive film which forms a transparent conductive film on the scattering layer of the board | substrate with a film of Claim 1 or 2, and whose specific resistance is 3 * 10 <^{-4> (} ohm) * cm or less. The transparent conductive film is formed on the low resistance layer of the board | substrate with a film of Claim 7, and the specific resistance of the transparent conductive film is 3x10 <^{-4> (} ohm) * cm or less, The board | substrate with a transparent conductive film. The light emitting element which forms a light emitting layer and a metal electrode in this order on the transparent conductive film of the board | substrate with a transparent conductive film of Claim 8. The light emitting element formed by forming a light emitting layer and a metal electrode in this order on the transparent conductive film of the board | substrate with a transparent conductive film of Claim 9.

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