CN100463578C - Electroluminescent device - Google Patents

Abstract

The electroluminescent device successively comprises a cathode, an electroluminescent layer, a transparent electrode layer, an evanescent light-scattering layer comprising a matrix composed of a low-refractive material containing light-scattering particles, and a transparent sheet/plate. Such an electroluminescent device is decreased in total reflection not only at a boundary surface between a transparent substrate and an outside air layer but also at a boundary surface of the transparent electrode layer on its light extraction side, and therefore, is considerably improved in light extraction efficiency. In addition, in the electroluminescent device provided with a barrier layer, the transparent electrode layer and the electroluminescent layer can be well protected so that deterioration of electroluminescent pigments and occurrence of dark spots can be effectively prevented, resulting in enhanced life of the device.

Description

Electroluminescent cell

Technical field

The present invention relates to electroluminescence (EL) element, in more detail, relate to from the light of electroluminescence layer and take out the high electroluminescent cell of efficient.

Background technology

The existing electroluminescent cell that uses in EL display or the EL illumination has the layer structure that comprises negative electrode, electroluminescence layer, transparency electrode (anode) layer and transparency carrier.Yet, utilization be electroluminescence layer, to carry out combination again from the anode injected holes with from the negative electrode injected electrons, by this binding energy again, luminescence center is excited, and carries out luminous principle of luminosity.

In the EL display, the light that requirement is sent takes out in transparent substrate side effectively, but cause reflection in the interface of transparency carrier and air layer, the light that takes out from transparency carrier takes out efficient (meaning the ratio that light that electroluminescence layer sends is fetched to the electroluminescent cell outside) and is low to moderate about 20%.

For the light reflection at the interface that reduces transparency carrier and air layer, the someone proposes between transparency carrier and transparent electrode layer low-index layer to be set, and the big light of the angle of emergence is reflected, and improves light taking-up efficient (spy opens the 2002-278477 communique).

Yet,, the light on the interface of transparent electrode layer and low-index layer is reflected is not also done any consideration though above-mentioned technology reduces the light reflection on the air layer interface with transparency carrier by low-index layer is set.Certainly, by low-index layer is set, the problem that exists the total reflection on the interface of transparent electrode layer and low-index layer to increase.This total reflection light again in transparent electrode layer inside or luminescent layer inside reflect by negative electrode, decay then takes place when guided wave and can not outwards send.

The present invention makes in view of above-mentioned truth, and it is a kind of except that the interface of transparency carrier and air layer that purpose provides, and the total reflection on the light taking-up side interface of transparent electrode layer is lowered the electroluminescent cell that the taking-up efficient of light is fully improved.

Summary of the invention

Above-mentioned purpose of the present invention reaches by the mode of following (1)～(8).

The 1st main points of (1) the 1st invention are a kind of electroluminescent cells, this electroluminescent cell is that negative electrode, electroluminescence layer, transparent electrode layer and light penetrating object dispose and the electroluminescent cell that forms successively, it is characterized in that the infiltration light diffusion layer A that the matrix that will be made of the low-index material of the particle that contains scattered light is made is arranged between transparent electrode layer and the light penetrating object.

The 2nd main points of (2) the 1st inventions are a kind of electroluminescent cells, this electroluminescent cell is that negative electrode, electroluminescence layer, transparent electrode layer, low-index layer and light penetrating object dispose and the electroluminescent cell that forms successively, it is characterized in that, the infiltration light diffusion layer A that will comprise the matrix that the low-index material by the particle that contains scattered light constitutes is arranged between transparent electrode layer and the low-index layer, and the refractive index of matrix that constitutes infiltration light diffusion layer A is equal and lower than the refractive index of transparent electrode layer in fact with the refractive index of low-index layer.

The 1st main points of (3) the 2nd inventions are a kind of electroluminescent cells, this electroluminescent cell is that negative electrode, electroluminescence layer, transparent electrode layer and light penetrating object dispose and the electroluminescent cell that forms in this order, it is characterized in that, the infiltration light diffusion layer A that will comprise the matrix that the low-index material by the particle that contains scattered light constitutes is arranged between transparent electrode layer and the light penetrating object, and the material that will prevent to permeate in the light diffusion layer A is arranged between infiltration light diffusion layer A and the transparent electrode layer to the separator of transparent electrode layer side diffusion.

About this separator, the absorptance transparent electrode layer of the visibility region more than refractive index and transparent electrode layer are equal or equal after a little while, a part of guided wave of transparent electrode layer moves to this layer, and the decay during guided wave descends, so also can expect the effect that extraction efficiency improves more.

The 2nd main points of (4) the 2nd inventions are a kind of electroluminescent cells, this electroluminescent cell is that negative electrode, electroluminescence layer, transparent electrode layer, low-index layer and light penetrating object dispose and the electroluminescent cell that forms in this order, it is characterized in that, the infiltration light diffusion layer A that will comprise the matrix that is made of the low-index material that contains the scattered light particle is arranged between transparent electrode layer and the low-index layer, and will prevent that the material in the low-index layer is arranged between infiltration light diffusion layer A and the transparent electrode layer to the separator of transparent electrode layer side diffusion.The refractive index that constitutes the matrix that permeates light diffusion layer A is equal and lower than the refractive index of transparent electrode layer in fact with the refractive index of low-index layer.

The 1st main points of (5) the 3rd inventions are a kind of electroluminescent cells, this electroluminescent cell is that negative electrode, electroluminescence layer, transparent electrode layer, low-index layer and light penetrating object dispose and the electroluminescent cell that forms in this order, it is characterized in that transparent electrode layer contains the particle of scattered light.

The 2nd main points of (6) the 3rd inventions are a kind of electroluminescent cells, this electroluminescent cell is that negative electrode, electroluminescence layer, transparent electrode layer, low-index layer and light penetrating object dispose and the electroluminescent cell that forms in this order, it is characterized in that, the infiltration light diffusion layer B that contains the particle of scattered light is arranged between transparent electrode layer and the light penetrating object, and the refractive index and the transparent electrode layer that constitute the matrix that permeates light diffusion layer B are equal in fact.

The 1st main points of (7) the 4th inventions are a kind of electroluminescent cells, this electroluminescent cell is that negative electrode, electroluminescence layer, transparent electrode layer, low-index layer and light penetrating object dispose and the electroluminescent cell that forms in this order, it is characterized in that the interface of transparent electrode layer and light penetrating object is the light scattering male and fomale(M﹠F).

The 2nd main points of (8) the 4th inventions are a kind of electroluminescent cells, this electroluminescent cell is that negative electrode, electroluminescence layer, transparent electrode layer, low-index layer and light penetrating object dispose and the electroluminescent cell that forms in this order, it is characterized in that, have and the high refractive index layer of the equal in fact refractive index of transparent electrode layer is arranged between transparent electrode layer and the light penetrating object, the interface of high refractive index layer and light penetrating object is the light scattering male and fomale(M﹠F).

Description of drawings

Fig. 1 (a) is the layer structure key diagram of the electroluminescent cell of the 1st invention, and Fig. 1 (b) is the total reflection key diagram of the big light of the angle of emergence.

Fig. 2 is another layer structure key diagram of the electroluminescent cell of the 1st invention.

Fig. 3 is the another layer structure key diagram of the electroluminescent cell of the 1st invention.

Fig. 4 is the layer structure key diagram of the electroluminescent cell of the 2nd invention.

Fig. 5 is another layer structure key diagram of the electroluminescent cell of the 2nd invention.

Fig. 6 is the another layer structure key diagram of the electroluminescent cell of the 2nd invention.

Fig. 7 is the layer structure key diagram of the electroluminescent cell of the 3rd invention.

Fig. 8 is another layer structure key diagram of the electroluminescent cell of the 3rd invention.

Fig. 9 is the another layer structure key diagram of the electroluminescent cell of the 3rd invention.

Figure 10 is the layer structure key diagram of the electroluminescent cell of the 4th invention.

Figure 11 is another layer structure key diagram of the electroluminescent cell of the 4th invention.

Figure 12 is the another layer structure key diagram of the electroluminescent cell of the 4th invention.

Figure 13 (a) is the layer structure key diagram of existing electroluminescent cell, and Figure 13 (b) is the total reflection key diagram of the big light of the angle of emergence.

Figure 14 is another layer structure key diagram of existing electroluminescent cell.

The preferred plan that carries out an invention

Explain the present invention below.

Before explanation the present invention, with Figure 13 (a), 13 (b) and Figure 14 existing electroluminescent cell is described earlier.Figure 13 (a) is the layer structure key diagram of existing electroluminescent cell, and Figure 13 (b) is the total reflection key diagram of the big light of the angle of emergence, and Figure 14 is another layer structure key diagram of existing electroluminescent cell.

Shown in Figure 13 (a), the layer structure of existing electroluminescent cell comprises substrate 5, transparent electrode layer (anode) 3, electroluminescence layer 2 and negative electrode 1 at least.In electroluminescent cell, the light that requires electroluminescence layer 2 to send is discarded to transparency carrier 5 sides effectively.Yet shown in Figure 13 (b), the light 11 that the angle of emergence of sending at electroluminescence layer 2 is big in the interface total reflection of substrate 5 and air 7, mainly forms the guided wave 12 that advances in the inside of substrate 5 to total reflection limit, face direction limit.By the generation of this guided wave 12, the light taking-up efficient of taking out from substrate 5 is low to moderate about 20%.

At such problem, in electroluminescent cell shown in Figure 14, because low-index layer 4 is arranged on electroluminescence layer 2 sides of substrate 5, so the big light 11 of the angle of emergence reflects at low-index layer 4, reduce the generation of guided wave, the result is that light takes out the efficient raising.Yet, in such electroluminescent cell, reduce in the total reflection of substrate 5, but the reflection of light on the interface of transparent electrode layer 3 and low-index layer 4 increases with the interface of air layer 7.

In addition, this total reflection light in transparent electrode layer inside or luminescent layer inside again by negative electrode reflection, when guided wave, decay, can not spread out of to the outside.List of references: チ ユ テ イ Na Application etc., answer spring thing association to give original text, 2003,27P-A-16, Fuji fields etc. answer thing association to give original text spring, and 2003,29-YN-13.

In view of above-mentioned actual conditions, electroluminescent cell of the present invention, can reach and reduce facing to the reflection of light on the interface of the side (that is an opposite side of a side that is connected with the electroluminescence layer 2 of transparent electrode layer 3) of the electroluminescence layer 2 of transparent electrode layer 3.

At first, as the basic layer that constitutes electroluminescent cell of the present invention, can enumerate substrate, negative electrode, electroluminescence layer, transparent electrode layer, low-index layer (not being provided with sometimes), as the substrate of light penetrating object or protective cover etc.

At first, the negative electrode that uses among the present invention, electroluminescence layer, transparent electrode layer, low-index layer, substrate, protective cover etc. are illustrated.

(A) about negative electrode:

Negative electrode, relative with transparent electrode layer, the clamping electroluminescence layer is provided with like that.This negative electrode is formed by aluminium, tin, magnesium, indium, calcium, gold, silver, copper, nickel, chromium, palladium, platinum, magnesium-silver alloy, magnesium-indium alloy, aluminum-copper-lithium alloys etc.Particularly, the negative electrode that is formed by aluminium is preferred.The thickness of negative electrode is generally 10～1000nm, preferred 30～500nm, more preferably 50～300nm.Negative electrode can become embrane method to form by evaporation or sputtering method equal vacuum.

(B) about electroluminescence layer:

Electroluminescence layer is by the material of scioptics constitutes by applying electric field.As this material, can use active oxidation zinc ZnS:X (in the formula, X is active elements such as Mn, Tb, Cu, Sm), CaS:Eu, SrS:Ce, SrGa ₂S ₄: Ce, CaGa ₂S ₄: Ce, CaS:Pb, BaAl ₂S ₄: organic EL material that the organic EL materials of low molecule pigment such as the inorganic EL material that Eu etc. use before this, the aluminium complex of oxine, aromatic amine, anthracene single crystal, poly-(to phenylene ethene) (Port リ (p-Off エ ニ レ Application PVC ニ レ Application)), poly-[2-methoxyl group-5-(2-ethyl hexyl oxy)-1,4-phenylene ethene], poly-(3-alkylthrophene), the organic EL material of Polyvinyl carbazole equiconjugate high score subclass etc. use before this.The thickness of electroluminescence layer is generally 10～1000nm, preferred 30～500nm, more preferably 50～200nm.Electroluminescence layer can become embrane method by evaporation or sputter equal vacuum, or forms with the rubbing method that chloroform etc. is made solvent.

(C) about transparent electrode layer 3:

The anode that transparent electrode layer can be used as electroluminescent cell works.As transparent electrode layer, can enumerate indium oxide (being commonly referred to ITO), the zinc oxide (being commonly referred to AZO) that adds aluminium that adds tin, the zinc oxide composite oxide films such as (being commonly referred to IZO) that adds indium.ITO is particularly preferred.

Transparent electrode layer can become embrane method to form by evaporation or sputter equal vacuum.The transparency electrode that forms is big more preferred more at the light transmittance of visible wavelength region, for example, is generally 50～99%.Its lower limit, preferred 60%, more preferably 70%.The resistance of transparency electrode, the smaller the better as the face resistance value, but be generally 1～100 Ω/ (=1cm ²).Preferred 70 Ω of its higher limit/, more preferably 50 Ω/.In addition, the thickness of transparency electrode as long as can satisfy above-mentioned light transmittance and face resistance value, is generally 0.01～10 μ m.From the viewpoint of conductivity, the preferred 0.03 μ m of its lower limit, more preferably 0.05 μ m.On the other hand, from the viewpoint of light transmittance, the preferred 1 μ m of its higher limit, more preferably 0.5 μ m.

Transparent electrode layer can be by formation such as photoetching processes as the necessary pattern of the electrode of electroluminescent cell.In addition, transparent electrode layer also can be formed by coating method.

(D) about low-index layer:

The refractive index of low-index layer, it is important hanging down than the refractive index of transparent electrode layer, preferably the refractive index than light penetrating object is low.This refractive index is generally 1.1～1.9, preferred 1.1～1.6, more preferably 1.2～1.5, especially preferred 1.2～1.35.Cross when low when refractive index, deficiency takes place in the mechanical strength of film easily, and when being silicate material, the ratio of silanol increases, and hydrophily strengthens, and is unfavorable as the EL instrument.When too high, the total reflection light quantity of the air side of low refractive index film and printing opacity side or light penetrating object increases, and the extraction efficiency of light descends.

The detecting refractive index of low refractive index film, D542 on principle, carry out with ellipsograph (ェ リ プ ソ メ--) (manufacturing of ソ プ ラ society), but the refractive index of the parent fraction of middle (nanometer) porous material or particle dispersion, owing to reasons such as formation incline structures, be difficult to sometimes measure with ellipsograph.When measuring at need with ellipsograph, available prism coupler model 2010 (U.S. メ ト リ コ Application society makes, and measures refractive index according to the kind of the wave guide mode that takes place in the film) is implemented detecting refractive index with the laser of wavelength 405nm or 633nm.

As the material of low-index layer, for example, can enumerate transparent fluororesin, magnesium fluorides etc. such as silicon dioxide, ring-type teflon, porous silica is specially suitable.In silicon dioxide, can import as required and be used for hydrophobization, give flexibility, prevent the organic principle of crackle etc.

The porous silica film, for example, can form by following operation: (1) is prepared the porous silica film and is formed the operation of using material liquid; (2) material liquid that obtains is coated in the operation that forms a film on the substrate; (3) make film macromolecule of coating quantize to form the operation of intermediate membrane; (4) make water-miscible organic solvent contact intermediate membrane, form the operation of porous silica film; (5) operation of dry porous silica film.

But, because purpose is to form low refractive index film, so, as long as satisfy above-mentioned condition to get final product its method for making is not particularly limited.For example, the perforated membrane (メ ソ Port-ラ ス film) by the manufacture method shown in the following document is made promptly can use as long as satisfy the necessary condition of film.

The spy opens 2002-278477 communique, 6,592, No. 764 communiques of United States Patent (USP), ア Le バ Star Network society skill newspaper and No. 57 in September, 2002 issues 34～36 pages, IDW 2002 and give 1163～1166 pages of original text collection.

Below each operation is illustrated.

(1) prepare the porous silica film and form the operation of using material liquid:

The porous silica film forms use material liquid, is with the alkoxyl silicone alkanes body of deciding, and contains the aqueous organic solution that can cause the starting compound of macromolecule quantification by hydrolysis and dehydration condensation.

As the aqueous organic solution of material liquid, contain alkoxyl silicone alkanes, hydrophilic organic solvent, water and catalyst as required.

As the alkoxyl silicone alkanes, can enumerate tetramethoxy-silicane, tetraethoxysilane, four (positive propoxy) silane, tetraisopropoxysilan, tetraalkoxysilane classes such as four (n-butoxy) silane, trimethoxy silane, triethoxysilane, methyltrimethoxy silane, methyl triethoxysilane, phenyltrimethoxysila,e, trialkoxysilanes such as phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, dialkoxy silicane classes such as diphenyl diethoxy silane, two (trimethoxysilyl) methane, two (triethoxysilyl) methane, 1, two (trimethoxysilyl) ethane of 2-, 1, two (triethoxysilyl) ethane of 2-, 1, two (trimethoxysilyl) benzene of 4-, 1, two (triethoxysilyl) benzene of 4-, 1,3, organic residues such as 5-three (trimethoxysilyl) benzene are in conjunction with the compound of the trialkoxysilyl more than 2 or 2, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-acryloxy propyl trimethoxy silicane, the alkyl that 3-carboxyl propyl trimethoxy silicane etc. replaces on silicon atom has the compound of reactive functional groups.Also have, can enumerate their partial hydrolystate and oligomer.

Wherein, particularly preferably be the oligomer of tetramethoxy-silicane, tetraethoxysilane, trimethoxy silane, triethoxysilane, tetramethoxy-silicane or tetraethoxysilane.The oligomer of tetramethoxy-silicane particularly is most preferred from the controlled consideration of reactive and gelation.

In addition, in above-mentioned alkoxyl silicone alkanes, can also be blended in the monoalkoxy silanes that 2～3 hydrogen, alkyl or aryl are arranged on the silicon atom.By mixing the monoalkoxy silanes, the porous silica film that obtains is carried out hydrophobization, resistance to water is improved.As the monoalkoxy silanes, for example, can enumerate triethyl group methoxy silane, triethyl-ethoxy-silicane alkane, tripropyl methoxy silane, triphenyl methoxy silane, triphenyl Ethoxysilane, diphenylmethyl methoxylsilane, diphenyl methyl Ethoxysilane etc.The combined amount of monoalkoxy silanes is 70 moles of % of whole alkoxyl silicone alkanes or 70 moles below the %.When the combined amount of monoalkoxy silanes surpassed 70 moles of %, gelation did not take place sometimes.

In addition, when with (3,3, the 3-trifluoro propyl) trimethoxy silane, (3,3, when the 3-trifluoro propyl) alkoxyl silicone alkanes with fluoroalkyl or fluoro aryl such as triethoxysilane, pentafluorophenyl group trimethoxy silane, pentafluorophenyl group triethoxysilane share, can obtain good resistance to water, moisture-proof, stain resistance etc.

In this material liquid, so-called oligomer also can be crosslinked, basket type molecule (シ Le セ ス キ ォ キ サ Application etc.).

The condensation ratio of the condensation product that contains in the water-containing organic solvent, as the transparency of this solution, for example, as wavelength 400nm, 23 ℃, the light transmittance of optical path length 10mm, usually in 90～100% scope.More than the light transmittance lower limit preferred 92% or 92% of solution, more preferably more than 95% or 95%.

Also have, when coating above-mentioned raw materials liquid, must reach to a certain degree macromolecule and quantize (that is, condensation carry out to a certain degree state).As the degree that its macromolecule quantizes, preferably reach naked eyes and do not see that the macromolecule of insoluble matter degree quantizes.Its reason is when having macroscopic insoluble matter in the material liquid before the coating, then to produce big concave-convex surface, membranous decline.

Organic solvent, the solvent with the ability that makes alkoxyl silicone alkanes, water and the following boiling point hydrophily organic compound mixing more than 80 ℃ or 80 ℃ that constitutes material liquid is preferred.For example, as spendable organic solvent, can enumerate the monohydric alcohol of carbon number 1～4, the alcohols such as polyalcohol such as dihydroxylic alcohols, glycerol or pentaerythrite of carbon number 1～4; The ether or the carboxylate of above-mentioned alcohols such as diethylene glycol (DEG), glycol monoethyl ether, glycol dimethyl ether, cellosolvo, propylene glycol monomethyl ether, propylene glycol methyl ether acetate; Ketone such as acetone, methylethylketone; Formamide, N-methylformamide, N-ethyl-formamide, N, dinethylformamide, N, N-diethylformamide, N-methylacetamide, N-ethyl acetamide, N, N-dimethylacetylamide, N, N-diethyl acetamide, N-methyl pyrrolidone, N-N-formyl morpholine N-, N-acetyl morphine, N-formylpiperidine, N-acetyl piperidine, N-formylpyrrole alkane, N-acetyl pyrrole alkane, N, N '-two formyl piperazine, N, N '-two formyl piperazine, N, N '-amide-types such as diacetyl piperazine; Lactone such as gamma-butyrolacton, tetramethylurea, N, N '-ureas such as methylimidazole quinoline; Methyl-sulfoxide etc.These water-miscible organic solvents can be used separately or as mixture.Wherein, from film forming (particularly volatility), as preferred organic to substrate, can enumerate the monohydric alcohol of acetone, methylethylketone, carbon number 1～4 etc., wherein, particular methanol, ethanol, normal propyl alcohol, isopropyl alcohol, acetone are more preferably methyl alcohol or ethanol.

As the hydrophily organic compound of boiling point more than 80 ℃ or 80 ℃, can enumerate in molecular structure, have hydroxyl, the hydrophilic functional group's of carbonyl, ehter bond, ester bond, carbonic acid ester bond, carboxyl, amido link, urethane bond, urea key etc. organic compound.In these hydrophily organic compounds, also can in molecular structure, have a plurality of hydrophilic functional groups in the middle of these.Here said boiling point is the boiling point under the pressure of 760mmHg.When using boiling point less than 80 ℃ hydrophily organic compound, the hole rate of porous silica film reduces terrifically sometimes.As the hydrophily organic compound of boiling point more than 80 ℃ or 80 ℃, can enumerate alcohols, the polyalcohols of carbon number 2～6, the phenols of carbon number 3～8.As preferred hydrophily organic compound, can enumerate the alcohols of carbon number 3～8, the glycols of carbon number 2～8, three alcohols of carbon number 3～8, the tetrol class of carbon number 4～8.As the hydrophily organic compound that is more preferably, can enumerate the alcohols of carbon numbers 4～7 such as n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, cyclopentanol, n-hexyl alcohol, cyclohexanol, benzylalcohol; Ethylene glycol, propylene glycol, 1, the glycols of carbon numbers 2～4 such as 4-butanediol; Three alcohols of carbon number such as glycerol or trimethylolethane 3～6; The tetrol class of carbon number such as erythrite or pentaerythrite 4～5.In these hydrophilic organic compounds, when carbon number was excessive, hydrophily descended too much sometimes.

Catalyst can add as required.Can enumerate the hydrolysis of the above-mentioned alkoxyl silicone alkanes of promotion and the material of dehydration condensation as catalyst.As object lesson, can enumerate acids such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetate, oxalic acid, maleic acid; Amines such as ammonia, butylamine, dibutylamine, triethylamine; Bases such as pyridine; Louis's acids such as the acetylacetone,2,4-pentanedione complex of aluminium; Metal chelate compound etc.

As the metal kind of the metal chelate compound that is used for catalyst, can enumerate titanium, aluminium, zirconium, tin, antimony etc.As concrete metal chelate compound, for example, can enumerate following compounds.

As the complex of aluminium, can enumerate diethoxy list (acetylacetone,2,4-pentanedione) and close aluminium, two positive propoxy lists (acetylacetone,2,4-pentanedione) close aluminium, diisopropoxy list (acetylacetone,2,4-pentanedione) closes aluminium, two n-butoxy lists (acetylacetone,2,4-pentanedione) close aluminium, two sec-butoxy lists (acetylacetone,2,4-pentanedione) close aluminium, two tert-butoxy lists (acetylacetone,2,4-pentanedione) close aluminium, monosubstituted ethoxy two (acetylacetone,2,4-pentanedione) closes aluminium, single positive propoxy two (acetylacetone,2,4-pentanedione) closes aluminium, single isopropoxy two (acetylacetone,2,4-pentanedione) closes aluminium, single n-butoxy two (acetylacetone,2,4-pentanedione) closes aluminium, single sec-butoxy two (acetylacetone,2,4-pentanedione) closes aluminium, single tert-butoxy two (acetylacetone,2,4-pentanedione) closes aluminium, tri acetylacetonato closes aluminium, diethoxy list (ethyl acetoacetate) closes aluminium, two positive propoxy lists (ethyl acetoacetate) close aluminium, diisopropoxy list (ethyl acetoacetate) closes aluminium, two n-butoxy lists (ethyl acetoacetate) close aluminium, two sec-butoxy lists (ethyl acetoacetate) close aluminium, two tert-butoxy lists (ethyl acetoacetate) close aluminium, monosubstituted ethoxy two (ethyl acetoacetate) closes aluminium, single positive propoxy two (ethyl acetoacetate) closes aluminium, single isopropoxy two (ethyl acetoacetate) closes aluminium, single n-butoxy two (ethyl acetoacetate) closes aluminium, single sec-butoxy two (ethyl acetoacetate) closes aluminium, single tert-butoxy two (ethyl acetoacetate) closes aluminium, three (ethyl acetoacetates) close chelate compound of aluminium such as aluminium etc.

As the complex of titanium, can enumerate triethoxy list (acetylacetone,2,4-pentanedione) and close titanium, three positive propoxy lists (acetylacetone,2,4-pentanedione) close titanium, three isopropoxy lists (acetylacetone,2,4-pentanedione) close titanium, three n-butoxy lists (acetylacetone,2,4-pentanedione) close titanium, three sec-butoxy lists (acetylacetone,2,4-pentanedione) close titanium, three tert-butoxy lists (acetylacetone,2,4-pentanedione) close titanium, diethoxy two (acetylacetone,2,4-pentanedione) closes titanium, two positive propoxies two (acetylacetone,2,4-pentanedione) close titanium, diisopropoxy two (acetylacetone,2,4-pentanedione) closes titanium, two n-butoxies two (acetylacetone,2,4-pentanedione) close titanium, two sec-butoxies two (acetylacetone,2,4-pentanedione) close titanium, two tert-butoxies two (acetylacetone,2,4-pentanedione) close titanium, the monosubstituted ethoxy tri acetylacetonato closes titanium, single positive propoxy tri acetylacetonato closes titanium, single isopropoxy tri acetylacetonato closes titanium, single n-butoxy tri acetylacetonato closes titanium, single sec-butoxy tri acetylacetonato closes titanium, single tert-butoxy tri acetylacetonato closes titanium, four (acetylacetone,2,4-pentanediones) close titanium, triethoxy list (ethyl acetoacetate) closes titanium, three positive propoxy lists (ethyl acetoacetate) close titanium, three isopropoxy lists (ethyl acetoacetate) close titanium, three n-butoxy lists (ethyl acetoacetate) close titanium, three sec-butoxy lists (ethyl acetoacetate) close titanium, three tert-butoxy lists (ethyl acetoacetate) close titanium, diethoxy two (ethyl acetoacetate) closes titanium, two positive propoxies two (ethyl acetoacetate) close titanium, diisopropoxy two (ethyl acetoacetate) closes titanium, two n-butoxies two (ethyl acetoacetate) close titanium, two sec-butoxies two (ethyl acetoacetate) close titanium, two tert-butoxies two (ethyl acetoacetate) close titanium, monosubstituted ethoxy three (ethyl acetoacetate) closes titanium, single positive propoxy three (ethyl acetoacetate) closes titanium, single isopropoxy three (ethyl acetoacetate) closes titanium, single n-butoxy three (ethyl acetoacetate) closes titanium, single sec-butoxy three (ethyl acetoacetate) closes titanium, single tert-butoxy three (ethyl acetoacetate) closes titanium, four (ethyl acetoacetates) close titanium, single (acetylacetone,2,4-pentanedione) three (ethyl acetoacetate) closes titanium, two (acetylacetone,2,4-pentanediones) two (ethyl acetoacetates) close titanium, tri acetylacetonato list (ethyl acetoacetate) closes titanium etc.

In addition, except that these catalyst, alkaline compound for example base catalyst such as ammonia also can use.At this moment, it is preferred suitably adjusting silica concentration, organic solvent kind etc.In addition, when adjusting aqueous organic solution, it is preferred not making the rapid enhancer of catalyst concn in the solution.As object lesson, can enumerate the alkoxyl silicone alkanes and mix with the part of organic solvent, then mix with water, at last the organic solvent of remnants and alkali are mixed the method for being mixed with this order.

As catalyst, Louis's acids such as acetylacetone,2,4-pentanedione complex of high volatile volatile and hydrochloric acid of removing easily or aluminium are particularly preferred.The addition of catalyst with respect to 1 mole of alkoxyl silicone alkanes, is generally 0.001～1 mole, preferred 0.01～0.1 mole.When the addition of catalyst during greater than 1 mole, produce the sediment that generates by thick gel particles, often can not get uniform porous silica film.

Porous silica film of the present invention forms the material liquid of usefulness, is to add above-mentioned raw materials to form.The cooperation ratio of alkoxyl silicone alkanes is with respect to preferred 10～60 weight % of whole material liquids, more preferably 20～40 weight %.When the cooperation ratio of alkoxyl silicone alkanes surpassed 60 weight %, the porous silica film broke sometimes during film forming.On the other hand, when the cooperation ratio of alkoxyl silicone alkanes was lower than 10 weight %, hydrolysis and dehydration condensation were extremely slow, caused the deterioration (film is inhomogeneous) of film forming sometimes.

The cooperation ratio of water is generally 0.01～10 times, preferred 0.05～7 times, more preferably 0.07～5 times with respect to the weight of the alkoxyl silicone alkanes that uses.The addition of water with respect to the alkoxyl silicone alkanes weigh less than 0.01 times the time, hydrolysis-condensation reaction to carry out degree insufficient, white casse appears in film sometimes.On the other hand, when the addition of water with respect to the weight of alkoxyl silicone alkanes during greater than 10 times, the surface tension of material liquid is extreme to become big, causes film forming to worsen (liquid produces the pearl etc. that contracts).

In addition, water is that the hydrolysis of alkoxyl silicone alkanes is necessary, from considering it is important as the viewpoint of making the film raising of the porous silica film of purpose.When the amount of water with respect to the mol ratio regulation of alcoxyl base unit weight the time, be generally 0.1～1.6 mole of doubly amount, preferred 0.3～1.2 mole of doubly amount, more preferably 0.5～0.7 mole of amount doubly with respect to 1 mole of the alkoxyl in the alkoxy silane.

The interpolation of water, after the alkoxyl silicone alkanes is dissolved in the organic solvent whenever carry out all can, be preferred but alkoxyl silicone alkanes, catalyst and other additives fully disperse the back to add water in solvent.

Used water is so long as getting final product of handling of any or dual mode of ion-exchange, distillation.Porous silica film of the present invention, when in use fields such as the semi-conducting material of detesting minute impurities especially and optical material, using, owing to need more highly purified silicon dioxide film, so it is preferred adopting the ultra-pure water that distilled water is obtained with ion-exchange treatment, at this moment, for example can use water by filter with 0.01～0.5 μ m aperture.

When adopting the hydrophily organic compound of boiling point more than 80 ℃ or 80 ℃ in the aqueous organic solution, the content of the hydrophily organic compound of boiling point more than 80 ℃ or 80 ℃, with respect to organic solvent and boiling point the total content of the hydrophily organic compound more than 80 ℃ or 80 ℃ usually at 90 weight % or below the 90 weight %, preferably at 85 weight % or below the 85 weight %.When the cooperation ratio of hydrophily organic compound surpassed 90 weight % of this total content, filming sometimes produced white casse midway in film forming, or the porous silica film breaks.

When the cooperation ratio of the hydrophily organic compound of boiling point more than 80 ℃ or 80 ℃ was very few, the porosity of porous silica film was minimum, and the porous silica film is difficult to reach low-refraction sometimes.Usually, the cooperation ratio of the total content of the hydrophily organic compound of boiling point more than 80 ℃ or 80 ℃ hydrophily organic compound more than 80 ℃ or 80 ℃ with respect to organic solvent and boiling point, usually at 30 weight % or more than the 30 weight %, preferably at 50 weight % or more than the 50 weight %, more preferably at 60 weight % or more than the 60 weight %.Therefore, the content of the hydrophily organic compound of the boiling point in the aqueous organic solution more than 80 ℃ or 80 ℃, the total content of the hydrophily organic compound more than 80 ℃ or 80 ℃ is generally 30～90 weight %, preferred 50～85 weight %, more preferably 60～85 weight % with respect to organic solvent and boiling point.

Atmosphere temperature degree and order by merging during the preparation coating fluid are arbitrarily, but in order to obtain forming in the coating fluid structure of homogeneous, last mixing water is preferred.In addition, in order to suppress the extreme hydrolysis or the condensation reaction of the alkoxyl silicone in the coating fluid, the adjustment of coating fluid usually 0～60 ℃, preferred 15～40 ℃, more preferably carry out under 15～30 ℃ the temperature range condition.

The stirring operation of coating fluid is arbitrarily when transferring liquid, but every kind is mixed that to adopt mixer to stir be preferred.

In addition, after coating fluid was adjusted, for carrying out the hydrolysis of alkoxyl silicone class, dehydration condensation, it was preferred making the coating fluid slaking.In between this maturation period, the alkoxyl silicone class hydrolytic condensate of generation, it is preferred being in homodisperse state in coating fluid, is preferred so stir coating solution.

Temperature between the maturation period is arbitrarily, generally both can be room temperature, perhaps also heats serially or intermittently.Wherein, in order to form 3 yuan of nano-porous structures that cause owing to alkoxyl silicone class hydrolytic condensate, it is preferred carrying out the Fast Heating slaking.In addition, when adding thermal maturation, it is preferred adding thermal maturation after the coating fluid adjustment at once, after the coating fluid adjustment usually can 15 days with interior, preferred 12 days with interior, more preferably began to add thermal maturation with interior on 3rd with interior, preferred especially 1 day.

Adding thermal maturation, concrete carried out 1～5 hour in 40～70 ℃ usually, at this moment, is preferred for obtaining uniform loose structure, stirring.Particularly consider that from the viewpoint of porous it 2～3 hours was preferred that near the temperature 60 ℃ adds thermal maturation.

The viscosity of material liquid considers from the viewpoint of making, and is generally 0.1～1000 centipoise, preferred 0.5～500 centipoise, more preferably 1～100 centipoise.

(2) form the operation of a film from material liquid:

A film is the aqueous organic solution as material liquid to be coated with form on substrate.As substrate, can enumerate semiconductors such as silicon, germanium, compound semiconductors such as gallium-arsenic, indium-antimony, substrates such as pottery, metal, transparency carriers such as glass substrate, synthetic resin substrate etc.

When porous silica film of the present invention forms on substrate, the character of the possible left and right sides of the character of substrate surface porous silica film.At this moment, not only to wash substrate surface but also can handle to substrate surface.As the surface washing of substrate, can enumerate acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, bases such as sodium hydrate aqueous solution, the hydrogen peroxide and the concentrated sulfuric acid, hydrochloric acid, ammonia etc. have in the mixed liquor of oxidizability and carry out impregnation process.Particularly from considering that with the viewpoint of the adaptation of porous silica film it is preferred with acids such as sulfuric acid, nitric acid silicon substrate, transparent glass substrate being carried out surface treatment.

As the method for coating material liquid, can enumerate the The tape casting using rod to be coated with machine, applicator or wing etc. material liquid is spread out on substrate, substrate is immersed in well-known methods such as the infusion process of drawing on the back in the material liquid or method of spin coating.In these methods, because The tape casting and method of spin coating can evenly be coated with material liquid, so be preferred.

Curtain coating speed with The tape casting coating material liquid the time is generally 0.1～1000m/ branch, preferred 0.5～700m/ branch, more preferably 1～500m/ branch.

Rotary speed during the coating material liquid of method of spin coating is generally 10～100000 rev/mins, preferred 50～50000 rev/mins, more preferably 100～10000 rev/mins.

In the dip coated method, with speed arbitrarily substrate is immersed in to draw on the back in the material liquid and gets final product.The last pulling rate degree of this moment for example is generally 0.01～50mm/ second, preferred 0.05～30mm/ second, more preferably 0.1～20mm/ second.The impregnating speed of substrate in coating fluid limits, and is preferred but with the speed with last pulling rate degree same degree substrate is immersed in the material liquid.Substrate is immersed in and also can continues to flood reasonable time in the material liquid during supreme the drawing.This continuation time is generally 1 second～and 48 hours, preferred 3 seconds～24 hours, more preferably 5 seconds～12 hours.In addition, the atmosphere gas in the coating can be in the air or in the non-active gas such as nitrogen or argon gas.Temperature is generally 0～60 ℃, preferred 10～50 ℃, more preferably 20～40 ℃, and the relative humidity of atmosphere gas is generally 5～90%, preferred 10～80%, more preferably 15～70%.Also have, the dip coated method is compared with method of spin coating, because rate of drying is slow, therefore because the sol gel reaction after the coating has the tendency of the distortion of forming stable film still less.Therefore, the preferably surface treatment by substrate, often may command membrane structure.

Film-forming temperature is generally 0～100 ℃, preferred 10～80 ℃, more preferably 20～70 ℃.

(3) Tu Bu film carries out the macromolecule quantification and the operation of formation intermediate membrane:

The film of coating carries out macromolecule and quantizes and the formation intermediate membrane.This reaction is called so-called sol-gel process, and this fundamental reaction comprises that alkoxyl silicone alkanes hydrolysis reaches 2 fundamental reactions of the dehydration condensation between the silanol group that generates by hydrolysis.

Hydrolysis causes by adding water, but water can be directly adds and is not particularly limited as the aqueous solution of liquid, alcohol or water vapour.When sharply adding water, depend on the kind of alkoxy silane, hydrolysis and dehydration condensation take place sometimes fast, produce precipitation.Therefore, in order not cause such precipitation, the preferred sufficient time of cost adds water, with the alcoholic solvent coexistence and reach the state that evenly adds water, way such as reaction carries out alone or in combination when low temperature adds water and suppresses to add.

When adopting sol-gel process to carry out alkoxyl silicone alkanes hydrolysis-condensation reaction, the condensation product of alkoxyl silicone alkanes carries out macromolecule lentamente and quantizes.In hydrolysis-condensation reaction, sometimes produce being separated of being considered to result from balance each other and change, but the equilibrium of the hydrophilicity of the alkoxyl silicone alkanes of the composition by material liquid, use and the hydrophily organic compound of boiling point more than 80 ℃ or 80 ℃ in the present invention, can control is separated takes place at nanoscale.The result is, the separation phase of hydrophily organic compound, and the state film forming on substrate with in the gel mesh that remains on alkoxyl silicone alkanes condensation product obtains intermediate membrane.

This shows that the hydrophily control of the hydrophily organic compound of boiling point more than 80 ℃ or 80 ℃ is important, when representing this hydrophily with relative dielectric constant, can stipulate to be preferably 10～20, more preferably 13～19.

From taking into account the viewpoint of such hydrophilicity, as the aqueous organic solution of material liquid, the organic solvents (concrete is methyl alcohol, ethanol etc.) that contain more than relative dielectric constant 23 or 23 are preferred.Particularly, when the weight ratio (weight of the weight of organic solvent/hydrophily organic compound) of the hydrophily organic compound more than 80 ℃ or 80 ℃ with organic solvent more than relative dielectric constant 23 or 23 and boiling point is set at preferred 5/5～2/8, more preferably 4/6～2/8 scope, can reach the behavior that is separated of expectation more.

(4) make water-miscible organic solvent contact intermediate membrane and form the operation (extraction process) of porous silica film:

By making water-miscible organic solvent contact intermediate membrane, the above-mentioned hydrophily organic compound in the intermediate membrane is removed in extraction, removes the water in the intermediate membrane simultaneously.The water that exists in the intermediate membrane is not only soluble in organic solvent, and is adsorbed on the inwall of film constitute, so in order effectively to remove the water in the intermediate membrane, the water content in the control organic solvent is necessary.Water content in the organic solvent is generally 0～10 weight %, preferred 0～5 weight %, more preferably 0～3 weight %.When the dehydration of intermediate film is insufficient when carrying out, in the heating of the film that carries out thereafter or drying process sometimes emptying aperture destroyed, disappear or diminish.

Extraction removal method as the hydrophily organic compound in the intermediate membrane, for example, can enumerate with intermediate membrane be immersed in the water-miscible organic solvent, the intermediate membrane surface is with water-miscible organic solvent washing, to intermediate membrane surface spray water-miscible organic solvent, purge methods such as water-miscible organic solvent to the intermediate membrane surface.Wherein, dipping method and washing methods are preferred.The time of contact of intermediate membrane and water-miscible organic solvent, be set in 1 second～24 hours scope usually.Consider the higher limit of time of contact preferred 12 hours, more preferably 6 hours from the viewpoint of productivity ratio.On the other hand, the lower limit of time of contact is because must fully remove hydrophily organic compound and the water of above-mentioned boiling point more than 80 ℃ or 80 ℃, so preferred 10 seconds, more preferably 30 seconds.

(5) operation of dry porous silica film:

The purpose of drying process is to remove volatile ingredient residual in the porous silica film and/or promote alkoxyl silicone alkanes hydrolysis-condensation reaction.Baking temperature is generally 20～500 ℃, preferred 30～400 ℃, more preferably 50～350 ℃, is generally 1 fen drying time～50 hours, preferred 3 minutes～30 hours, more preferably 5 minutes～15 hours.Drying mode can adopt well-known modes such as air-supply drying, drying under reduced pressure to carry out, and these modes is made up also can.Also have, when undue strong drying can be removed volatile ingredient fast owing on the porous silica film, break, thus the drying of blowing etc. slowly drying mode be preferred.After the air-supply drying,, also can append drying under reduced pressure in order fully to remove volatile ingredient.

Also have, this drying process also can replace above-mentioned extraction process.That is, as the operation that the intermediate membrane that forms from the operation of above-mentioned (3) is removed the hydrophily organic compound of boiling point more than 80 ℃ or 80 ℃, do not rely on the extraction process of above-mentioned (4), the available drying process of explanation is here implemented.

Can adopt such drying process to remove the manufacture method of the laminated base plate of above-mentioned hydrophily organic compound, the formation that can special provision has following operation at least: on substrate, be coated with as the starting compound of main body and the aqueous organic solution that contains the hydrophily organic compound of boiling point more than 80 ℃ or 80 ℃ containing the alkoxyl silicone alkanes that causes hydrolysis and dehydration condensation, form the operation of a film; Form the aqueous organic solution generation hydrolysis of an above-mentioned film and dehydration condensation and form the operation of intermediate membrane; Make to promote the catalytic specie of hydrolysis and dehydration condensation to contact above-mentioned intermediate membrane, and form the operation of compacted zone at the surf zone of this intermediate membrane; And, make above-mentioned intermediate membrane drying, remove the hydrophily organic compound of above-mentioned boiling point more than 80 ℃ or 80 ℃, form the operation of porous silica film.

(E) about substrate:

As substrate, can adopt that its refractive index is generally 1.4～1.9, the substrate of preferred 1.45～1.70, more preferably 1.47～1.65, most preferably 1.48～1.60 scopes.When the refractive index of substrate surpasses 1.9, because the refringence of substrate and air is big, so total reflection amount thereon strengthens.Because of the common 100 μ m that surpass of the thickness of substrate, during in particular as the EL display, when the total reflection here is big, the light of total reflection once is back to diffusion layer scattering and the amount of ejaculation is increased once more, so between the pixel of 100 μ m or the following size of 100 μ m squares, the light of ejaculation mixes usually, the phenomenon that resolution such as pixel is oozed out, bleeding reduce takes place, so be unfavorable.

Also have, consider from this reason, by making the light removing layer of light diffusion or scattering, when particularly in the EL display, using, it is preferred being provided with near transparent electrode layer as far as possible, from the distance of transparent electrode layer be pixel on one side size be preferred below 2 times or 2 times, be pixel size or be most preferred below it on one side.

In addition, when the refractive index of substrate surpasses 1.9, the outer illumination of substrate surface is gone into to strengthen, this also is the reason that exploration on display resolution ratio descends, and is unfavorable therefore.When the refractive index of substrate is lower than 1.4, owing to do not have suitable material as self-supporting transparency carrier material, so be not preferred.

This refractive index is according to ASTM D-542, and the mean refractive index of the total depth direction of determining when measuring with ellipsograph is used the value representation to 23 ℃ sodium D-line (589.3nm).As transparency carrier, can enumerate the transparency carrier that constitutes by versatile material with above-mentioned refractive index.For example, can enumerate various solids glass (シ ヨ Star ト ガ ラ ス) such as BK7, SF11, LaSFN9, BaK1, F2, glass such as synthetic alloy-type fused silica, optics crown glass, low-expansion boron silicate glass, sapphire (サ Off ア イ ヤ), soda-lime glass, alkali-free glass; Acrylic resin such as polymethyl methacrylate or cross linked acrylic; Aromatic polycarbonate resins such as bisphenol-a polycarbonate; Styrene resins such as polystyrene; Mylar such as amorphous polyolefins resin, epoxy resin, PETG such as poly-cyclic olefin; Polysulfone resins such as polyether sulfone; Synthetic resin such as polyetherimide resin.Wherein, solids such as BK7, BaK1 glass, synthetic alloy-type fused silica, optics crown glass, low-expansion boron silicate glass, soda-lime glass, alkali-free glass, acrylic resin, aromatic polycarbonate resin, amorphous polyolefins resin are preferred, BK7 solids glass, synthetic alloy-type fused silica, optics crown glass, low-expansion boron silicate glass, soda-lime glass, alkali-free glass, acrylic resin, aromatic polycarbonate resin, polyethersulfone resin are preferred.

The thickness of substrate is generally 0.1～10mm.Consider the preferred 0.2mm of lower thickness limit value of substrate, more preferably 0.3mm from the viewpoint of mechanical strength and gas barrier.From the viewpoint of light weight, small-sized property and light transmittance, the preferred 5mm of upper thickness limit value of substrate, more preferably 3mm.

The transmitance of laminated base plate, to sodium D-line wavelength (589.3nm) preferred 80% or 80% above, more preferably more than 85% or 85%, more than especially preferred 90% or 90%.

(F) protective cover:

Material as protective cover; so long as material transparent and can planarization can and not be particularly limited; the various glass that use except that aforesaid substrate, the resin material; the transparent coating material that does not have self-supporting be can enumerate, UV or thermoset acrylics resinoid, solgel reaction material (silicate material) etc. for example can be enumerated.The thickness of protective cover is generally 10～1000 μ m, preferred 100～200 μ m.

(G) other layers:

Electroluminescent cell also can be between electroluminescence layer and transparent electrode layer further known hole injection layer or the hole transporting layer of lamination.In addition, electron injecting layer or the electron supplying layer that also lamination is known again between electroluminescence layer and negative electrode.In the taking-up light side of substrate, can also form film or films such as preventing reflective film, light polarizing film, phasic difference film as required.

Below, electroluminescent cell of the present invention is described with reference to the accompanying drawings.Fig. 1 (a) is the layer structure key diagram of the electroluminescent cell of the 1st invention, and Fig. 1 (b) is the total reflection key diagram of the big light of the angle of emergence.Fig. 2,3 is another layer structure key diagrams of the electroluminescent cell of the 1st invention.Fig. 4 is the layer structure key diagram of the electroluminescent cell of the 2nd invention.Fig. 5,6 is another layer structure key diagrams of the electroluminescent cell of the 2nd invention.Fig. 7 is the layer structure key diagram of the electroluminescent cell of the 3rd invention.Fig. 8,9 is another layer structure key diagrams of the electroluminescent cell of the 3rd invention.Figure 10 is the layer structure key diagram of the electroluminescent cell of the 4th invention.Figure 11,12 is another layer structure key diagrams of the electroluminescent cell of the 4th invention.

[the 1st invention]

The layer structure that electroluminescent cell shown in Fig. 1 (a) (scheme (1)) has is negative electrode 1, electroluminescence layer 2, transparent electrode layer 3, infiltration light diffusion layer A 4a and transparency carrier 5 stacked arrangement in this order.

Infiltration light diffusion layer A 4a is the layer that comprises matrix that is made of low-index material and the particle that makes light scattering.As matrix, can use the material of above-mentioned low-index layer.As the light scattering particle that contains among the infiltration light diffusion layer A4a, can enumerate silicon dioxide (refractive index 1.46), cataloid (refractive index 1.3～1.4, because of manufacture method or structure variant), titanium dioxide (refractive index 2.4～2.7, the occasion of noncrystalline or crystalline is variant because of crystal habit), zirconium dioxide (refractive index 2.0), ITO (tin indium oxide) (refractive index 1.8～1.9, because of composition and crystal habit variant), ATO (antimony tin) (refractive index 1.9), aluminium oxide (refractive index 1.8) etc.Particularly the least possible, promptly transparent in the light absorption of visible region, and with the big as far as possible particle of the refringence of above-mentioned matrix be preferred.

In the present invention, the scattering of matrix and dispersion is important with the refringence of particle, and its size of any refractive index is not a problem.As the example of the particle littler than matrix refractive index, can enumerate fine bubble, in addition,, adopt the particle bigger usually than matrix refractive index though can be used in this purposes.Refractive index poor, usually more than 0.1 or 0.1, more than preferred 0.3 or 0.3, more preferably more than 0.5 or 0.5, more than especially preferred 0.9 or 0.9.The upper limit of refringence does not have in principle, but obtains easily considering from material, is generally about 1.5.

Also have, be contained in the above-mentioned matrix, can form with in the operation (1) of material liquid, add in the material liquid at the porous silica film in preparing above-mentioned low-index layer for making this light diffusing particles.

Scattering gets final product and is not particularly limited as long as have the function of scattering and permeating light (also claiming a エ バ ネ Star セ Application ト ripple or an adjacent light sometimes) with the size and the shape of particle.That is, scattering has with particle and can prevent to permeate light and be back to the transparency electrode side, and it is important entering the function of getting light side (printing opacity side).The infiltration light quantity (seepage distance) of infiltration light, (interface of transparency electrode and infiltration light diffusion layer A) is generally about 100～600nm to permeating light diffusion layer A side from the interface, so scattering is present in this scope with particle, and the particle diameter that presents the diffused light function is important.The size or the shape that particularly cause self-scattering are suitable.

For example, light scattering is with the particle diameter of particle, as optical dimensions, when the scattering light wavelength (be generally visible light, reach 400～700nm) during for λ, bigger than 1/20 λ usually, preferably big than 1/10 λ.Also have, when particle diameter was excessive, the flatness of diffusion barrier easily went wrong, and was not preferred.When the flatness generation problem of diffusion barrier, the electric field in the EL luminescent layer becomes inhomogeneous, and the brightness of generating device descends degradation problem under the life-span easily.

In addition, when particle diameter was too small, dispersion effect was little, and the refractive index of low-index layer matrix rises, and is unfavorable.Because above-mentioned reason,, (be sometimes referred to as " 60% weight ratio particle diameter ") more than 60% or 60% and be generally 20～400nm, preferred 40～200nm, the more preferably scope of 60～120nm by the weight ratio of particle as the physics particle diameter.

60% weight ratio particle diameter is measured by laxative remedy.

(1) observes with the section of FIB-SEM enforcement diffusion layer

FIB (focused ion beam) brings the abbreviation of ion beam processing finder together, the FB-2000A that device adopts the Hitachi to make.As the section processing conditions, system film Pt (platinum) sputtered film before FIB processing.

Leave to observe at the FIB of the local system film W (tungsten) of this place film with FIB before being used in section and making and use hole (squarish of 20 μ * 30 μ), the reduction ion beam current is processed the face that is used to observe.Ion species is Ga ⁺, the ion beam accelerating voltage is 30KV.

SEM observes, and the S4100 that makes with the Hitachi implements.Observation condition is accelerating voltage 5.0KV, makes sample film vertical direction about 80 degree (being equivalent to almost the section from the top view film) that tilt, and the sightingpiston with the hole of FIB making is produced into image.Multiplication factor is * 10000.

Above-mentioned section is observed image, implement to observe by following main points.

From sample film, take the wide image of 20 μ of 20 places arbitrarily in diffusion face direction, the observed particle in this image is observed particle diameter.When particle section configuration when being oval, the particle diameter when almost being circular cross section particle of the same area to regard as is as the particle diameter of this particle.

To observed each particle here, particle diameter cube proportional with the weight of particle carries out weight and converts, and the particle diameter by afore mentioned rules converts, and points out with respect to 60 weight % of all particles or studies carefully to compete to be in which scope more than the 60 weight %.

When particle coacervation becomes block, it is handled as a particle.

Diffusion barrier is crisp or be difficult to determine reason such as shape of particle with SEM or TEM and can not adopt above-mentioned way the time, can adopt following way to measure particle diameter.

This evaluation method also is suitable for when particle has trickle space.

(2) in the stage of modulation masking liquid before diffusion barrier forms, the suspension-turbid liquid of particle is decided particle size distribution by the particle size distribution instrumentation.

The particle size distribution meter uses the MICROTEC particle size distribution meter model 9230UPA of Nikkiso Company Limited, as long as getting final product of can suspending of the solvent of suspended particles is not particularly limited, but when TiO 2 particles being disperseed in silicate solutions and use collosol and gel legal system film, alcohols solvent is preferred.

Particle size distribution from measuring can obtain particle diameter and compare data with the accumulation of frequency.Particle diameter can be regarded as almost spherical particle diameter from these data, study carefully to compete to be in what scope with above-mentioned 60 the weight % particle diameter of similarly pointing out.

The thickness of infiltration light diffusion layer, the thickness more than 2 times or 2 times of average grain diameter that reaches the particle of scattered light is preferred.Like this, by setting the thickness of particle diameter and scattering layer, particle can effectively be brought into play dispersion effect.

The average grain diameter of particle can be passed through said method (FIB-SEM when inapplicable, measures the particle size distribution of the preceding particle dispersion of coating), measures particle size distribution, adopts the value that reaches 50vol%.

Light scattering is generally 1～40 volume %, preferred 5～20 volume % with the content of particle.When the content of particle is very few, can not get sufficient dispersion effect.Served as for a long time, hidden effect uprises, and the ratio of taking out light reduces.

The thickness of infiltration light diffusion layer A is generally the thickness more than 2 times or 2 times of average grain diameter of the particle of scattered light.Like this, by setting the thickness of particle diameter and scattering layer, particle can effectively be brought into play dispersion effect.Particularly, be generally 100～1000nm, preferred 300～700nm.The thickness of infiltration light diffusion layer A, yes, and to be present in the coverage area of permeating light with scattering particles be prerequisite.That is, though also depend on thickness, the used wavelength of the infiltration light diffusion layer A that contains scattering particles, scattering particles be present in usually from the interface 1 μ m (1000nm) of transparency electrode with interior, preferably be present in 600nm with interior be important.Particularly, more than 1/3 of the particle of scattered light or 1/3 (weight ratio) be present in from the interface 600nm of transparency electrode with interior be preferred.

When infiltration light diffusion layer A crosses when thin, scattering bed thickness (oozing out the particle amount portion in) oozes out apart from diminishing with respect to following, and dispersion effect is insufficient.When blocked up, though scattering is no problem, from planarization or prevent that crackle from considering is disadvantageous.Also have, the transparency electrode side interface of expectation infiltration light diffusion layer A is smooth.Its reason is that by the ELD that vacuum method (meaning vacuum vapour deposition etc.) forms, the concavo-convex of substrate almost can directly reflect.

That is, for even and stable light takes place, the electric field in the electroluminescence layer must keep homogeneous.When transparency electrode has when concavo-convex, it is inhomogeneous that electric field becomes, and causes the deterioration of EL pigment, and problems such as defective such as blackspot take place easily to cause.

Secondly, the total reflection at the interface of transparent electrode layer in the electroluminescent cell and infiltration light diffusion layer A describes with Fig. 1 (a) and Fig. 1 (b).

The light that electroluminescence layer 2 sends directly or by negative electrode 1 reflects, and by electroluminescence layer 2, penetrates to transparent electrode layer 3 sides.Then, enter the light of infiltration light diffusion layer A4a, by infiltration light diffusion layer A4a, the approximately perpendicular incidence angle of the real estate of transparency carrier 5 being incident to the interface of transparency carrier 5 and infiltration light diffusion layer A4a, so in the total reflection minimizing at the air layer side interface of transparency carrier 5.In addition, by the light scattering particle that contains among the infiltration light diffusion layer A4a, reduce from the total reflection of transparent electrode layer 3 with the light of the contacting permeation of infiltration light diffusion layer A4a, therefore, light takes out efficient and improves.

That is, from electroluminescence layer 2, by transparent electrode layer 3, be incident in the light at transparent electrode layer 3 and the interface of infiltration light diffusion layer A4a, the light that incidence angle is littler than critical angle directly enters infiltration light diffusion layer A4a from transparent electrode layer 3.On the other hand, the light 11a that incidence angle is bigger than critical angle is from this contacting permeation and total reflection is back to transparent electrode layer side 3 as total reflection light 12a.When carrying out this total reflection, light also oozes out into infiltration light diffusion layer A4a side from this interface, and the electric field of incident light and magnetic field are also by this contacting permeation and be present in light diffusion layer A4a side.The maximum distance that arrives of the essence of this infiltration light 13 when the refractive index of transparency electrode bed thickness 100nm, infiltration light diffusion layer A4a is 1.3, reaches 500～600nm in the vertical direction of transparency electrode.

Ooze out into the light 13 of infiltration light diffusion layer A4a, carry out scattering with particle by the light scattering that this near interface that permeates light diffusion layer A4a exists.The result is, the light 13 that oozes out can not be back to the earliest in the transparent electrode layer 3 as total reflection light, enters the infiltration light diffusion layer A4a side that contains scattering particles.Enter the light of the infiltration light diffusion layer A4a side that contains scattering particles, after being scattered, spreading by scattering particles, directly or after for example aluminium mirror coating reflection by negative electrode, diffuse among the infiltration light diffusion layer A4a that contains scattering particles.The result is, by the light diffusing particles that contains among the infiltration light diffusion layer A4a, reduces at the reflectivity of the total reflection light at interface, and more light enters infiltration light diffusion layer A4a side from transparent electrode layer 3, and the light of electroluminescent cell takes out efficient and improves.

Electroluminescent cell shown in Figure 2 (scheme (2)) has: negative electrode 1, electroluminescence layer 2, transparent electrode layer 3, infiltration light diffusion layer A4b, low-index layer 4 and transparency carrier 5 be the layer structure of stacked arrangement in this order.

The matrix composition refractive index of infiltration light diffusion layer A4b is identical in fact with the refractive index of low-index layer 4.

Also have, in this specification so-called " refractive index of Xiang Denging in fact ", mean poor with as the refractive index of the interlayer of object, the difference of refractive index of for example permeating the matrix composition refractive index of light diffusion layer A4b and low-index layer 4 is usually below 0.3 or 0.3, below preferred 0.2 or 0.2, more preferably below 0.1 or 0.1.

The matrix composition of low-index layer 4 and low-index layer 4b can use the same composition of matrix composition (composition beyond the particle) with the infiltration light diffusion layer A4a of Fig. 1 (a).Particularly, the matrix composition of infiltration light diffusion layer A4b is preferably with low-index layer 4 same compositions, but differently also can.

The thickness of low-index layer 4 from the planarization of oozing out distance and film when the total reflection at interface or prevent that the viewpoint of crackle from considering, is generally 100～1000nm, preferred 300～700nm.The thickness of infiltration light diffusion layer A4b is generally 100～1000nm, preferred 300～700nm.

The light scattering that contains among the infiltration light diffusion layer A4b is with particle and containing ratio thereof, and is identical with the particle and the containing ratio that contain among the above-mentioned infiltration light diffusion layer A4a.

The electroluminescent cell of scheme (2), same with the electroluminescent cell of scheme (1), the total reflection at the interface of transparent electrode layer 3 and low-index layer 4b reduces.That is, from electroluminescence layer 2 light by transparent electrode layer 3, at the interface of transparent electrode layer 3 and infiltration light diffusion layer A4b with than the big incidence angle incident of reflection critical angle the time, this light from this interface to infiltration light diffusion layer A4b side infiltration and total reflection.When this total reflection, same fully with the occasion of Fig. 1 (b), light oozes out from this interface to infiltration light diffusion layer A4b side, and the electric field of incident light and magnetic field are present in from the interface to infiltration light diffusion layer A4b side.

This near interface in infiltration light diffusion layer A4b makes the particle of this light scattering of oozing out owing to exist, so ooze out into light scattering by this particle of infiltration light diffusion layer A4b side.The result is, is not back to the total reflection light of transparent electrode layer 3 sides the earliest, directly or indirectly diffuses among the infiltration light diffusion layer A4b.Like this, contain in infiltration light diffusion layer A4b with particle by making light scattering, the reflectivity of total reflection descends, and more light enters infiltration light diffusion layer A4b side from transparent electrode layer 3.

Because of this matrix that permeates light diffusion layer A4b equates in fact with the refractive index of low-index layer 4, so, total reflection does not take place at the interface of infiltration light diffusion layer A4b and low-index layer 4.The result is, enters infiltration light diffusion layer A4b from transparent electrode layer, arrives the light at the interface of this infiltration light diffusion layer A4b and low-index layer 4, almost directly enters low-index layer 4.Like this, the light from electroluminescent cell takes out the efficient raising.

Electroluminescent cell shown in Figure 3, negative electrode 1 form on substrate 5, set gradually thereon: electroluminescence layer 2, transparent electrode layer 3, infiltration light diffusion layer A4a are provided as the protective cover 6 of light penetrating object on this infiltration light diffusion layer A4a.Also have, in this scheme, substrate 5 is unnecessary transparent, and protective cover plays the optical function of the transparency carrier in scheme (1).Scheme (1) is called the organic EL of bottom emissive type, and the scheme of Fig. 3 is called the organic EL of top emission structure.

In addition, in the electroluminescent cell of Fig. 3 (top emission structure), even do not contain low-index layer 4 air layers (space) of particle, also no problem on device constitutes.At this moment, its refractive index is 1.0, because its thickness can solve the planarization or the crack problem of film, so be not particularly limited.

The scheme of Fig. 3 be substrate 5 to be configured in negative electrode 1 side in the scheme of Fig. 1, and in the scheme of Fig. 2, similarly, substrate 5 also can be configured in negative electrode 1 side.

In the present invention,,, the extraction efficiency of specific look is improved so can utilize the wavelength dependency of scattered power energetically owing to the guided wave that utilizes in the scattering of light phenomenon taking-up transparent electrode layer, or the life-span of improving the luminescent pigment of this look.

For example, by discussion to particle diameter or particle refractive index, by utilizing Rayleigh scattering, or and with self-scattering and Rayleigh scattering, after guaranteeing sufficient scattered power, can take out blueness more expeditiously.

In addition, about the composition of particle, for example, if near the zooming material of the refractive index blueness of visible region such as selected titanium dioxide then with respect to its allochromatic colour, can take out blueness more efficiently.

Also have, otherwise, for example having the bubble that is equivalent to particle size when disperseing when making, the refractive index of air is hardly because of wavelength changes, so, when suppressing light and take out the wavelength dependency of efficient, more effective sometimes.

In white or panchromatic electroluminescent cell, the pigment brightness of general short wavelength side is low, or the brightness of sending same brightness light time life-span that reduces by half is short.Therefore, for example,, then do not need to design the only area increase of blue picture element if can improve blue extraction efficiency, relevant with the brightness raising of unit are, in addition, owing to can reduce the electric current that flows through blue picture element, so can improve the life-span.Even when using white light source,, the offset width of the white from timing can be suppressed to Min. by improving blue extraction efficiency, life-span.

Also have, in the top emission structure shown in the scheme of Fig. 3, must after forming electroluminescence layer, form transparency electrode and light removing layer.At this moment, since electroluminescence layer at the high temperature more than 100 ℃ or 100 ℃ by crystallization or the aging possibility that makes the luminosity reduction that exists, therefore, to the formation of light removing layer, treatment temperature usually below 150 ℃ or 150 ℃, preferred below 120 ℃ or 120 ℃, more preferably below 100 ℃ or 100 ℃.Handle the atmosphere atmospheric pressure and be generally normal pressure.

In said method, when forming low-index layer, for example, be preferred as being molded into the film formation technology of carrying out porous under the lower temperature with above-mentioned higher boiling point hydrophily organic compound with the porous silica material.

In addition,, can be in advance on other transparent base such as plastic film, form low-index layer, infiltration light diffusion layer A as required successively, this blooming is sticked on the transparency electrode, form light and take out film as other method.When pasting, infiltration light diffusion layer A becomes adhesive layer or double as adhesive layer.At this moment, the technology that heating or conducts such as organic solvent must measures when making, is finished film, so, do not cause damage to electroluminescence layer, can form the light removing layer, be preferred mode.

As the transparent base of plastic film, can preferably use so long as have the transparent flexible base material.For example, can preferably use PET (PETG) film, PEN (PEN) film, PES (polyether sulfone) film, PC (Merlon) film, APO (amorphous polyolefin, cyclic polyolefin) film etc., but be not only to be defined in this.

This transparent base also can be used as the substitute of Fig. 3 protective cover.In addition, on this transparent base film, can as required functional layers such as gas barrier layer, anti-reflection layer, circular polarization lamella be set at the light emitting side mainly.

On this film, form earlier low-index layer as required, when transparent base is plastic film, when forming the porous silica film thereon, because of not handling being higher than under 200 ℃ the high temperature, so can preferably adopt above-mentioned manufacture method.

[the 2nd invention]

Electroluminescent cell shown in Figure 4 (scheme (3)) is to be provided with separator 10 between the transparent electrode layer 3 of the electroluminescent cell of scheme (1) and infiltration light diffusion layer A4a, particularly, have: negative electrode 1, electroluminescence layer 2, transparent electrode layer 3, separator 10, infiltration light diffusion layer A4a and transparency carrier 5 be the layer structure of stacked arrangement in this order.

And, as the electroluminescent cell of scheme (3), can enumerate the A scheme of using with the equal or above high index of refraction separator of transparent electrode layer, and the B scheme of use low-refraction separator below equal with transparent electrode layer.

In the A scheme, because separator 10 has the high index of refraction equal or above with transparent electrode layer 3, so be incident to the not total reflection of light of separator 10 from transparent electrode layer 3.As the constituent material of separator 10, can enumerate ZrO ₂, TiO ₂, Al ₂O ₃, CeO ₂, TiN, Ta ₂O ₃, Ta ₂O ₅, SiO _xN _y, SiN, SiO _x, SnO ₂, Sb ₂O ₅, Y ₂O ₃, La ₂O ₃, In ₂O ₃Deng or their mixture.As long as visible light is not absorbed or absorbs few, and have all can the using of membrane structure of densification, be preferred as principal component particularly with inorganic compound.In this scheme, separator 10 is owing to have the refractive index equal or above with transparent electrode layer 3, so the part of guided wave moves from transparency electrode course separator, at this moment, at visible wavelength, the absorption of light person less is preferred than the material of transparent electrode layer.It is maximum that its uptake reaches in the visible region, and every 100nm is thick to be preferred below 5% or 5%, is being especially preferred below 3% or 3%, is being most preferred below 1% or 1%.When considering to use guided wave apart from displacement thickness, the guided wave distance of every 100nm, reach several % even absorb, when guided wave distance reaches more than several microns in the face of transparent electrode layer or separator (1 pixel size reaches more than tens of microns the square in the common EL device), consider that from improving light extraction efficiency its uptake reaches very important big amount.Therefore, have, except that isolation effect, can also expect the effect that light extraction efficiency improves with the equal or above refractive index of transparent electrode layer 3 and at the few separator of visible wavelength extinction.

The thickness of separator 10 is not particularly limited, and in order to give full play to isolation characteristic, is generally 20nm or more than the 20nm, preferred 50nm or more than the 50nm, more preferably 100nm or more than the 100nm.In addition, in order to suppress the absorption of light, its upper limit is generally 1000nm, preferred 400nm.

In the B scheme, separator 10 has and transparent electrode layer 3 equal following low-refractions.As the constituent material of low-refraction and separator as thin as a wafer 10, can enumerate MgF ₂, fluoride materials, SiO such as NaF ₂Or various porous materials or their mixture such as sodium rice porous silica.The thickness of separator is generally 500nm or below the 500nm, preferred 300nm or below the 300nm, more preferably 200nm or below the 200nm, as thin as a wafer.Also have, consider that from preventing diffusion the lower limit of the thickness of separator is generally 20nm, preferred 50nm, more preferably 100nm.In the B scheme, at the interface of the separator 10 and the transparent electrode layer 3 of low-refraction, from the light total reflection sometimes of transparent electrode layer 3 sides.Yet in order to reduce bed thickness, the seepage areas at the interface during from total reflection not only reaches separator 10, and reaches infiltration light diffusion layer A4a.The light that oozes out owing to the particle among the infiltration light diffusion layer A4a is scattered, takes out from infiltration light diffusion layer A4a.When the thickness of layer was bigger than above-mentioned higher limit, this oozes out light can not arrive infiltration light diffusion layer A, so extraction efficiency can not improve.

About this separator, refractive index and transparent electrode layer equal or more than, at the absorptance transparent electrode layer of visible region after a little while, a part of guided wave of transparent electrode layer is shifted to this layer, and the decay during guided wave descends, so can expect the effect that extraction efficiency improves more.To this situation,, needn't consider to ooze out the arrival distance of light especially about the upper limit of thickness.But, about the vacuum technology film, when thick above 1000 μ, membranous becoming fragile, film itself becomes and peels off easily, is unfavorable.From then on viewpoint is considered, preferred 500nm or below the 500nm.

In addition, even in the wet type coated film, when thick,, be unfavorable because of being difficult to guarantee the flatness of EL element necessity above 10 μ.From then on viewpoint is considered, thick or 5 μ of preferred 5 μ thick following, more preferably thick or 3 μ of 3 μ thick following, most preferably thick or 1 μ of 1 μ thick below.

Separator for example, can form by vapour deposition method.

Separator, prevent low molecular weight compositions such as residual monomer in the low-index layer or moisture etc. easily diffusible substance spread to the transparent electrode layer side.For example, infiltration light diffusion layer A4a, preferably the hydrolysis by the alkoxyl silicone alkanes forms, in the infiltration light diffusion layer A4a of formation, alkoxy silane monomer or oligomer, or low molecular weight substances such as solvent, water, catalyst are residual sometimes.In addition, in the assembling procedure of EL element, low molecular weight substance or mobility material infiltrate from the outside and residual sometimes.This low molecular weight substance has diffusivity, has by transparent electrode layer 3 danger that electroluminescence layer is exerted an influence.Separator 10 can prevent the diffusion of such material, protection transparent electrode layer or electroluminescence layer.

The electroluminescent cell of scheme (3), same with such scheme (1), descend in the total reflection of separator 10 with the light at the interface of infiltration light diffusion layer A4a.From electroluminescence layer 2, by transparent electrode layer 3 and separator 10, at the interface of separator 10 and infiltration light diffusion layer A4a, when light with than the big incidence angle incident of critical angle the time, this light at this interface by total reflection.When carrying out this total reflection, identical with the 1st invention, the phenomenon of oozing out to infiltration light diffusion layer A4a side from this interface as light takes place.That is, the electric field of incident light and magnetic field are present in from the interface to permeating light diffusion layer A4a side.

This near interface in infiltration light diffusion layer A4a, because existing makes this ooze out the particle of light scattering, so permeating the light that light diffusion layer A4a side is oozed out, under this particle effect, be scattered, be not back to the total reflection light of separator 10 sides the earliest, directly or indirectly diffuse among the infiltration light diffusion layer A4a.Like this, contain in infiltration light diffusion layer A4a with particle by making light scattering, the reflectivity of total reflection reduces, and more light enters infiltration light diffusion layer A4a side from separator 10, and the result is that the light taking-up efficient of electroluminescent cell improves.

Electroluminescent cell shown in Figure 5 (scheme (4)) is the element that has disposed separator 10 between the transparent electrode layer 3 of the electroluminescent cell of scheme (2) and infiltration light diffusion layer A4b, particularly, have: negative electrode 1, electroluminescence layer 2, transparent electrode layer 3, separator 10, infiltration light diffusion layer A4b, low-index layer 4 and transparency carrier 5 are with the layer structure of this order stacked arrangement.

Separator 10 can adopt any of the A scheme of scheme (3) and B scheme.

In the electroluminescent cell of scheme (4), when separator 10 has A scheme with the equal or above high index of refraction of transparent electrode layer 3, same with the A scheme of scheme (3), reduce in the total reflection of separator 10 with the light at the interface of infiltration light diffusion layer A4b.

Matrix and the low-index layer 4 of infiltration light diffusion layer A4b are because refractive index is equal in fact, so at the interface of infiltration light diffusion layer A4b and low-index layer 4 total reflection does not take place.The result is, enters the light of infiltration light diffusion layer A4b from the transparent electrode layer side, arrive the interface of infiltration light diffusion layer A4b and low-index layer 4 after, almost former state enters low-index layer 4.Like this, the light from electroluminescent cell takes out the efficient raising.

In scheme (4), also can be same with scheme (3) B schemes, separator 10 is low-refractions and has as thin as a wafer film.In this case, same with above-mentioned A scheme, light takes out efficient and improves.

Fig. 6 illustrates the electroluminescent cell of the top emission structure of scheme (3); negative electrode 1 forms on substrate 5; form electroluminescence layer 2, transparent electrode layer 3, separator 10, infiltration light diffusion layer A4a thereon successively, on this infiltration light diffusion layer A4a, form protective cover 6.Optically, this protective cover plays the effect of the substrate in the scheme (3).

Also have, as shown in Figure 6, only limit to substrate 5 is configured in the element of the top emission structure structure of negative electrode 1 side, air layer (space) is set, also no problem on the formation of device even replace not containing the low-index layer 4 of particle.In this occasion, the refractive index of air layer is 1.0.In addition, about thickness, owing to also can solve the planarization or the crack problem of film, so be not subjected to the special restriction of the upper limit.

Fig. 6 is the top emission structure element at the substrate 5 of negative electrode 1 side allocation plan (3), but also can be the top emission structure at the same substrate 5 of configuration of negative electrode 1 side and scheme (4).

Also have, the thickness of the transparency electrode of the 2nd invention, as long as satisfy above-mentioned light transmittance and face resistance value, preferred 10～500nm considers from the conductivity viewpoint, its lower limit is 50nm, especially preferred 100nm more preferably.On the other hand, from light transmittance or prevent that film from peeling off, preventing that the viewpoint of the be full of cracks of film from considering that its higher limit is 300nm, especially preferred 200nm more preferably.

[the 3rd invention]

Electroluminescent cell shown in Figure 7 (scheme (5)) has: negative electrode 1, electroluminescence layer 2, contain light scattering with transparent electrode layer 3a, low-index layer 4 and the transparency carrier 5 of the particle layer structure of stacked arrangement in this order.

The above-mentioned transparent electrode layer 3a that contains light scattering with particle is the layer that light scattering disperses in the matrix of transparency electrode with particle.As matrix, can use the material of above-mentioned transparent electrode layer.

Contain the transparent electrode layer 3a of light scattering, can contain the rubbing method formation of light scattering by coating with the material liquid of particle with particle.Contain the coating fluid of light scattering as being used to form with the transparent electrode layer 3a of particle, for example, can use the particulate of conductive materials such as ITO or semi-conducting material is distributed to composition in organic solvent etc. with electric conductive polymer or other resin binders, or use electric conductive polymer itself etc., but be not limited thereto.For this light scattering is contained in the above-mentioned matrix with particle, as long as in above-mentioned coating fluid, add.Adopt this coating fluid,, form pattern as necessity of electroluminescent cell electrode by print processes such as photoetching process or ink-jet methods etc.Also have, the live width behind the composition is standard about common 1～10 μ m, but is not limited thereto.Contain the thickness of light scattering,, and be not particularly limited so long as the thickness of above-mentioned transparent electrode layer gets final product with the transparent electrode layer of particle, but reach the scattered light particle average grain diameter be preferred more than 2 times or 2 times.

As containing the particle that contains among the transparent electrode layer 3a of light scattering with particle, can use with above-mentioned infiltration light diffusion layer A4a in the light scattering that contains with the same particle of particle.

Light scattering is generally 0.1～40 volume %, preferred 1～10 volume % with the content of particle.When the content of particle is very few, can not get sufficient dispersion effect.Served as for a long time, hidden effect increases, and light taking-up ratio reduces.

In the electroluminescent cell of scheme (5), contain the transparent electrode layer 3a of light scattering with particle, as follows, make from containing light scattering and enter the light quantity increase of low-index layer 4, thereby the taking-up efficient of light is improved with the transparent electrode layer 3a of particle.That is, be incident to and contain in the light of light scattering with the interface of the transparent electrode layer 3a of particle and low-index layer 4, the light that incidence angle is littler than critical angle directly enters the low-index layer 4 with the transparent electrode layer 3a of particle from containing light scattering.The light that incidence angle is bigger than critical angle, with the interface of low-index layer 4 on by total reflection, be back to and contain light scattering with among the transparent electrode layer 3a of particle.Like this, be back to a part of light of the transparent electrode layer 3a side that contains light scattering usefulness particle, be scattered with the particle among the transparent electrode layer 3a of particle by containing light scattering.The part of this scattered light is incident to the interface with low-index layer 4 once again.Wherein, the light that incidence angle is littler than critical angle is not by total reflection and enter low-index layer 4 from containing light scattering with the transparent electrode layer 3a of particle.Be incident in this scattered light at this interface, the light that incidence angle is bigger than critical angle is back to the transparent electrode layer 3a side that contains light scattering usefulness particle once again, and its part is again by particle scattering.By to its repeatable operation successively, remaining light also enters low-index layer 4 successively.

At low-index layer 4 with contain the light that light scattering arrives electroluminescence layer 2 with the interface of the transparent electrode layer 3a of particle in by the light of total reflection and contains the transparent electrode layer 3a interface of light scattering usefulness particle, when to the incidence angle at this interface when bigger than critical angle, in this interface total reflection, point to low-index layer 4 once again and contain the interface of light scattering with the transparent electrode layer 3a of particle.Thereafter, the behavior of this light and above-mentioned same enters low-index layer 4 successively.

On the other hand, at the transparent electrode layer 3a that contains light scattering usefulness particle and the interface of electroluminescence layer 2, from containing the light scattering light of the transparent electrode layer 3a side of particle with the incidence angle incident littler than critical angle, directly enter electroluminescence layer 2, be reflected at the interface of electroluminescence layer 2 with negative electrode 1, see through electroluminescence layer 2 once more and contain the transparent electrode layer 3a of light scattering, be back to and contain light scattering with the transparent electrode layer 3a of particle and the interface of low-index layer 4 with particle.Thereafter, the behavior of this light and above-mentioned same.

Like this, the total reflection of transparent electrode layer side reduces than low-index layer 4, and light takes out efficient and improves.

Electroluminescent cell shown in Figure 8 (scheme (6)) has: negative electrode 1, electroluminescence layer 2, transparent electrode layer 3, infiltration light diffusion layer B3b, low-index layer 4 and transparency carrier 5 be the layer structure of stacked arrangement in this order.

The refractive index of the matrix composition of infiltration light diffusion layer B3b equates in fact with the refractive index of transparent electrode layer 3.For example, in scheme (6), the difference of the refractive index of the matrix composition of infiltration light diffusion layer B3b and the refractive index of transparent electrode layer 3 is usually below 0.3 or 0.3, below preferred 0.2 or 0.2, more preferably below 0.1 or 0.1.

The basis material of the infiltration light diffusion layer B3b of scheme (6) can adopt the material same with transparent electrode layer 3.In addition, the matrix composition of this infiltration light diffusion layer B3b, the composition same with transparent electrode layer 3 is preferred, but difference also can.

Infiltration light diffusion layer B3b in the invention of scheme (6), can with the transparent electrode layer 3 same film forming of scheme (5).The transparent electrode layer 3 that does not contain particle can adopt the coating fluid that does not contain particle and forms.In addition, adopting film build methods such as evaporation or sputter to form also can.

The thickness of the transparent electrode layer 3 of scheme (6) generally is more than 2 times or 2 times of average grain diameter of the particle of scattered light, is generally 100～5000nm, preferred 200～1000nm.The thickness of infiltration light diffusion layer B3b is generally 100～5000nm, preferred 200～1000nm.

As contained particle among the infiltration light diffusion layer B3b, can adopt with above-mentioned infiltration light diffusion layer A in contained light scattering with the same particle of particle.

Light scattering is generally 0.1～40 volume %, preferred 1～10 volume % with the content of particle.When the content of particle is very few, can not get sufficient dispersion effect.And too much the time, hidden effect increases, and the taking-up ratio of light reduces.

In the electroluminescent cell of scheme (6), be arranged on the infiltration light diffusion layer B3b between transparent electrode layer 3 and the low-index layer 4, as described below, make the light quantity increase that enters low-index layer 4 from transparent electrode layer 3, light takes out efficient and improves.That is, total reflection owing to equate with the refractive index of transparent electrode layer 3, does not take place at the interface of transparent electrode layer 3 and infiltration light diffusion layer B3b in the matrix refractive index of this infiltration light diffusion layer B3b.

Enter in the infiltration light diffusion layer B3b from transparent electrode layer 3, through being incident among this infiltration light diffusion layer B3b in the light of infiltration light diffusion layer B3b and low-index layer 4, the light that incidence angle is littler than critical angle directly enters the low-index layer 4 from infiltration light diffusion layer B3b.The light that incidence angle is bigger than critical angle, with the interface of this low-index layer 4 by total reflection, be back to infiltration light diffusion layer B3b side.Like this, be back to a part of light of infiltration light diffusion layer B3b side, be scattered under the particle effect in this infiltration light diffusion layer B3b.The part of this scattered light is incident to the interface with low-index layer 4 once again.Wherein, the light that incidence angle is littler than critical angle enters low-index layer 4 not by total reflection from infiltration light diffusion layer B3b.Be incident in this scattered light at this interface, the light that incidence angle is bigger than critical angle is back to infiltration light diffusion layer B3b side once again, and its part is again by particle scattering.By to its repeatable operation successively, remaining light also enters low-index layer 4 successively.

Interface at low-index layer 4 and infiltration light diffusion layer B3b, arrive the light at infiltration light diffusion layer B3b and transparent electrode layer 3a interface in the light of total reflection, at this interface, directly do not enter transparent electrode layer 3 owing to there is refringence, be back to the interface of transparent electrode layer 3 and electroluminescence layer 2.The incidence angle at this interface when bigger than critical angle, in this interface total reflection, is pointed to the interface of low-index layer 4 and infiltration light diffusion layer B3b once again.Thereafter, the behavior of this light and above-mentioned same enters low-index layer successively.

On the other hand, interface at transparent electrode layer 3 and electroluminescence layer 2, from the light of transparent electrode layer 3 sides with the incidence angle incident littler than critical angle, directly enter electroluminescence layer 2, be reflected at the interface of electroluminescence layer 2 with negative electrode 1, see through electroluminescence layer 2 and transparent electrode layer 3 once more, be back to transparent electrode layer 3 and the interface of permeating light diffusion layer B3b.Thereafter, the behavior of this light and above-mentioned same.

Like this, the electroluminescent cell of employing scheme (6) reduces than low-index layer 4 in the total reflection of transparent electrode layer 3 sides, and light takes out efficient and improves.

Also have, infiltration light diffusion layer B3b is set in scheme (6), also available formation and the equal in fact refractive index materials of the transparent electrode layer 3 that does not contain particle contain layer as the particle of matrix and replace.As such basis material, can enumerate aromatic resins such as polyether sulfone, or the particulate of high-index material such as dispersed titanium dioxide, zirconium dioxide makes it the material of transparence therein, as light diffusing particles, can enumerate and make titanium dioxide, zirconium dioxide, silicon dioxide, air etc. with light diffusing particles of the size scattering of scattered light etc.

In scheme (5), (6), substrate 5 is seen from electroluminescence layer 2 to be arranged on top layer (bottom emissive type), at the arranged outside substrate of negative electrode, and see from electroluminescence layer 2 layer that forms top layer is provided with protective cover also can (top emission structure).

Fig. 9 illustrates the formation of the top emission structure of scheme (5), forms negative electrode 1 on substrate 5, forms electroluminescence layer 2, transparent electrode layer 3, infiltration light diffusion layer B3b and low-index layer 4 thereon successively, forms protective cover 6 on this low-index layer 4.Fig. 9 is configured in the structure of negative electrode 1 side with substrate 5 in the scheme (5), and also can similarly substrate 5 be configured in negative electrode 1 side in the scheme (6).

[the 4th invention]

Electroluminescent cell shown in Figure 10 (scheme (7)) has: negative electrode 1, electroluminescence layer 2, transparent electrode layer 3, low-index layer 4 and transparency carrier 5 be the layer structure of stacked arrangement in this order, and the interface of low-index layer 4 and transparency carrier 3 forms the male and fomale(M﹠F) of light scattering.

For making the low-index layer 4 and the interface of transparency carrier 3 form the male and fomale(M﹠F) of light scattering, after making these low-index layer 4 film forming, implement male and fomale(M﹠F) and form processing, then, on the male and fomale(M﹠F) of this low-index layer, form transparent electrode layer 3.

Male and fomale(M﹠F) as low-index layer 4 forms processing, can enumerate: after low-index layer forms, with corona treatment, plasma treatment, blasting treatment etc., coarse etching is carried out on the surface, or male and fomale(M﹠F) carried out the physics transfer printing, or this male and fomale(M﹠F) rubbed, or under the state of engagement concavity convex surface, form low-index layer, or with trickle and can make methods such as the particle of the size of light scattering diffusion is coated with or imbeds with some method.

This transparent electrode layer 3, because low-index layer 4 is carried out after male and fomale(M﹠F) form to handle, even film forming on male and fomale(M﹠F) is so this transparent electrode layer 3 wishes to form with the rubbing method of material liquid by the coating formation of filming.

Form as the coating fluid that is used to form transparent electrode layer 3, for example, can use the ITO fine particle is dispersed in material in the organic solvent with electric conductive polymer or other resin binders, or conductive polymer material etc., but not only be defined in this.

Adopt this coating fluid,, form pattern as necessity of electroluminescent cell electrode by photoetching process or ink-jet method etc.About live width 1～10 μ m behind the composition is standard, but is not limited thereto.

In scheme (7), because the interface of transparent electrode layer 3 and low-index layer (also not being provided with sometimes) forms the light scattering male and fomale(M﹠F), so the total reflection on this interface reduces, the light quantity that enters low-index layer 4 from transparent electrode layer 3 increases, and light takes out efficient and improves.In order fully to reduce this total reflection, the surface roughness Ra at this interface is generally 5～200nm, preferred 10～100nm, more preferably 20～50nm.

The surface roughness Ra at this interface is generally 5～200nm, preferred 10～100nm, more preferably about 20～50nm.Rmax is generally 30～600nm, preferred 50～500nm, more preferably about 100～300nm.

About surface roughness Ra and Rmax, can in addition, estimate according to JIS B0601 specified standard as the KLA-Tencor P-15 type contact pin type surface roughness meter that evaluation appts can adopt ケ-エ Le エ-テ Application コ-Le society to make.Common 1 time scanning distance is 0.5 μ, and it is carried out 3 scanning, and its mean value is as its measured value.

The shape of matsurface or size promptly can be used as long as have the function of the light scattering of making.The size of matsurface, be surpass be scattered light wavelength (because of being generally visible light, thus be 400～700nm) 1/10 size, and, generally reach the several times of wavelength, concavo-convex size is bigger, the scattered power height of healing.Yet when matsurface concavo-convex oversize, the flatness of the coated film on it easily goes wrong, and is unfavorable.

In the electroluminescent cell of scheme (7), because the interface of transparent electrode layer 3 and low-index layer is the male and fomale(M﹠F) of light scattering, so the total reflection at this interface reduces, from transparent electrode layer 3 sides directly, or increase by the light quantity that the reflection at negative electrode enters low-index layer 4 indirectly, light takes out efficient and improves.That is,, take out the guided wave of luminescent layer side, by approximately perpendicular refraction in the low-refraction course transparency carrier, incident, thus, can be suppressed at the total reflection at the air layer interface of transparency carrier again by transparency electrode from the matsurface (male and fomale(M﹠F)) of light scattering.

Electroluminescent cell shown in Figure 11 (scheme (8)) has: negative electrode 1, electroluminescence layer 2, transparent electrode layer 3c, high refractive index layer 8, low-index layer 4 and transparency carrier 5 be the layer structure of stacked arrangement in this order, and the interface of low-index layer 4 and high refractive index layer 8 is the male and fomale(M﹠F) of light scattering.

The refractive index of high refractive index layer 8 equates in fact with the refractive index of transparent electrode layer 3c.That is, the refringence of high refractive index layer 8 and transparent electrode layer 3c is usually below 0.3 or 0.3, below preferred 0.2 or 0.2, more preferably below 0.1 or 0.1.

The composition of high refractive index layer 8 and transparent electrode layer 3c both can be identical also can be different.As the composition of the high index of refraction different with transparent electrode layer 3c, can enumerate high refractive index resins such as polyethersulfone resin, polyetherimide resin or the particulate (nano particle) of high-index materials such as ATO (antimony tin oxide), ITO, zirconium dioxide, titanium dioxide is disperseed, the material of transparence.Coating is preferred after making these substance dissolves or being scattered in the organic solvent.

High refractive index layer 8, the transparent electrode layer 3 same rubbing method film forming of employing and scheme (7) are preferred.The reason of preferred rubbing method is because the electroluminescence layer side interface of transparency electrode must be smooth.So long as rubbing method, then can be and can planarization with concavo-convex the burying of substrate.Adopt evaporation or sputter equal vacuum technology, then the concavo-convex of substrate reflected easily, is difficult to make it planarization.Also having, wish that the interface of the electroluminescence layer side of transparency electrode is smooth reason, is because due to the electric field in the electroluminescence layer required evenly, when it was inhomogeneous, defectives such as black splotch took place EL pigment generation deterioration easily.Transparent electrode layer 3c can adopt with the same rubbing method of transparent electrode layer 3 to form, and in addition, also can form by film-forming process such as evaporation or sputters.

The thickness of transparent electrode layer 3c is and the same in fact thickness of above-mentioned transparent electrode layer 3.For example, the thickness of high refractive index layer 8 reaches the concavo-convex viewpoint of carrying out planarization of substrate easily from the formation with film, is generally 100～3000nm, preferred 500～1000nm.

In this electroluminescent cell, because the interface of high refractive index layer 8 and low-index layer 4 is light scattering male and fomale(M﹠F)s, so, reducing in this interface total reflection, the light quantity that enters low-index layer 4 from transparent electrode layer 3c side increases, and light takes out efficient and improves.The range of surface roughness of the male and fomale(M﹠F) at this interface is the degree same in fact with the occasion of above-mentioned Fig. 7.

In scheme (7), (8); substrate 5 is seen from electroluminescence layer 2 and is arranged on top layer (bottom emissive type); as shown in figure 12, substrate is located at the outside of negative electrode, and can see that from electroluminescence layer the layer as top layer is provided with protective cover (top emission structure).In the scheme of the top emission structure of Figure 12, on substrate 5, form negative electrode 1, form electroluminescence layer 2, transparent electrode layer 3 and low-index layer 4 thereon successively, on this low-index layer 4, form protective cover 6.Also have, in this scheme, substrate 5 is unnecessary transparent, and optically, the protective cover in this scheme plays the function of transparency carrier in the scheme (7).In addition, only limit to this scheme, even low-index layer is air layer (space), also no problem on the formation of element.

The scheme of Figure 12 is substrate 5 to be configured in negative electrode 1 side in scheme (7), but also can similarly substrate 5 be configured in negative electrode 1 side in scheme (8).

Embodiment

Reference example below by being equivalent to embodiment illustrates in greater detail the present invention, but the present invention only otherwise exceed its main points, just not limited by following reference example.Also have, in following reference example and comparative example, do not form negative electrode and electroluminescence layer, on transparent electrode layer, form the fluorchrome layer, to this fluorchrome layer irradiation exciting light, take out fluorescence from substrate-side,, obtain the light quantity of taking-up according to following main points with fluorescence spectrophotometer luminance meter (manufacturing of (strain) Hitachi).Promptly, at the back side of the laminated body that obtains (fluorchrome evaporation side), exciting light from fluorchrome layer side irradiation 400nm or the following wavelength of 400nm, be used in the wave detector that is provided with on the angle of emergence 45 degree directions of glass substrate side surface, measure the taking-up luminous intensity of 420～750nm, obtain luminous energy with the long integration of all-wave.Measure the fluorescence spectrophotometer luminance meter F-4500 type (manufacturing of Hitachi society) that adopts.Also have, the measurement result of luminous energy is used with the relative value of comparative example 1 and is represented.

Average grain diameter is measured with the FIB-SEM method.

Detecting refractive index, D542 on principle, implement with ellipsograph (ソ プ ラ (strain) manufacturing), but when the refractive index of the body portion of middle (nanometer) porous material or particle dispersion is difficult to measure with ellipsograph, adopt prism coupler 2010 types (manufacturing of U.S. メ ト リ コ Application society), carry out detecting refractive index in 25 ℃ with the laser of wavelength 633nm.

＜reference example 1～5 〉

These reference examples are used for the explanation of the 1st invention.

Reference example 1 (scheme (1) that is equivalent to Fig. 1)

Will be by alkali-free glass (Asahi Glass (strain) manufacturing, " AN100 ") thickness 0.7mm, the 75mm square glass baseplate surface made, in 0.1N nitric acid dipping about 1 hour and carry out ungrease treatment after, wash with pure water, dry in 60 ℃ of baking ovens, obtain glass substrate 1.

In addition, (Mitsubishi Chemical's (strain) makes toward the oligomer by tetramethoxy-silicane, " MS51 ") add small amount of acid catalyst (acetyl acetone aluminium) in the mixed liquor that constitutes of 30 weight %, butanols (BtOH) 50 weight %, desalted water 8 weight %, methyl alcohol 12 weight %, then, add the above particle diameter of its 60 weight % or 60 weight % in 70～150nm scope, and the silicon dioxide microparticle of average grain diameter 120nm, and make it reach weight ratio 10% to MS51, in 60 ℃ of stirrings 3 hours, placed for 1 week and carry out slaking.

The coating fluid that on above-mentioned glass substrate 1, obtains with the coating of dip coated instrument, after dry 15 minutes, dipping is 5 minutes in methyl alcohol, and also after dry 5 minutes, heating is 15 minutes in 150 ℃ of baking ovens, obtains permeating light diffusion layer A4a in taking-up.In addition, when dip coated, paste diaphragm overleaf, peel off after the coating, only on single face, form and film.

The thickness of resulting infiltration light diffusion layer A4a is 600nm, observes scattering particles with approximate 5 sections overlapping structures.When measuring the refractive index of the body portion that permeates light diffusion layer A4a with ellipsograph (manufacturing of ソ プ ラ society), the result is 1.27 when wavelength 550nm.In addition, also use prism coupler 2010 types (manufacturing of U.S. メ ト リ コ Application society) to measure refractive index.Result with the laser determination of wavelength 633nm is that refractive index is 1.29.

The thickness of vapor-deposited film and sputtered film is confirmed from the time management or the crystal oscillation formula film thickness gauge of normal line.The thickness of coated film causes the ladder of damage to measure by the light interference type film thickness gauge or to film.Glass substrate uniform thickness base material is measured with miniature vernier caliper etc.

Permeate on light diffusion layer A4a with 1000 at this Thickness normal temperature sputtering ITO, form transparent electrode layer 3, again with 1000

Thickness evaporation ALQ3 (aluminium chinoline coordination compound: the pigment of green-emitting fluorescence).The refractive index of measuring the ITO layer is 1.9.

Take out light quantity, count 170% with the relative value of taking out light quantity for following comparative example 1.

Comparative example 1 (the original example that is equivalent to Figure 14)

Except that in the infiltration light diffusion layer forms with coating fluid, not adding silicon dioxide microparticle, fully similarly make the fluorescent element of the layer structure that is equivalent to Figure 14 with above-mentioned reference example 1, carry out identical taking-up actinometry.

Comparative example 2 (the original example that is equivalent to Figure 13 a)

Remove and omit the infiltration light diffusion layer, and form beyond the structure of layer shown in Figure 13 a, similarly make the fluorescence radiation element, carry out identical taking-up actinometry with above-mentioned reference example 1.

The taking-up light quantity is 91% with respect to the taking-up light quantity of comparative example 1.

Reference example 2 (scheme (2) that is equivalent to Fig. 2)

Adopt the coating fluid that does not contain silicon dioxide microparticle of comparative example 1, form the low-index layer 4 of thick 500nm,, form the infiltration light diffusion layer 4b of thick 600nm thereon with the coating fluid that contains silicon dioxide microparticle of above-mentioned reference example 1.

Similarly form thickness 1000 with reference example 1 thereon, with the normal temperature sputtering method

The transparent electrode layer 3 of ITO, evaporation 1000 again

Thick ALQ3.

The taking-up light quantity is 190% with respect to the taking-up light quantity of comparative example 1.

Reference example 3

Similarly prepare glass substrate with reference example 1.In addition, coating fluid is prepared by laxative remedy.Add small amount of acid catalyst (acetyl acetone aluminium) in MS51 (oligomer of tetramethoxy-silicane) 30 weight %, the butanols 50 weight % that make toward Mitsubishi Chemical society, the mixed liquor that desalted water 8 weight %, methyl alcohol 12 weight % constitute.At this moment, in butanols, disperse the TiO 2 particles of average grain diameter 200nm in advance, make the weight percent that contains in the layer at the particle that obtains reach 8 weight %.Also have, particle contains the weight percent in the layer, obtains by the method same with obtaining particle size distribution in the above-mentioned film.The weight of volume converts, and the density of particle and matrix is implemented by inquiry.Density when matrix is porous body is from obtaining the X ray reflection rate or obtaining refractive index and calculate.The gained mixed liquor was placed for 1 week and is carried out slaking in 60 ℃ of stirrings 3 hours.

The mixed liquor of slaking similarly is coated with and film forming on glass substrate with reference example 1.The thickness that contains the low-index layer (infiltration light diffusion layer) of particle is 500nm, and the detecting refractive index result of body portion is 1.40.

Under this state to the light transmission capacity of basal lamina determination vertical direction, by with reference example 1 in the light transmission capacity of glass substrate vertical direction of record compare the ratio of investigation amount of scattered light.When measuring light transmittance, adopt UV, visible light extinction photometer HP8453 type (ヒ ユ-レ Star De パ Star カ-De society makes).

In addition, itself be level and smooth (not being the surface of scattering) in order to confirm the surface, decide surface roughness with contact pin type surface roughness instrumentation.The P-15 type that uses ケ-エ Le エ-テ Application コ-Le society to make during mensuration.0.5 the result of μ sweep measuring is Ra=4nm.

On this laminated body,, form 1000 with reference example 1 sputtering ITO under normal temperature similarly

Thick transparent electrode layer.In addition, will be by thereon with 1000

Thickness respectively the fluorchrome ALQ3 (oxine aluminium), the sample that red fluorchrome PPD (phenanthryl phenylenediamine) forms of evaporation green respectively prepare 1 part.

The laminated body that use obtains is similarly measured fluorescence intensity with reference example 1.But, the peak fluorescence intensity of 30 degree directions of the vertical direction of mensuration glass substrate emitting side (angle of emergence 30 degree).Evaporation the sample of ALQ3, under wavelength 550nm, measure the peak fluorescence intensity, evaporation the sample of PPD, under wavelength 450nm, measure the peak fluorescence intensity.

The scattering loss light quantity, as follows according to the result that above-mentioned main points are measured.

To the scattering loss light quantity of the laminated body light transit dose that obtains, when wavelength 450nm, be 39%, when wavelength 550nm, be 28%.

In addition, with respect to the light extraction efficiency of following comparative example 3, respectively as following to each fluorchrome evaporation laminated body.

Light extraction efficiency is 240% (PPD) when wavelength 450nm, is 190% (ALQ3) when wavelength 550nm.

Can confirm, take out when efficient improves,, the taking-up efficient of green light is significantly improved particularly at blue region at the light of visible light universe.

Comparative example 3

In reference example 3, not to coating fluid adds TiO 2 particles, similarly make fluorescent element, carry out identical taking-up actinometry.When measuring surface roughness equally with reference example 3, Ra=2nm.

Reference example 4

The polycarbonate resin 7020AD2 that the エ of Mitsubishi Application ジ ニ ア リ Application グ プ ラ ス チ ソ Network society is made is dissolved in the carrene, then, the TiO 2 particles (titanium dioxide) of particle diameter 200nm is disperseed, and make the weight percent that contains in the layer at the particle that obtains reach 10 weight %.It is being carried out in drying at room temperature, obtaining permeating light diffusion layer (layer that contains particle) after solvent is coated with the dip coated method on same glass substrate of preparing by reference example 1.

The thickness of infiltration light diffusion layer is 600nm.The refractive index of measuring body portion is 1.59.Also have, when measuring surface roughness equally with reference example 3, Ra=4nm.

Use this substrate, similarly form ITO film and uvea, carry out fluorescent strength determining again with reference example 3.But measure the fluorescence intensity of the direction of emitting side vertical direction 30 degree that leave glass substrate.

Taking out light quantity, is 170% (wavelength: 550nm) with respect to the relative value of the taking-up light quantity that records at equidirectional in the following comparative example 4.

Comparative example 4

The aluminium oxide particles in not adding above-mentioned reference example 4, similarly make fluorescent element, carry out identical taking-up actinometry.When similarly measuring surface roughness with reference example 4, Ra=2nm.

Reference example 5

On the film of the PET film 125 μ thickness that the Port リ エ ス テ of Mitsubishi Chemical Le Off イ Le system society makes, with 200

Thick formation as fixing coating held concurrently behind the silica steam plating film of barrier coat, similarly forms with reference example 4 and permeates light diffusion layer (contain particle layer).In addition, before this infiltration light diffusion layer bone dry, on the glass substrate of band ITO, this film can be bonding with ito surface by driving fit.

On the infiltration light diffusion layer of this film, similarly form ITO film and ALQ3 layer with reference example 3, estimate again.

The thickness of infiltration light diffusion layer is 600nm.The refractive index of measuring body portion is 1.59.In addition, be 4nm with contact pin type surface roughness meter (P-15 that ケ-エ Le エ-テ Application コ-Le society makes) mensuration surface roughness Ra.

Use this substrate, similarly measure fluorescence intensity with reference example 3.Mensuration is from the peak fluorescence intensity of the 30 degree directions (angle of emergence 30 degree) of the vertical direction of glass substrate emitting side.

Take out light quantity, with respect to the same taking-up light quantity (wavelength of measuring: be 160% 550nm) in the following comparative example 5.From then on the result can expect, uses up the optical thin film that takes out usefulness even make in top emission structure, and extraction efficiency also can improve.

Comparative example 5

Except the thickness of reference example 5 is made as 2700nm,, implement same taking-up actinometry with the reference example 5 same fluorescence radiation elements of making.Nesa coating is formed preceding surface, during with contact pin type surface roughness meter (P-15 that ケ-エ Le エ-テ Application コ-Le society makes) mensuration surface roughness, Ra=3nm.

Reference example 6

Except the thickness of the infiltration light diffusion layer of reference example 4 is decided to be 1000nm, similarly form element with reference example 4, implement actinometry.Extraction efficiency with respect to comparative example 4 is 150% (wavelength: 550nm).

Comparative example 6

Except the thickness of the infiltration light diffusion layer of reference example 4 is decided to be 2700nm, similarly form element with reference example 4, implement actinometry.Be not limited to this reference example, wall thickening then can reach by the repeated multiple times painting process if desired.Extraction efficiency with respect to comparative example 4 is 80% (wavelength: 550nm).The infiltration light diffusion layer is blocked up, then is considered to opaque.

＜reference example 7～8, comparative example 7～8 〉

These examples are used to illustrate the 2nd invention.

Reference example 7 (scheme (3) that is equivalent to Fig. 4)

Thickness 0.7mm, the 75mm square glass baseplate surface that to make by alkali-free glass (Asahi Glass (strain) make " AN100 "), in 0.1N nitric acid the dipping about 1 hour and carry out ungrease treatment after, with the pure water washing, dry in 60 ℃ of baking ovens, obtain glass substrate 1.

In addition, (Mitsubishi Chemical's (strain) makes toward the oligomer by tetramethoxy-silicane, " MS51 ") add small amount of acid catalyst (acetyl acetone aluminium) in the mixed liquor that constitutes of 30 weight %, butanols (BtOH) 50 weight %, desalted water 8 weight %, methyl alcohol (MeOH) 12 weight %, then, with the above particle diameter of its 60 weight % of surfactant-rise to add or 60 weight % in 70～150nm scope, and the silicon dioxide microparticle of average grain diameter 120nm, and make it reach weight ratio 10% to MS51, in 60 ℃ of stirrings 3 hours, placed for 1 week and carry out slaking.

The slaking coating fluid that on above-mentioned glass substrate 1, obtains with the coating of dip coated instrument, after dry 15 minutes, dipping is 5 minutes in methyl alcohol, and also after dry 5 minutes, heating is 15 minutes in 150 ℃ of baking ovens, obtains permeating light diffusion layer 4a in taking-up.In addition, when dip coated, paste diaphragm overleaf, peel off after the coating, only on single face, form and film.

The thickness of resulting infiltration light diffusion layer 4a is 600nm, has confirmed that scattering particles is approximate 5 sections overlapping structures.Measure the low refractive index film that is only formed by basis material (removing the material of particulate) with ellipsograph (manufacturing of ソ プ ラ society), the detecting refractive index result of film is, is 1.27 at wavelength 550nm.

In addition, the prism coupler model 2010 of also available U.S. メ ト リ コ Application society is measured refractive indexes.During with the laser determination of wavelength 633nm, refractive index is 1.29.

Evaporation zirconia on this infiltration light diffusion layer 4a forms the thick separator 10 of 300nm.Thereon with 1000 Thickness sputtering ITO at normal temperatures forms transparent electrode layer 3, evaporation ALQ3 (fluorchrome three (oxine) aluminium) 1000 again

Thick.The detecting refractive index result of ITO layer is 1.9.

The taking-up light quantity is 170% with respect to the taking-up light quantity of following comparative example 7.

Comparative example 7

In the infiltration light diffusion layer in following reference example 8 forms with coating fluid, do not add the titanium dioxide fine particles, fully similarly make the fluorescence radiation element of the layer structure that is equivalent to Figure 14, carry out same taking-up actinometry.

Comparative example 8

Except omitting low-index layer 4, form beyond the layer structure shown in Figure 13 a, similarly make electroluminescent cell with comparative example 7, carry out same taking-up actinometry.

The taking-up light quantity of this comparative example 8 is 91% of a comparative example 7

Reference example 8 (scheme (4) that is equivalent to Fig. 5)

Adopt the coating fluid that does not contain titanium dioxide fine particles of comparative example 7, form the low-index layer 4 of thick 500nm,, form the infiltration light diffusion layer 4b of thick 600nm thereon with the coating fluid that contains titanium dioxide fine particles of above-mentioned reference example 7.

The evaporation zirconia forms the thick separator 10 of 300nm thereon.Similarly form 1000 with reference example 7 thereon, with the normal temperature sputtering method

The transparent electrode layer 3 of thick ITO is again with 1000

Thickness evaporation ALQ3.

To this reference example 8, when carrying out taking out light quantity, be 190% of comparative example 7 with the same mensuration of reference example 7.

＜reference example 9～13, comparative example 9～11 〉

These examples are used to illustrate the 3rd invention.

Reference example 9 (scheme (5) that is equivalent to Fig. 7)

Will be by alkali-free glass (Asahi Glass (strain) manufacturing, " AN100 ") thickness 0.7mm, the 75mm square glass baseplate surface made, in 0.1N nitric acid dipping about 1 hour and carry out ungrease treatment after, wash with pure water, dry in 60 ℃ of baking ovens, obtain glass substrate 1.

In addition, (Mitsubishi Chemical's (strain) makes toward the oligomer by tetramethoxy-silicane, " MS51 ") add small amount of acid catalyst (acetyl acetone aluminium) in the mixed liquor that constitutes of 30 weight %, butanols 50 weight %, desalted water 8 weight %, methyl alcohol 12 weight %, then, in 60 ℃ of stirrings 3 hours, placed for 1 week and carry out slaking.

The coating fluid that on above-mentioned glass substrate 1, obtains with the coating of dip coated instrument, after dry 15 minutes, dipping is 5 minutes in methyl alcohol, and also after dry 5 minutes, heating is 15 minutes in 150 ℃ of baking ovens, obtains low-index layer 4 in taking-up.In addition, when dip coated, paste diaphragm overleaf, peel off after the coating, only on single face, form and film.

The thickness of low-index layer 4 is 600nm, when measuring the refractive index of film with ellipsograph (ソ プ ラ (strain) manufacturing), is 1.27 at wavelength 550nm.In addition, when measuring, be 1.31 at wavelength 633nm with the prism coupler model 2010 of U.S. メ ト リ コ Application society.

On this low-index layer 4, form infiltration light diffusion layer B3a by laxative remedy.Promptly, in the particulate of the ITO of average grain diameter 50nm, add a small amount of polythiophene class electric conductive polymer and poly-(3-alkylthrophene), then, the TiO 2 particles that disperses the about 120nm of average grain diameter, make the amount of the mixture that obtains is reached 5 heavy %, it is dissolved in chloroform, disperses, with carrying out drying after the coating of rotary coating instrument.The thickness of layer is 1000nm, and the detecting refractive index result of body portion is 1.8.

Evaporation 1000 on this infiltration light diffusion layer B3a

Thick ALQ3 (fluorchrome).

The taking-up light quantity is 170% with respect to the taking-up light quantity of following comparative example 9.

Comparative example 9

In the transparent electrode layer in above-mentioned reference example 9 forms with coating fluid, do not add the titanium dioxide fine particles, fully similarly make the fluorescent element of the layer structure that is equivalent to Figure 14, and carry out identical taking-up actinometry.

Comparative example 10

Remove and omit low-index layer 4, formation is equivalent to similarly make fluorescence with above-mentioned comparative example 9 and estimate element beyond the structure of layer shown in Figure 13 a, carries out identical taking-up actinometry.

The taking-up light quantity of this comparative example 10 is 91% of a comparative example 9.

Reference example 10 (scheme (6) that is equivalent to Fig. 8)

Except employing coating fluid in reference example 9 forms the infiltration light diffusion layer B3b of thick 500nm, and do not add thereon beyond the titanium dioxide fine particles, adopt and the same coating fluid of above-mentioned coating fluid, form the transparent electrode layer 3 of thick 500nm, evaporation 1000 again

Thick ALQ3.

160% of the taking-up light quantity that its taking-up light quantity is a comparative example 9.

Reference example 11

Except low refractive index film is not set, similarly make the fluorescence radiation element with reference example 9, carry out identical taking-up actinometry.Taking out light quantity is 150% of comparative example 9.

Reference example 12

Similarly prepare glass substrate with reference example 9.Then, adjust high index of refraction scattering film coating fluid with following method.Tetraisopropoxy titanium (Ti (O-iC ₃H ₇) ₄) and absolute ethyl alcohol (C ₂H ₅OH), mix in stirring at room with mol ratio 1:4.At this moment, in absolute ethyl alcohol, disperse the silicon dioxide granule of average grain diameter 200nm in advance, make at the weight percent that contains in the particle layer that obtains to reach 10 weight %.Also have, contain the weight percent in the layer of particle, obtain with the above-mentioned same method of particle size distribution of obtaining in the film.The weight of volume converts, and the density of particle and matrix is implemented by inquiry.Density when matrix is porous body is calculated by obtaining X ray reflection rate or refractive index.

Liquid ethanol, water, hydrochloric acid mix with mol ratio 4:1:0.08 adds wherein with pipette in 0 ℃, makes it to be hydrolyzed, and obtains being coated with behind the TiO 2 sol.This film in 300 ℃ of heating 10 minutes, is obtained permeating light diffusion layer.The thickness of infiltration light diffusion layer is 500nm.The refractive index of measuring body portion is 2.1.

Carry out the normal temperature sputter thereon, form 500

Nesa coating.The detecting refractive index result of this nesa coating is 1.9.Similarly form luminescent layer with reference example 9 again, make fluorescence and estimate element, when implementing to take out the mensuration of light quantity, taking out light quantity is 170% of comparative example 11.

Comparative example 11

Except the silicon dioxide granule that does not add reference example 12, fully similarly make the fluorescence radiation element, implement to take out the mensuration of light quantity.

Reference example 13

Similarly make the fluorescence radiation element with reference example 11, implement to take out the mensuration of light quantity.But, before luminescent layer forms, similarly form the nesa coating of ITO with reference example 12.Taking out light quantity is 140% of comparative example 9.

＜reference example 14～17, comparative example 12～15 〉

These examples are used to illustrate the 4th invention.

Reference example 14 (scheme (7) that is equivalent to Figure 10)

Will be by alkali-free glass (Asahi Glass (strain) manufacturing, " AN100 ") thickness 0.7mm, the 75mm square glass baseplate surface made, in 0.1N nitric acid dipping about 1 hour and carry out ungrease treatment after, wash with pure water, dry in 60 ℃ of baking ovens, obtain glass substrate 1.

In addition, (Mitsubishi Chemical's (strain) makes toward the oligomer by tetramethoxy-silicane, " MS51 ") add small amount of acid catalyst (acetyl acetone aluminium) in the mixed liquor that constitutes of 30 weight %, butanols 50 weight %, desalted water 8 weight %, methyl alcohol 12 weight %, then, in 60 ℃ of stirrings 3 hours, placed for 1 week and carry out slaking.

The coating fluid that on above-mentioned glass substrate 1, obtains with the coating of dip coated instrument, after dry 15 minutes, dipping is 5 minutes in methyl alcohol, and also after dry 5 minutes, heating is 15 minutes in 150 ℃ of baking ovens, obtains low-index layer 4 in taking-up.In addition, when dip coated, paste diaphragm overleaf, peel off after the coating, only on single face, form and film.

The thickness of low-index layer 4 is 600nm, when measuring the refractive index of film with ellipsograph (ソ プ ラ (strain) manufacturing), is 1.27 at wavelength 550nm.In addition, also having carried out detecting refractive index with the prism coupler model 2010 of U.S. メ ト リ コ Application society, is 1.30 during with the laser determination of wavelength 633nm.

This low-index layer 4 is carried out the male and fomale(M﹠F) processing by laxative remedy.That is, make fully blowing after the chap, remove surperficial cast with having the trickle concavo-convex sand paper of the 1000 purposes whole surface that rubs gently.The surface roughness Ra of the low-index layer 4 after this processing is 100nm, Rmax=500nm.

On this low-index layer 4, form transparent electrode layer 3 by laxative remedy.That is, in the ITO of average grain diameter 50nm particulate, add polythiophene class electric conductive polymer and poly-(the 3-alkylthrophene) of equivalent, their are dissolved, are dispersed in the chloroform, with carrying out drying after the coating of rotary coating machine.Bed thickness is 800nm, and the detecting refractive index result of body portion is 1.8.

Evaporation 1000 on this transparent electrode layer 3

Thick ALQ3 (fluorchrome).

The taking-up light quantity is 190% with respect to the taking-up light quantity of following comparative example 12.

Comparative example 12

Except that the low-index layer 4 in the above-mentioned reference example 14 not being carried out the male and fomale(M﹠F) processing, fully similarly make the fluorescent element of the layer structure that is equivalent to Figure 14, carry out identical taking-up actinometry.Surface roughness Ra=the 2nm of low-index layer 4, Rmax=20nm.

Comparative example 13

Remove and omit low-index layer 4, form beyond the layer structure shown in Figure 13 a, similarly make the fluorescence radiation element, carry out identical taking-up actinometry with above-mentioned comparative example 12.Surface roughness Ra=the 1nm of glass baseplate surface, Rmax=5nm.

The taking-up light quantity of this comparative example 13 is 91% of a comparative example 12.

Reference example 15 (scheme (8) that is equivalent to Figure 11)

Except in reference example 14, adopting coating fluid to form the high refractive index layer 8 of thick 1000nm (1 μ m), make the transparent electrode layer 3A that forms thick 100nm with the normal temperature sputtering ITO thereon, evaporation 1000 again

Thick ALQ3.The detecting refractive index result of ITO layer is 1.85.

Take out light quantity and be comparative example 12 the taking-up light quantity 170%.

Reference example 16

Similarly prepare glass substrate with reference example 14.Single side surface to this glass substrate is carried out blasting treatment.The blasting treatment device use only make ニ ユ-マ Off ラ ス -SGK type.After the processing, after the surface flooded about 1 hour and carrying out ungrease treatment, use the pure water ultrasonic washing in 0.1N nitric acid, dry in 60 ℃ of baking ovens.The Ra measurement result of treated side is 100nm, Rmax=600nm.

Adopt the coating fluid by following condition adjustment to carry out dip coated thereon, formation is filmed.Also have, when dip coated, paste diaphragm overleaf, peel off after the coating, only form and film at single face.

Tetraisopropoxy titanium (Ti (O-iC ₃H ₇) ₄) and absolute ethyl alcohol (C ₂H ₅OH), mix in stirring at room with mol ratio 1:4.Liquid ethanol, water, hydrochloric acid mix with mol ratio 4:1:0.08 adds wherein with pipette in 0 ℃, makes it to be hydrolyzed, and obtains being coated with behind the TiO 2 sol.This film in 300 ℃ of heating 10 minutes, is obtained thick the filming of 600nm.The refractive index of measuring body portion is 2.1.

Similarly form nesa coating with the normal temperature sputtering method of ITO with reference example 15 thereon, in addition, form luminescent layer equally, make fluorescence and estimate element, when implementing to take out the mensuration of light quantity, taking out light quantity is 220% of following comparative example 14.

Comparative example 14

Except not carrying out blasting treatment in the reference example 16 do not carry out, fully similarly form the fluorescence radiation element and estimate.

Reference example 17

Similarly prepare the glass substrate that carried out blasting treatment with reference example 16.Then, polycarbonate resin 7020 AD2 that the エ of Mitsubishi Application ジ ニ ア リ Application グ プ ラ ス チ Star Network society is made are dissolved in the coating fluid in the carrene thereon, and are dry with rotary coating machine coating back, obtain coated film.The thickness of layer is that the detecting refractive index result of 800nm, body portion is 1.59.

Similarly form nesa coating with the normal temperature sputtering method of ITO with reference example 15 thereon, in addition, similarly form luminescent layer, make fluorescence and estimate element, when implementing to take out the mensuration of light quantity, taking out light quantity is 160% of following comparative example 15.

Comparative example 15

Glass substrate in reference example 17 does not carry out fully similarly making fluorescence radiation element and implementation evaluation the blasting treatment.

Industrial applicibility

According to the present invention of above-mentioned explanation, the light that can significantly improve electroluminescent cell takes out efficient. Press According to the present invention, no matter inorganic, organic, in addition, no matter display is used, surface luminous light source usefulness, all can Take out efficient with the light that increases substantially electroluminescent cell.

When particularly separation layer being set, transparent electrode layer or electroluminescence layer can be protected, and electricity can be suppressed Cause the deterioration of luminescent pigment or the generation of black splotch, the life-span that can seek to improve element.

Claims (19)

1. electroluminescent cell, it is that negative electrode, electroluminescence layer, transparent electrode layer and light penetrating object dispose and the electroluminescent cell that forms successively, it is characterized in that, comprise that refractive index by the particle that contains scattered light is the infiltration light diffusion layer A of the matrix that constitutes of 1.1～1.9 material, be arranged between transparent electrode layer and the light penetrating object, the refractive index of refractive index ratio transparent electrode layer of matrix that constitutes infiltration light diffusion layer A is low, and the particle of scattered light more than 1/3 or 1/3 (weight ratio) be present in from transparent electrode layer or with the interface 600nm of separator in.

2. electroluminescent cell, it is that negative electrode, electroluminescence layer, transparent electrode layer and light penetrating object dispose and the electroluminescent cell that forms in this order, it is characterized in that, to comprise that refractive index by the particle that contains scattered light is that the infiltration light diffusion layer A of the matrix that constitutes of 1.1～1.9 material is arranged between transparent electrode layer and the light penetrating object, between infiltration light diffusion layer A and transparent electrode layer, separator is set, is used to prevent that the material that permeates in the light diffusion layer A from spreading to the transparent electrode layer side.

3. electroluminescent cell, it is a negative electrode, electroluminescence layer, transparent electrode layer and light penetrating object dispose and the electroluminescent cell that forms in this order, it is characterized in that, comprise that refractive index by the particle that contains scattered light is the infiltration light diffusion layer A of the matrix that constitutes of 1.1～1.9 material, be arranged between transparent electrode layer and the light penetrating object, between infiltration light diffusion layer A and transparent electrode layer, separator is set, be used to prevent permeate material in the light diffusion layer A to the diffusion of transparent electrode layer side, the difference that constitutes the refractive index of the refractive index of matrix of infiltration light diffusion layer A and light penetrating object be below 0.3 and the refractive index of the refractive index ratio transparent electrode layer of matrix low.

4. according to the electroluminescent cell of any one record in the claim 1～3, wherein, the particle content of the scattered light among the above-mentioned infiltration light diffusion layer A is 1～40 volume %, in the weight ratio of the particle of scattered light, is particle diameter 20～400nm more than 60% or 60%.

5. according to the electroluminescent cell of any one record in the claim 1～3, wherein, the thickness of above-mentioned infiltration light diffusion layer A is more than 2 times or 2 times of average grain diameter of the particle of scattered light.

6. according to the electroluminescent cells of claim 2 or 3 records, wherein, the particle of scattered light more than 1/3 or 1/3 (weight ratio) be present in from transparent electrode layer or with the interface 600nm of separator in.

7. according to the electroluminescent cell of any one record in the claim 1～3, wherein, the particle of scattered light is silicon dioxide, cataloid, titanium dioxide, zirconium dioxide, ITO (tin indium oxide), ATO (antimony tin) or aluminium oxide.

8. according to the electroluminescent cell of claim 2 or 3 records, wherein, the difference of the refractive index of this separator and the refractive index of this transparent electrode layer is below 0.3 or is the above size of the refractive index of transparency electrode.

9. according to the electroluminescent cell of claim 2 or 3 records, wherein, the thickness of this separator is 50～400nm.

10. according to the electroluminescent cell of claim 2 or 3 records, wherein, the thickness of this separator is 100～200nm.

11. electroluminescent cell, it is that negative electrode, electroluminescence layer, transparent electrode layer and light penetrating object dispose and the electroluminescent cell that forms in this order, it is characterized in that, transparent electrode layer contains the particle of scattered light, and has the layer lower than the refractive index of light penetrating object between this transparent electrode layer and this light penetrating object.

12. according to the electroluminescent cell of claim 11 record, wherein, the content of the particle of the scattered light in the above-mentioned transparent electrode layer is 1～40 volume %, in the weight ratio of the particle of scattered light, is particle diameter 30～400nm more than 60% or 60%.

13. according to the electroluminescent cell of claim 11 record, wherein, the thickness of above-mentioned transparent electrode layer is more than 2 times or 2 times of average grain diameter of the particle of scattered light.

14. electroluminescent cell, it is that negative electrode, electroluminescence layer, transparent electrode layer and light penetrating object dispose and the electroluminescent cell that forms in this order, it is characterized in that, the infiltration light diffusion layer B that contains the particle of scattered light is arranged between transparent electrode layer and the light penetrating object, the difference of the refractive index of the matrix of formation infiltration light diffusion layer B and the refractive index of transparent electrode layer is below 0.3, and has the layer lower than the refractive index of light penetrating object between infiltration light diffusion layer B and light penetrating object.

15. according to the electroluminescent cell of claim 14 record, wherein, the content of the particle of the scattered light among the above-mentioned infiltration light diffusion layer B is 1～40 volume %, in the weight ratio of the particle of scattered light, is particle diameter 30～400nm more than 60% or 60%.

16. according to the electroluminescent cell of claim 14 record, wherein, the thickness of above-mentioned infiltration light diffusion layer B is more than 2 times or 2 times of average grain diameter of the particle of scattered light.

17. according to the electroluminescent cell of claim 11 or 14 records, wherein, the particle of scattered light is silicon dioxide, cataloid, titanium dioxide, zirconium dioxide, ITO (tin indium oxide), ATO (antimony tin) or aluminium oxide.

18. according to the electroluminescent cell of any one record in the claim 1～3,11,14, wherein, this light penetrating object is a transparency carrier.

19. according to the electroluminescent cell of any one record in the claim 1～3,11,14, wherein, this negative electrode forms on transparency carrier, and above-mentioned light penetrating object is a protective cover.

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