JP2002222691A - Luminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a luminescent element, equipped with base materials and protection materials with superior translucency, passivation (gas barrier property), oligomer discharge resistance, outgas lowering), anti-water (moisture)- absorbing property, chemical deterioration stability, dimensional and form stability, surface antireflection property, electrical insulation, ultraviolet-ray degradation resistance, and moreover, weather resistance in that film-forming under normal pressure is possible, and further, to provide a luminescence element of high reliability. easy manufacturing and low cost. SOLUTION: The luminescent element is composed of a base material 1, having elasticity, translucency and heat resistance, a lower electrode 4 formed on it having light permeability, a luminescent layer 4, and an upper electrode 4, and further, is of a structure having a silica film and/or a silica series film 3 obtained by oxidation, after applying polysilazane at least on the base material size, as seen from the luminescent layer 3 or both sides, including the opposite side.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting device having a substrate or a protective member having flexibility, translucency, weather resistance, heat resistance, electric insulation and improved passivation. In particular, the present invention relates to an organic EL device using the same.

[0002]

2. Description of the Related Art In an organic EL device, a hole transporting material such as triphenyldiamine is formed on a hole injection electrode such as tin-doped indium oxide (ITO), and a phosphor such as aluminum quinolinol complex (Alq3) is further formed. An element having a basic configuration in which a metal electrode (electron injection electrode) having a small work function, such as Mg, is stacked as a light emitting layer and further formed.
Several hundred to several 10,000 cd / m ² at a voltage of around 10V
And extremely high luminance can be obtained.

As a base material of such an organic EL element, a flexible material such as a resin film has attracted attention in terms of application to portable equipment. When a highly heat-resistant film such as a polyimide or an aramid film is used as the substrate as a flexible substrate, these films have a strong hydrophilicity, so that the outgassing due to water absorption or moisture absorption of the film causes the electrode material to be damaged. In addition, the quality of thin films such as EL films is deteriorated. In addition, the thin film laminate including the base material may be curled, warped, or bumped, or adversely affect factors such as a heat shrinkage coefficient and a coefficient of linear expansion coefficient, such as dimensions and shape deformation.

On the other hand, as a display using an organic EL element, application to a color display such as obtaining three primary colors of blue, green, and red using a fluorescence conversion layer and / or a color filter layer made of a fluorescent material is required. Are being considered.

[0005] A method of combining a single light-emitting layer with a fluorescence conversion layer and / or a color filter layer made of a fluorescent material to form a color display is based on a single organic E-layer.
Since it can be composed only of L elements, it can be said that the method is excellent not only in that the constitution is simple and inexpensive, but also that full color can be obtained by patterning the fluorescent conversion layer and / or the color filter layer.

However, it is extremely difficult to provide a fluorescent conversion layer and / or a color filter layer in a predetermined pattern on the organic EL structure in terms of a patterning technique and damage to the organic EL structure. Further, when a fluorescent conversion layer and / or a color filter layer is formed on a substrate by patterning and an organic EL structure is laminated thereon, a step is formed, so that breakage (discontinuous portion of the film) occurs. Problems such as the inability to function as an organic EL element due to the inability to connect wiring and current flow, and damage to the organic layer and electrodes due to moisture and gas from the fluorescence conversion layer and / or the color filter layer. Or corroded.

As a means for solving such a problem, a method of further forming an overcoat layer on the fluorescence conversion layer and / or the color filter layer has been taken, but the organic layer and the electrode are still formed by moisture and gas. Problems such as damage and corrosion remain.

On the other hand, various studies have been made to form a passivation film. However, the effect of preventing moisture and gas permeation of the film is not sufficient, there is a problem in surface flatness, and the conditions at the time of film formation are different from those of the underlayer. However, this method has a problem that it is not practical because the fluorescent conversion layer and / or the color filter layer, the overcoat layer and the like are damaged.

In particular, when the passivation film is formed by a vacuum process, a method of increasing the thickness of the passivation film to overcome the above-mentioned problem may be considered. However, a thick passivation film takes a long time to manufacture and has low productivity.In addition, a film manufactured by a dry process has a large internal stress and cracks are formed in the obtained passivation film. There is a problem that the effect cannot be exhibited.

[0010]

The object of the present invention is to provide a light-transmitting property, heat resistance, passivation property (gas barrier property, oligomer ejection prevention property, reduction of outgassing), and water absorption resistance (wet).
Excellent productivity, such as excellent stability, chemical degradation stability, dimensional stability, surface anti-reflection properties, electrical insulation, ultraviolet light degradation resistance, and weather resistance, and film formation under normal pressure. Material, to provide a light-emitting element having a protective member,
Accordingly, it is an object of the present invention to provide a light-emitting element which is highly reliable, easy to manufacture, and inexpensive.

[0011]

This and other objects are achieved by the present invention described below. (1) a base material having at least translucency and heat resistance, and a light-transmissive lower electrode formed thereon;
A silica film having a light emitting layer and an upper electrode, and further obtained by applying and oxidizing polysilazane on at least both the substrate side and the opposite side of the substrate as viewed from the light emitting layer;
Alternatively, a light-emitting element having a silica-based film. (2) The light emitting device according to (1), wherein the substrate is formed of glass or a resin material. (3) The light emitting device according to the above (1), which has the silica film and / or the silica-based film between at least the substrate and the light emitting layer. (4) A TFT is formed on the base material.
The light-emitting element according to the above (3), having a light-emitting layer on the FT. (5) the silica film and / or
Alternatively, the light emitting device according to any one of the above (1) to (4), having a silica-based film. (6) The light emitting device according to any one of (1) to (5), wherein the silica film and / or the silica-based film is oxidized under heating and / or humidification. (7) The polysilazane and / or a modified product thereof has a structural unit represented by the following structural formula (1).
The light-emitting element according to any one of (1) to (6).

[0012]

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[R ¹ , R ² and R ³ represent an alkyl group. However, at least one of R ¹ , R ² and R ³ is a hydrogen atom. (8) The light-emitting device according to (7), wherein the total number of carbon atoms in the alkyl group is 6 or less. (9) The silica film and / or silica-based film has a polysilazane having a number average molecular weight of 100 to 50,000 and / or
Alternatively, the light emitting device according to the above (7) or (8), wherein the denatured product is a ceramicized film. (10) The light emitting device according to any one of the above (1) to (9), which is an EL device.

According to (1), a more stable Si ₃ N ₄ film can be obtained by heat treatment in a vacuum.

According to (2) and (3), by forming an SiO _x N _y film between the color filter and the transparent lower electrode, the device can be protected from outgas from the color filter and the like.

According to (4) and (5), the gas generated from the substrate can be suppressed by the passivation film.

According to (6), even with a thick passivation film,
It can be easily formed without using a vacuum device such as sputtering.

According to (7), (8) and (9), the flexibility of the film is improved, and the film having a crack of 0.5 μm is obtained.
Cracks do not occur even at 1.0 micron. As the alkyl, a simple one such as a methyl group is preferable.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

In the light emitting device of the present invention, at least one surface of a substrate is coated with a coating solution in which polysilazane such as perhydropolysilazane is dissolved in, for example, xylene or the like, and is oxidized, that is, steam-oxidized. Or a silica film obtained by heat treatment in the air at the same time or thereafter. The base material is preferably formed of a material such as a resin having flexibility, translucency and heat resistance, and exists as a protective member (for example, a protective film) of a coating body such as various electronic devices. And may be present as a component thereof, for example, as a substrate.

For example, when a silica film as described above is provided on a resin base material, the heat resistance, the surface flatness, and the light transmission are maintained while the flexibility of the resin is maintained. And improvement of many properties such as improvement of the passivation of the base material, resistance to water absorption (wet), chemical deterioration, dimensional stability, UV light deterioration resistance, and surface reflection reduction. it can. In addition, a long life and weather resistance can be provided as a combined action of these. That is,
Since the water vapor and oxygen permeability are extremely low, the light emitting element can be prevented from deteriorating in performance and have a long life. Further, since a dense film can be obtained, the strength is improved and the corrosion resistance is excellent. further,
Since a flat film can be obtained, in addition to the translucency, an electronic device such as a light emitting element does not cause a reduction in optical function. Also, the adhesion between the substrate and the silica film is good.

A substrate, a functional film formed on the substrate,
For example, it is possible to passivate an optical functional film such as a filter and an electrode layer formed thereon and a functional thin film such as a light-emitting layer, and the substrate is released from the functional film formed on the substrate or the substrate. These element constituent layers can be protected from moisture, gas, and the like.

Further, such a silica film is obtained by applying a polysilazane-containing coating solution such as perhydropolysilazane and performing steam oxidation and / or heat treatment (including drying treatment). This manufacturing method is a suitable method that enables a silica film to be generally formed on a resin substrate having low heat resistance under normal pressure by a process technique having high productivity such as wet coating. As a method of forming a silica film at a low temperature, there are CVD and PVD methods, but compared to these methods, a special device unique to a vacuum film forming device is not required, and the film is formed by application under normal pressure. It is easy, productivity is improved, and cost is advantageous. Therefore, it can be easily formed on a substrate on which a filter layer or the like has already been formed, and the damage to the underlying layer such as the filter layer is extremely small.

In applications where flexibility is not so required, glass may be used as a base material. By coating on soda glass, elution of Na ⁺ ions can be prevented, and
Even when immersed in pure water of about 24 hours for about 24 hours, the eluted Na ⁺ becomes equivalent to 1.6 wt% or less of alkali-free glass due to the silica coat made of polysilazane. Therefore, the cost of the substrate glass can be reduced. For example, a 0.7 mm thick soda lime glass and 20
% Solution is wet-coated by spin coating to a thickness of 1.5 μm, dried, and then subjected to a heat treatment at 500 ° C. for 1 hour in an N ₂ atmosphere to prevent contamination due to components inside the glass, and to prevent expensive alkali-free substrates. It became possible to substitute. In this case, the obtained barrier layer is a SiO _x N _y film having better barrier properties than the SiO ₂ film, more specifically, a mixed structure of SiO _x and SiN _y (nitrogen and oxygen ratio O / (O
+ N) (approximately 50 to 80%).

The flexible base material used in the present invention is preferably a resin material. Further, particularly, the glass transition point Tg
A resin base material having translucency and heat resistance at 65 ° C or higher and / or 70 ° C or higher is preferable.

As a substrate made of a resin having translucency and heat resistance, a polyethylene terephthalate film (Tg69) is used.
° C), polyethylene naphthalate heat-resistant film (Tg1
13 ° C); ethylene trifluoride chloride resin [PCTFE: NEOFLON CTFE (manufactured by Daikin Industries, Ltd.)] (heat-resistant temperature 1
50 ° C.), polyvinylidene fluoride [PVDF: Denka DX film (manufactured by Denki Kagaku Kogyo)] (heat-resistant temperature 1
50 ° C .: Tg 50 ° C.), polyvinyl fluoride (PV
F: Tedlar PVF film (manufactured by DuPont)] (heat-resistant temperature: 100 ° C.) or a homopolymer such as ethylene tetrafluoride-perfluorovinyl ether copolymer [PFA: neoflon: PFA film (manufactured by Daikin Industries, Ltd.) (heat-resistant temperature 260 ° C), ethylene tetrafluoride-propylene hexafluoride copolymer [FEP: Toyofuron film FEP type (manufactured by Toray Industries, Inc.)] (heat-resistant temperature 200 ° C), ethylene tetrafluoride-ethylene copolymer [ETFE: Tefzel ETFE film (manufactured by DuPont) (heat-resistant temperature 150 ° C), AFL
EX film (manufactured by Asahi Glass Co., Ltd .: Tg83 ° C.)] or other fluorine-based film such as a copolymer; aromatic dicarboxylic acid (for example, terephthalic acid / isophthalic acid) -bisphenol-
Copolymerized aromatic polyester with a divalent phenol such as A [PAR: Casting (manufactured by Kaneka Chemical Co., Ltd.) Elmec, heat resistance temperature 290 ° C: Tg 215 ° C], [new PA
R "MF series" (made by Unitika), MF-200
Polysulfate [PSF: Sumilite FS-1200 (manufactured by Sumitomo Bakelite)] (Tg 190 ° C), polyether sulfone (PES: Sumilite FS-5300 (Sumitomo Bakelite)] (Tg 223 ° C) Polycarbonate film [PC: Panlite (manufactured by Teijin Chemicals Ltd.)] (Tg 150 ° C.), [ITO film, buffer film, laminated composite heat-resistant PC film (manufactured by Teijin Limited) HT-60, Tg205 ° C]; amorphous polyolefin-based resin [APO (manufactured by Mitsui Chemicals, Inc.), cycloolefin resin; ZEONOR: ZEON CORPORATION (Tg: 105 to 16)
3 ° C)], functional norbornene resin [AR
TON (Japanese synthetic rubber)] (Heat-resistant temperature 164 ° C: Tg1
71 ° C.), polycyclohexene (PCHE: manufactured by Asahi Kasei Corporation) Tg 218 ° C .; polymethacrylate resin (PMM
A) (Mitsubishi Rayon and Sumitomo Chemical: Tg80-114
C); olefin-maleimide copolymer [TI-160
(Manufactured by Tosoh Corporation)] (Tg 150 ° C or more), para-aramid (Aramika R: Asahi Kasei) (heat-resistant temperature 200 ° C), fluorinated polyimide (heat-resistant temperature 200 ° C or more), polystyrene (Tg 90 ° C), polyvinyl chloride (Tg 70 to 80)
° C) and cellulose triacetate (Tg 107 ° C).

[0027] From among these, it may be appropriately selected and used according to the purpose and application. In particular, non-halides are preferred from the viewpoint of environmental purification. Specifically, polyether sulfone (PES) resin, heat-resistant polycarbonate resin, which has particularly good transparency, heat resistance, and dimensional stability,
Amorphous polyolefin resin [polycyclohexene (P
CHE)], aromatic polyester-based resins (eg, polyarylate resins), and the like, and these are preferably used for at least a part of the base material. In particular, of course, a resin having high water absorption is of course, and an EL light-emitting film is extremely weak to water vapor and moisture as an outgas component, and silica and / or a silica-based passivation film obtained by low-temperature wet coating with polysilazane are used on at least one surface of the film. Is effective in improving the gas barrier properties of water, water vapor, O _{2 and the} like. In addition, long wide film processing,
Both single-wafer batch processing is effective from the viewpoint of economy.

Further, a composite film for LCDs (Eleclear, HT-60, manufactured by Teijin Limited) in which a polycarbonate film is coated on both upper and lower sides with a gas-barrier solvent-resistant layer and an ITO conductive film is provided on one side thereof, etc. It can be used as it is as a base film.

The glass transition point Tg of the resin substrate is 65 ° C. or higher, preferably 70 ° C. or higher, more preferably 180 ° C. or higher, and particularly 230 ° C. or higher, although the upper limit is not particularly limited. Especially 300 ° C, and even 2
It is about 50 ° C. Further, the heat-resistant temperature or the continuous use temperature is 80 ° C. or higher, preferably 160 ° C. or higher, particularly 200 ° C.
The above is preferred, and the upper limit is preferably as high as possible. Although not particularly limited, it is usually about 250 ° C. However, it can be used as a package protection member for an element (for example, a resin base material for a laminate film) at 80 ° C. or higher. The thickness of the resin substrate is appropriately determined depending on the purpose and application, required strength, bending rigidity, and the like. When used as a protective member, the thickness is usually 5 to 150 μm, preferably 35 μm.
１135 μm. In general, when the resin base material is thin, it is difficult to obtain the effect of surface protection.
In general, when the thickness is increased to about 000 μm, flexibility,
The light transmittance tends to decrease. In addition, for example, PES
(Sumitomo Bakelite optical grade, smoothing FS-
1300 series) is 50 μm thick and has a visible light transmittance of almost 90
%, And the color filter is provided on the substrate immediately adjacent to the viewer.
The L element can be sufficiently used at this level of light transmittance.

Note that having translucency means transmitting 60%, preferably 70%, and more preferably 80% or more of light in the visible light region (particularly, the emission wavelength region of the device).

The resin substrate has an MOR showing the degree of molecular orientation.
The value (Molecular Orientation Ratio) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, and particularly preferably 1.0 to 1.8. When the MOR is within the above range, the deformation of the coated body is reduced. The MOR value indicating the degree of molecular orientation is, for example, Compartec 1998.
"Quality Control of Films and Sheets Using Microwave Molecular Orientation Meter" Shigeyoshi Osaki, Seikei-Kakou Vol.7 No.11 1995
`` Molecular orientation behavior with biaxial extension '' Yasunobu Zushi, Takahiro Niwa,
It is described in the literature of Sadao Hibii, Shinichi Nagata, Tachi.
The greater the MOR value, the greater the anisotropy, with 1.0 representing random.

Regarding the degree of molecular orientation, even in the case of the same resin film, the MOR value may differ depending on the portion. In particular, in a film manufactured by the biaxial stretching method, the degree of orientation tends to be high at an end portion held for stretching. For this reason, even if the resin is excellent in the degree of molecular orientation, it may be used after checking the degree of molecular orientation in each part of the resin film to be used and confirming that it is within the above-mentioned degree of orientation.

The MOR can be measured, for example, by measuring the transmitted microwave intensity while rotating the sample. That is, the interaction between the microwave electric field of a certain frequency and the dipole constituting the polymer substance is related to the inner product of the vectors of the two, and when the sample is rotated in the microwave polarized electric field, the dielectric constant Due to the anisotropy of
The transmitted microwave intensity changes, and as a result, the degree of molecular orientation can be known. As the microwave used for the measurement,
Although not particularly limited, for example, 4 GHz, 12 GHz
And so on. As a measuring instrument applying this principle,
For example, a molecular orientation meter MOA-5 manufactured by Shin Oji Paper Co., Ltd.
001A, 5012A, MOA-3001A / 3012
A and so on. In addition, X-ray diffraction, infrared dichroism,
It can also be determined by a polarized fluorescence method, an ultrasonic method, an optical method, an NMR method, or the like.

The silica film coated on the substrate, preferably a resin substrate, of the present invention is formed using polysilazane and / or a partially modified product. The thickness of such a silica film is preferably about 0.01 to 15 μm, and more preferably about 0.1 to 10 μm. With such a thickness, the function as a protective film is sufficient, and flexibility can be maintained in applications requiring flexibility. On the other hand, if it is too thin, it cannot function as an insulating and heat-resistant surface flattening passivation film required for a protective film and a color filter overcoat film, and if it is too thick, it needs flexibility. Then it becomes easy to be inhibited.

The sol-gel method of obtaining a silica film by a typical wet coating method requires baking at about 450 ° C. in the air to achieve almost complete silica conversion, as shown below. Large weight loss due to elimination of alkoxy group,
Therefore, volume shrinkage is large, and cracks occur at a film thickness of at least 0.5 μm or more. However, in the case of silica conversion using polysilazane and / or a partially modified product thereof, due to the reaction mechanism described below, weight increase occurs at the time of silica conversion, volume shrinkage is small, and cracking is sufficiently performed at a temperature that can withstand the resin at the time of silica film conversion. Is less likely to occur.

[0036]

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The polysilazane used in the present invention is a polymer having a silicon-nitrogen bond as shown below.
i-N, Si-H, SiO 2 consisting of N-H or the like, Si ₃ N
₄ and a ceramic precursor inorganic polymer such as an intermediate solid solution of SiO _x N _y . Usually, perhydropolysilazane whose side chains are all hydrogen is used. It is presumed that perhydropolysilazane has a linear structure and a ring structure centered on a 6- and 8-membered ring. Its molecular weight is about 600-2000 in terms of number average molecular weight (Mn) (in terms of polystyrene), is a liquid or solid substance, and differs depending on the molecular weight.

[0038]

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These are commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane-containing coating solution.

As the organic solvent, it is not preferable to use an alcohol which easily reacts with polysilazane. Specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, and ethers such as aliphatic ethers and alicyclic ethers can be used. Specifically, pentane, hexane,
Hydrocarbons such as isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride And halogenated hydrocarbons such as ethylidene chloride, trichloroethane and tetrachloroethane, and ethers such as ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyl dioxane, tetrahydrofuran and tetrahydropyran.

When these solvents are used, they may be selected to adjust the solubility of the polysilazane, the evaporation rate of the solvent, and the increase in the concentration of the solution, and a plurality of types of solvents may be mixed according to the purpose.

The content of polysilazane in the polysilazane-containing coating solution is about 0.2 to 35% by weight, although it depends on the intended thickness of the silica film and the pot life of the coating solution.

The organic polysilazane may be a derivative in which a hydrogen moiety bonded to Si is partially substituted with an alkyl group or the like. By having an alkyl group, especially a methyl group having the lowest molecular weight, the adhesion to the underlying material is improved, and the hard and brittle silica film can have toughness. Generation is suppressed. As the alkyl group, an alkyl group having preferably 1 to 4 carbon atoms, in particular, improvement of the purity of amorphous silica after silica conversion and passivation property, outgas generation by heat, thermal expansion and the like are rarely reduced. From the viewpoint, those having 1 carbon atom are preferred. However, in order to increase the viscosity of the non-aqueous solution or increase the thickness of the silica film depending on the application conditions, a tertiary butyl group having 4 carbon atoms can be used.

The degree of substitution by this alkyl group is as follows.

[0045]

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[R ¹ , R ² and R ³ represent an alkyl group. However, at least one of R ¹ , R ² and R ³ is a hydrogen atom. ], 20% or less of the hydrogen atoms in the structural unit are preferably substituted with an alkyl group, particularly a methyl group, particularly preferably 10% or less, more preferably about 0.5 to 10%.

The derivative having an alkyl group may be used as an underlayer of a polysilazane silica film. That is, the first base which is a polysilazane derivative having an alkyl group
After forming this layer, a second layer is further formed with polysilazane to form a two-layer structure. Such a two-layer structure includes a color filter on a glass substrate and a patterned color filter layer, or a color filter having a structure in which a color resist is overcoated with a UV curable acrylic resin or the like. This is effective as a means for increasing affinity when providing a passivation layer. That is, a first layer for improving affinity is provided, and a second layer having excellent passivation is formed thereon. Therefore, the first layer does not need to have such a large thickness as the underlayer, and is at least equal to or less than the second thickness.

Further, by simplifying the above process only for the first layer, particularly when a glass substrate is used as a measure for improving productivity and yield, a part of hydrogen of polysilazane which can be made to have a large limit film thickness is converted to an alkyl group. It is good to use the substituted one. That is, when an alkyl group-substituted one is used, flattening of the color filter layer as an overcoat layer and outgas passivation from the color filter or the like by the converted silica film are simultaneously performed with Na from the low-cost blue plate glass substrate. Since the transfer of ions is also passivated, there is no problem even if non-alkali glass is not used.

Further, if necessary, a photopolymerization initiator may be contained. By containing a photopolymerization initiator, particularly when the alkyl group site of the first layer of the base is a reactive double bond such as an alkylene group, a silica forming reaction is promoted, and a more dense silica film is obtained. The performance as an underlayer for forming the second layer is particularly enhanced. Perhydropolysilazane promotes the composite of a micro inorganic filler (SiO ₂ ) and an organic polymer by introducing the organic silazane in a range that does not impair the inherent characteristics of the inorganic polymer. In addition, it contributes to “thickening the film”, “improving the stability”, “improving the film thickness limit”, and “improving the flatness”. In particular, it promotes alloying due to high compatibility with an acrylic resin or the like.
It has been confirmed that they are compatible in a size of about 00 °.

As the photopolymerization initiator, known to known photopolymerization initiators can be used. Particularly, commercially available products that are easily available are preferable.
Further, a plurality of photopolymerization initiators may be used. Examples of the photopolymerization initiator include arylketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoylbenzoates, α-acylo) Oxime esters), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, and other photopolymerization initiators. In particular, the use of an acylphosphine oxide-based photopolymerization initiator is preferred. Further, the photopolymerization initiator can be used in combination with a photosensitizer such as an amine. Specific examples of the photopolymerization initiator include the following compounds.

4-phenoxydichloroacetophenone,
4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)
-2-hydroxy-2-methylpropan-1-one, 1
-(4-dodecylphenyl) -2-methylpropane-1
-One, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-
{4- (Methylthio) phenyl} -2-morpholinopropan-1-one.

Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 3,3 ', 4,4'-tetrakis (t-
Butylperoxycarbonyl) benzophenone, 9.1
0-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4 "-
Diethyl isophthalophenone, α-acyloxime ester, methylphenylglyoxylate.

4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone. 2,4
6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2,6
-Dimethylbenzoyldiphenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-
Trimethylpentyl phosphine oxide.

The photopolymerization initiator contributes little to the conversion of the inorganic polysilazane to silica, and if it is too large, the denseness of the converted silica film is impaired. Therefore, in the coating solution, about 0.01 to 5% by mass, and in the case of organic polysilazane, the UV curable resin component 100
Preferably, the content is 20% by mass or less based on parts by weight.

If necessary, a catalyst may be used to accelerate the reaction. As the catalyst, a catalyst capable of curing polysilazane at a lower temperature is preferable. For example, gold,
Metal catalysts composed of fine particles of a metal such as silver, palladium, platinum, and nickel (Japanese Patent Application Laid-Open No. 7-19686), and their carboxylic acid complexes (Japanese Patent Application Laid-Open No. 5-93275) are exemplified. Further, instead of adding the catalyst to the polysilazane solution, the coated molded article is directly contacted with a catalyst solution, specifically, an aqueous amine solution, as proposed in JP-A-9-31333, or It is also preferable to adopt a method such as exposing to the vapor for a certain period of time.

As described above, polysilazane is a ceramic precursor polymer, and forming a silica film using the same requires 450 ° C. or more by baking in air. By combining steam oxidation and / or heat oxidation in an air atmosphere below, a dense silica film can be obtained even at 100 ° C. or less, and a film having low heat resistance such as a plastic film can be formed. In particular, a methyl group-substituted polysilazane capable of increasing the critical film thickness at which cracks occur has a particularly effective silica conversion efficiency by humidification. Therefore, any method of heating, steam oxidation, or a combination of heating, steam oxidation, and heating in an air atmosphere may be used for forming the silica film. In particular, the vapor of a 5 wt% aqueous solution of trimethylamine as a catalyst (no phase)
Polysilazane coating solution (Mn 100-5 of polysilazane)
0000) at 25 ° C. for 2 minutes after gas phase contact,
By holding for 5 minutes in an H atmosphere, a siliceous ceramic is formed. This method makes it possible to form a ceramic silica layer by continuous application and curing on the plastic long film or the like.

Further, for example, a Mn of 100 to 50,000
Lysilazane and acetylacetonato complex (Ni, Pt, P
d, Al, Rh, etc.)
／/ polysilazane atomic ratio is 1.0 × 10^-6 Range of ~ 2
And the complex-added polysila having an Mn of about 200,000 to 500,000.
Low temperature baking at 50-350 ° C .;
Metals of 5 μm or less (Ag, Au, Pd, Ni, etc.)
In addition to 100-50,000 polysilazane, 150-3
By firing at 70 ° C at low temperature, silica ceramic film
Is obtained. In this case, N_Two Or NH_Three Under atmosphere
When baked at 250 ° C or more, silicon nitride was partially formed.
Although it deviates slightly from the stoichiometric composition, _xN layer, Si
N_yFilm close to the layer (SiO_xN_y : O / (O + N) is about 50
To 80%), and passivation even for thin layers
Performance is improved.

Further, a silicide nitride film described in JP-A-10-194873 can also be used. That is, a 20 wt% xylene solution of modified polysilazane of Mn = 500 to 10,000 obtained by dehydrocondensing polysilazane using ammonia or hydrazine is applied to a thickness of 0.3 μm by a spin coater, and dried on a hot plate (100 ° C.). Then, in a vacuum heating furnace under a vacuum of 0.001 Pa, 600
Baking at 30 ° C. for 30 minutes to obtain a film thickness of 0.1 μm
And a denser silicide nitride film having good passivation properties can be obtained.

The means for applying the polysilazane-containing liquid is not particularly limited, and any known to well-known methods can be employed. For example, methods such as dipping, flow coating, spraying, bar coating, gravure coating, roll coating, blade coating, air knife coating, spin coating, slit coating, microgravure coating, etc. are used. it can. If the coating composition contains a solvent after coating, it is dried to remove the solvent, and for the organic polysilazane-containing system, then, if necessary, cured by irradiating ultraviolet rays or the like, and then heated or left at room temperature. Let it cure. Curing can also be accelerated by contact with an aqueous solution or vapor of amines or acids.

The wet film thickness is 2 times the final film thickness.
It becomes thicker by about 0 to 30%.

Particularly, in an organic polysilazane containing an acrylic resin having an ethylenically unsaturated double bond,
When forming the silica film, an active energy ray such as an ultraviolet ray or an electron beam may be irradiated. In particular, when the coating contains a photopolymerization initiator, it is necessary to irradiate light having a wavelength necessary for exciting the photopolymerization initiator, for example, UV light. In addition, even when no photopolymerization initiator is contained, the reaction is promoted by irradiating an electron beam, and a dense silica film hybridized with an organic polymer is easily obtained.

As an active energy ray for curing polysilazane, ultraviolet rays are particularly preferable. However, it is not limited to ultraviolet rays, and an electron beam or other active energy rays can be used. Xenon lamps, pulsed xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps and the like can be used as the ultraviolet light source.

Further, a plasma treatment may be performed when and / or after the formation of the silica film. By performing the plasma treatment, the surface is ashed and cleaned, and a silica film having a stoichiometric composition is obtained. The plasma treatment is preferably an O ₂ plasma treatment.

The silica film of the present invention may have a base layer for improving the adhesion to a substrate, a fluorescent conversion layer containing a fluorescent substance, a color filter layer, a coating layer, and the like.

The underlayer has a light-transmitting property, an insulating property, and a heat-resistant property and has good adhesion to a substrate, a fluorescent conversion layer containing a fluorescent substance, a color filter layer, a coating layer, and the like. Although not particularly limited, an organic-inorganic hybrid resin layer connected by a covalent bond or a resin layer highly filled with ultrafine particles is preferable.

Examples of the organic-inorganic hybrid resin layer connected by a covalent bond include the following.

(1) 10 g of urethane acrylate (containing an average of 15 acryloyl groups per molecule) and a xylene solution of perhydropolysilazane (solid content: 20% by weight,
Number average molecular weight Mn ≒ 1000, manufactured by Tonen, trade name: L11
0) 15 g, and stirred for about 1 hour at room temperature (urethane acrylate: 150 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator, 2-hydroxy- 5- (2-acryloyloxyethyl) phenylbenzotriazole: 1000 mg, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sevanate: 200 mg as a light stabilizer: butyl acetate: 30 g Is coated with a solution of several μm using a doctor blade or the like, and after drying the solvent, using a high-pressure mercury lamp,
A transparent cured product obtained by UV irradiation in an air atmosphere at 3000 mJ / cm ² and a wavelength of 300 to 390 nm.

(2) UV / optical parts for optical components manufactured by JSR Corporation
In the case of EB-curable resin (Z series), especially the wavelength of visible light
Of smaller particle size 0.01μm (10nm)
SiO _Two De with a photosensitive acryloyl group introduced into the particles
solite Z7500 series (Z7501, Z7503, KZ71714)
Organic / inorganic hybrid materials containing organic solvents
After drying the coating film, 1.0 J / cm^Two U
V cured resin layer.

(3) Zirconia-modified polysilsesquioxane (trade name: ZR, manufactured by Kasei Kagaku Kogyo KK)
S, partially Zr-substituted, R-,
Thermosetting organic-inorganic hybrid resin of a ladder structure similar polymer having an RO-group).

Further, after forming any one of the underlayers (1), (2) and (3), an oxygen plasma treatment is performed so that the underlayer becomes closer to a siliceous material, and the polysilazane conversion of the upper layer is performed. When the layer is formed, the coverage due to the improvement of the affinity between the two is also improved, and the effect of improving the passivation of the underlayer is added.

The resin layer in which the ultrafine particles are highly filled is made of UV / EB having an acrylic double bond in the resin material.
Curing, organic peroxide thermosetting resin, ring-opening polymerization thermosetting resin of epoxy ring, co-condensation resin with alkoxysilyl group-containing acrylic resin as aluminum chelate compound as condensation reaction catalyst, non-yellowing isocyanate group-containing urethane polymer, It is preferable to use one or two or more of a hydroxyacrylate resin, a polyester and a transparent polyurethane resin condensed with a polyether (based hydroxyl group-containing polyol) prepolymer. The ultrafine particles highly filled in this resin include SiO ₂ , Al ₂ O ₃ , ZrO ₂ , Ce ₂
O ₃ , SiO, SiO _x N _y , Si ₃ N _{4 and the} like can be mentioned, and particularly, SiO ₂ fine particles and SiO _x N _y fine particles are preferable. The average primary particle size of these ultrafine particles is 0.005.
About 1.0 μm is preferable.

The thickness of these underlayers is 0.05 to 10
It is preferably about μm.

By forming the silica film of the present invention directly on a color filter layer, a fluorescence conversion layer or the like without using an overcoat layer, good flatness can be obtained. In this case, the obtained surface roughness is Rmax 3
It is within 0 nm.

The transmittance of the silica film for emitted light is preferably 60% or more, more preferably 70% or more, and particularly preferably 8% or more.
It is preferably 0% or more. When the transmittance decreases,
Light emission from the light emitting layer itself is attenuated, and the luminance required for the light emitting element tends not to be obtained.

In addition, when inorganic ultraviolet absorbing fine particles (preferably zinc oxide (ZnO) fine particles) are contained in the silica film, they are added to the coating solution.
The size of the fine particles is preferably 0.01 to 0.5 μm in average particle size, and about 25 to 35 vol.
%.

Unlike inorganic semiconductor particles such as CdS, ZnO is non-polluting and more stable in various environments than organic materials. In addition, some are preferable as an organic ultraviolet absorber, and as such, a polymer type obtained by combining a reactive ultraviolet absorber and a polymer is preferable.

For example, as a reactive ultraviolet absorber, there is one having the following structure, and it is RUVA-93 (Otsuka Chemical Co., Ltd.)
Commercially available).

Further, it is also commercially available as a copolymer with MMA or styrene. As such,
For example, there are PUVA-30M and PUVA-30S (both manufactured by Otsuka Chemical Co., Ltd.).
VA-30M-30T, PUVA-50MBA-30
T, PUVA-50MEH (both Otsuka Chemical Co., Ltd.)
Commercially available.

These organic ultraviolet absorbers are used by laminating on a silica film, and the thickness thereof is about 1 to 15 μm.

Further, as the ultraviolet absorber, an ultraviolet long-wavelength fluorescent conversion organic compound or an organometallic complex molecule can be used, such as [Tb (bp
y) ₂ ] Cl ₃ .xH ₂ O (bpy = 2,2′-bipyridine), [Tb (phen) ₂ ] Cl ₃ .xH ₂ O (phe
(n = 1,10-phenanthroline), and a rare earth planar complex, and a symmetric dicyanopyrazine derivative having the following structure are also effective.

As described above, polysilazane is a ceramic precursor polymer, and forming a silica film using the same requires 450 ° C. or more by baking in air. That is, by combining steam oxidation in the presence of a catalyst, a dense silica film can be obtained even at 100 ° C. or less, and a film can be formed on a substrate having low heat resistance such as a plastic film. Particularly, as a catalyst, a polysilazane coating solution (Mn of polysilazane 100 to 50,000) is applied to a vapor (gas phase) of a 5 wt% aqueous solution of trimethylamine.
Is gas-phase contacted at 25 ° C. for 2 minutes, and then maintained at 95 ° C. in an 80% RH atmosphere for 5 minutes to form a siliceous ceramic. This method enables continuous coating and curing on the plastic long film and the like. Further, for example, Mn 100 to 5
0000 polysilazane and acetylacetonato complex (N
i, Pt, Pd, Al, Rh, etc.) by heat reaction, the glycidol / polysilazane atomic ratio is 1.0 × 10 ^−6.
To 2 and a Mn of about 200,000 to 500,000, a low-temperature baking at 50 to 350 ° C. or a metal (Ag, Au, Pd, Ni
Etc.) to a polysilazane having Mn of 100 to 50,000,
By firing at a low temperature of 150 to 370 ° C., a silica ceramic film is obtained. The specific operation is performed by a known method.

The wet film thickness is 2 times the final film thickness.
It becomes thicker by about 0 to 30%.

As described above, the light emitting device of the present invention having a silica film on a resin substrate may be composed of a resin substrate and a silica film. It may be provided as a member, an antireflection film, or a constituent member. Alternatively, it may be provided as a passivation member between a base material and an underlayer having various functions formed on the base material, and a functional film further formed thereon.

For applications where the EL element emission life is not so severe, polyvinylidene fluoride, ETFE, PC
Fluorine film with high water vapor barrier properties such as TFE (Asahi Glass CS treatment is applied to the surface), partially methyl-substituted polysilazane (thickness of 1 μm or more) converted, fine methyl group-containing silica film, package film, especially film base Use as a package film that wraps the entire flexible EL device using the material is also effective in improving the reliability of the EL device.

FIG. 1 shows a configuration example of a color display using the light emitting device of the present invention. The color display shown in FIG. 1 has a fluorescent conversion layer and / or a color filter layer 2 containing a fluorescent substance and a barrier layer 3 on a substrate 1.
And a light emitting element structure 4 including an electron injection electrode, a hole injection electrode, a light emitting layer, and the like. The fluorescence conversion layer and / or the color filter layer may be two or more layers as necessary. Further, a sealing plate 5 for sealing the light emitting element structure 4 as necessary may be provided.

In the light emitting device of the present invention, emitted light is extracted from the substrate side preferably through a fluorescence conversion layer and / or a color filter layer.

[Organic EL Element] An organic EL structure that is preferable as a light emitting element structure is usually made of an IT
It has a structure in which a hole injection electrode (positive electrode) such as O, an organic layer such as a hole injection / transport layer, a light emitting layer, and an electron injection / transport layer, and an electron injection electrode (negative electrode) are sequentially stacked.
In addition, the base may have a color filter layer, a fluorescence conversion layer, and an overcoat layer.

For the color filter layer, a color filter used in a liquid crystal display or the like may be used, but the characteristics of the color filter are adjusted in accordance with the light emitted from the organic EL element to optimize the extraction efficiency and color purity. It should just be. The light to be cut at this time is 560 nm in the case of green.
Light of the above wavelength and light of a wavelength of 480 nm or less,
In the case of blue, the light has a wavelength of 490 nm or more.
This is light having a wavelength of 0 nm or less. It is preferable to adjust the chromaticity coordinates of the NTSC standard or the current CRT using such a color filter. Such chromaticity coordinates can be obtained by using a general chromaticity coordinate measuring instrument, for example,
It can be measured using M-7, SR-1, or the like. The thickness of the color filter layer may be about 0.5 to 20 μm.

Further, an optical thin film such as a dielectric multilayer film may be used instead of the color filter.

The fluorescence conversion layer absorbs EL light and emits light from the phosphor in the fluorescence conversion layer, thereby converting the color of the emitted light. The composition is formed from a binder, a fluorescent material, and a light absorbing material.

As the fluorescent material, basically, a material having a high fluorescence quantum yield may be used, and it is preferable that the material has strong absorption in an EL emission wavelength region. Specifically, a fluorescent substance having a maximum emission wavelength λmax of the fluorescence spectrum of 580 to 630 nm is preferable. Actually, dyes for laser are suitable, and rhodamine-based compounds, perylene-based compounds, cyanine-based compounds, phthalocyanine-based compounds (including subphthalocyanine, etc.), naphthalimide-based compounds, condensed-ring hydrocarbon-based compounds, condensed-heterocycles Compounds, styryl compounds and the like may be used.

As the binder, basically, a material that does not quench the fluorescence may be selected, and a binder that can be finely patterned by photolithography, printing, or the like is preferable. In addition, a material that does not suffer damage during the formation of ITO or IZO as the positive electrode is preferable.

The light absorbing material is used when the light absorption of the fluorescent material is insufficient, but may be omitted when unnecessary. As the light absorbing material, a material that does not quench the fluorescence of the fluorescent material may be selected.

By using such a fluorescence conversion filter layer, x and y preferable in CIE chromaticity coordinates are obtained.
Value is obtained. Further, the thickness of the fluorescence conversion filter layer may be about 0.5 to 20 μm.

The overcoat layer does not need to be particularly provided in the present invention, and the function of the overcoat layer can be shared by forming a silica film directly on the color filter layer and the fluorescence conversion layer. In the case where an overcoat layer is provided as necessary, a thermosetting resin or an ultraviolet-curing resin is preferable, and in particular, the thermosetting resin is preferable because the surface of the organic layer is further flattened by heat at the time of curing. Among them, polysilsesquioxane resin (ladder silicone resin) and acrylic resin are particularly preferable. One type of resin may be used, or two or more types may be used in combination. The overcoat layer is usually applied on the substrate, the fluorescence conversion layer and / or the color filter layer, and is formed by heat curing or ultraviolet curing. The curing temperature of ordinary thermosetting resin is 140-1.
It is about 80 ° C. In the case of an ultraviolet curable resin, UV light is usually applied so that the integrated light amount becomes 1000 to 10000 mJ.

When a color filter for liquid crystal display is diverted, its surface roughness is measured by AFM to obtain Rmax 3
Even if it is sporadically, the irregularity defect which greatly exceeds 30 nm even if it is sporadically should not exist even if it is small. In order to prevent such large protrusions, the 1 μm
Providing a surface flattening overcoat layer having the above thickness is also effective in preventing image degradation such as “black spot” and “short”.

Next, an organic EL structure preferred as a light emitting device of the present invention will be described. The organic EL structure is usually laminated on a silica film as shown in FIG. An example of the configuration is such that a transparent electrode, that is, a positive electrode, a hole injection / transport layer, a light emitting layer, an electron injection / transport layer, and a negative electrode are sequentially laminated.

The organic EL structure of the present invention is not limited to the above example, but may have various structures.
The transport layer may be omitted, or integrated with the light emitting layer, or the hole injection transport layer and the light emitting layer may be mixed. Further, two or more light emitting layers may be provided.

The negative electrode and the positive electrode can be formed by vapor deposition or sputtering, and the organic layer such as the light emitting layer can be formed by vacuum vapor deposition. Each of these films can be patterned by a method such as mask evaporation or etching after film formation, if necessary, whereby a desired light emitting pattern can be obtained.

Next, the organic layer provided in the organic EL device of the present invention will be described.

The organic layer includes a light emitting layer. The light emitting layer is composed of a laminated film of at least one kind or two or more kinds of organic compound thin films involved in the light emitting function.

The light emitting layer has a function of injecting holes (holes) and electrons, a function of transporting them, and a function of generating excitons by recombination of holes and electrons. By using a relatively electronically neutral compound for the light emitting layer, electrons and holes can be easily injected and transported in a well-balanced manner.

The light emitting layer may have a hole injection / transport layer, an electron injection / transport layer, etc. in addition to the light emitting layer in a narrow sense, if necessary.

The hole injecting and transporting layer has a function of facilitating the injection of holes from the hole injecting electrode, a function of stably transporting holes, and a function of preventing electrons.
The electron injection transport layer has a function of facilitating injection of electrons from the electron injection electrode, a function of stably transporting electrons, and a function of preventing holes. These layers increase and confine holes and electrons injected into the light emitting layer, optimize the recombination region, and improve luminous efficiency.

The thickness of the light emitting layer, the thickness of the hole injecting and transporting layer, and the thickness of the electron injecting and transporting layer are not particularly limited, and vary depending on the forming method.
It is preferable that the thickness be in the range of 10 to 300 nm.

The thickness of the hole injecting / transporting layer and the thickness of the electron injecting / transporting layer depend on the design of the recombination / light emitting region, but may be about the same as the thickness of the light emitting layer or about 1/10 to 10 times. When the hole / electron injection layer and the transport layer are separated, the thickness of the injection layer is preferably 1 nm or more, and the thickness of the transport layer is preferably 1 nm or more. At this time, the upper limit of the thickness of the injection layer and the transport layer is usually about 500 nm for the injection layer and about 500 nm for the transport layer. Such a film thickness is the same when two injection / transport layers are provided.

The light emitting layer of the organic EL device contains a fluorescent substance which is a compound having a light emitting function. Examples of such a fluorescent substance include, for example, JP-A-63-26469.
No. 2 discloses at least one compound selected from compounds such as quinacridone, rubrene, and styryl dyes. Also, Tris (8
Quinolinol derivatives such as metal complex dyes having 8-quinolinol or a derivative thereof as a ligand, such as (quinolinolato) aluminum; tetraphenylbutadiene, anthracene, perylene, coronene, and 12-phthaloperinone derivatives. Further, phenylanthracene derivatives described in JP-A-8-12600, JP-A-8-1600
For example, a tetraarylethene derivative described in JP-A-2969 can be used.

It is also preferable to use in combination with a host substance capable of emitting light by itself, and it is also preferable to use it as a dopant. In such a case, the content of the compound in the light emitting layer is preferably 0.01 to 10% by volume, more preferably 0.1 to 5% by volume. Particularly, in the case of a rubrene-based material, the content is preferably 0.01 to 20% by volume. When used in combination with a host substance, the emission wavelength characteristics of the host substance can be changed, light emission shifted to a longer wavelength becomes possible, and the luminous efficiency and stability of the device are improved.

The host substance is preferably a quinolinolato complex, and more preferably an aluminum complex having 8-quinolinol or a derivative thereof as a ligand. Such an aluminum complex is disclosed in JP-A-63-26469.
No. 2, JP-A-3-255190, JP-A-5-7707
3, JP-A-5-258859, JP-A-6-2158
No. 74 and the like.

Specifically, first, tris (8-quinolinolato) aluminum, bis (8-quinolinolato) magnesium, bis (benzo {f} -8-quinolinolato) zinc, bis (2-methyl-8-quinolinolato) aluminum Oxide, tris (8-quinolinolato) indium,
Tris (5-methyl-8-quinolinolato) aluminum, 8-quinolinolatolithium, tris (5-chloro-
8-quinolinolato) gallium, bis (5-chloro-8-
Quinolinolato) calcium, 5,7-dichloro-8-quinolinolatoaluminum, tris (5,7-dibromo-
8-hydroxyquinolinolato) aluminum and poly [zinc (II) -bis (8-hydroxy-5-quinolinyl) methane].

Further, in addition to 8-quinolinol or its derivative, an aluminum complex having another ligand may be used.
8-quinolinolato) (phenolato) aluminum (III)
, Bis (2-methyl-8-quinolinolato) (ortho-
Cresolato) aluminum (III), bis (2-methyl-
8-quinolinolato) (meth-cresolate) aluminum
(III), bis (2-methyl-8-quinolinolato) (para-cresolato) aluminum (III), bis (2-methyl-8-quinolinolato) (ortho-phenylphenolate)
Aluminum (III), bis (2-methyl-8-quinolinolato) (meth-phenylphenolato) aluminum (II
I), bis (2-methyl-8-quinolinolato) (para-
Phenylphenolato) aluminum (III), bis (2-
Methyl-8-quinolinolato) (2,3-dimethylphenolato) aluminum (III), bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolato) aluminum (III), bis (2-methyl- 8-quinolinolato)
(3,4-dimethylphenolato) aluminum (III),
Bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolato) aluminum (III), bis (2-methyl-8-quinolinolato) (3,5-di-tert-butylphenolato) aluminum (III) ), Bis (2-methyl-8)
-Quinolinolato) (2,6-diphenylphenolato) aluminum (III), bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenolato) aluminum (III), bis (2-methyl- 8-quinolinolato)
(2,3,6-trimethylphenolato) aluminum (I
II), bis (2-methyl-8-quinolinolato) (2,
3,5,6-tetramethylphenolato) aluminum (I
II), bis (2-methyl-8-quinolinolato) (1-naphthrat) aluminum (III), bis (2-methyl-8
-Quinolinolato) (2-naphthrat) aluminum (II
I), bis (2,4-dimethyl-8-quinolinolato)
(Ortho-phenylphenolato) aluminum (III),
Bis (2,4-dimethyl-8-quinolinolato) (para-
Phenylphenolato) aluminum (III), bis (2,
4-dimethyl-8-quinolinolato) (meta-phenylphenolato) aluminum (III), bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenolato) aluminum (III), bis (2 4-dimethyl-8
-Quinolinolato) (3,5-di-tert-butylphenolato) aluminum (III), bis (2-methyl-4-ethyl-8-quinolinolato) (para-cresolato) aluminum (III), bis (2-methyl) -4-methoxy-8-quinolinolato) (para-phenylphenolato) aluminum (III), bis (2-methyl-5-cyano-8-quinolinolato) (ortho-cresolato) aluminum (III),
Bis (2-methyl-6-trifluoromethyl-8-quinolinolato) (2-naphthrat) aluminum (III);

In addition, bis (2-methyl-8-quinolinolato) aluminum (III) -μ-oxo-bis (2-
Methyl-8-quinolinolato) aluminum (III), bis (2,4-dimethyl-8-quinolinolato) aluminum
(III) -μ-oxo-bis (2,4-dimethyl-8-quinolinolato) aluminum (III), bis (4-ethyl-
2-methyl-8-quinolinolato) aluminum (III)-
μ-oxo-bis (4-ethyl-2-methyl-8-quinolinolato) aluminum (III), bis (2-methyl-4
-Methoxyquinolinolato) aluminum (III) -μ-oxo-bis (2-methyl-4-methoxyquinolinolato)
Aluminum (III), bis (5-cyano-2-methyl-
8-quinolinolato) aluminum (III) -μ-oxo-
Bis (5-cyano-2-methyl-8-quinolinolato) aluminum (III), bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum (III) -μ
-Oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum (III) and the like.

Other host materials include those disclosed in
Also preferred are phenylanthracene derivatives described in JP-A-12600 and tetraarylethene derivatives described in JP-A-8-12969.

The light emitting layer may also serve as an electron transporting layer. In such a case, tris (8-quinolinolato)
It is preferable to use aluminum or the like. These fluorescent substances may be deposited.

The light emitting layer is preferably a mixed layer of at least one kind of hole injecting and transporting compound and at least one kind of electron injecting and transporting compound, if necessary.
Further, it is preferable that a dopant is contained in the mixed layer. The content of the compound in such a mixed layer is 0.01 to 20% by volume, further 0.1 to 15% by volume.
% Is preferable.

In the mixed layer, a carrier hopping conduction path is formed, so that each carrier moves in a material having a favorable polarity, and injection of a carrier having the opposite polarity is less likely to occur, so that the organic compound is less likely to be damaged. This has the advantage that the element life is extended. Further, by including the above-described dopant in such a mixed layer, the emission wavelength characteristics of the mixed layer itself can be changed, the emission wavelength can be shifted to a longer wavelength, and the emission intensity is increased, The stability of the device can be improved.

The hole injecting and transporting compound and the electron injecting and transporting compound used in the mixed layer may be selected from the hole injecting and transporting compound and the electron injecting and transporting compound described below, respectively.

As the compound capable of injecting and transporting electrons, it is preferable to use a quinoline derivative, furthermore a metal complex having 8-quinolinol or a derivative thereof as a ligand, particularly tris (8-quinolinolato) aluminum (Alq3). It is also preferable to use the above-mentioned phenylanthracene derivatives and tetraarylethene derivatives.

As the compound for the hole injecting / transporting layer, it is preferable to use an amine derivative having strong fluorescence, for example, a triphenyldiamine derivative, a styrylamine derivative, or an amine derivative having an aromatic condensed ring.

The mixing ratio in this case depends on the respective carrier mobility and carrier concentration. In general, the weight ratio of the hole injection / transport compound / electron injection / transport compound is 1
/ 99-99 / 1, more preferably 10 / 90-90
/ 10, particularly preferably about 20/80 to 80/20.

The thickness of the mixed layer is preferably not less than the thickness corresponding to one molecular layer and less than the thickness of the organic compound layer. Specifically, the thickness is preferably 1 to 100 nm, more preferably 5 to 60 nm, particularly preferably 5 to 50 nm.

As a method for forming the mixed layer, co-evaporation in which evaporation is performed from different evaporation sources is preferable. However, when the vapor pressures (evaporation temperatures) are the same or very close, the mixed layers are previously mixed in the same evaporation board. Alternatively, it can be deposited. In the mixed layer, it is preferable that the compounds are uniformly mixed, but in some cases, the compounds may exist in an island shape. The light-emitting layer is generally formed to a predetermined thickness by vapor-depositing an organic fluorescent substance or by dispersing and coating the resin in a resin binder.

Examples of the hole injecting / transporting compound include, for example, JP-A-63-295695 and JP-A-2-19.
1694, JP-A-3-792, JP-A5-
JP-A-234681, JP-A-5-239455,
JP-A-5-299174, JP-A-7-12622
No. 5, JP-A-7-126226, JP-A-8-
Various organic compounds described in, for example, Japanese Patent No. 100172 and EP0650955A1 can be used. For example, a tetraarylbendicine compound (triaryldiamine or triphenyldiamine: TPD), an aromatic tertiary amine, a hydrazone derivative, a carbazole derivative,
Triazole derivatives, imidazole derivatives, oxadiazole derivatives having an amino group, polythiophene and the like. These compounds may be used alone or in combination of two or more. When two or more kinds are used in combination, they may be stacked as separate layers or mixed.

The electron injecting and transporting compound includes quinoline derivatives such as organometallic complexes having 8-quinolinol such as tris (8-quinolinolato) aluminum (Alq3) or derivatives thereof as ligands, oxadiazole derivatives, perylene derivatives, and the like. A pyridine derivative, a pyrimidine derivative, a quinoxaline derivative, a diphenylquinone derivative, a nitro-substituted fluorene derivative, or the like can be used.

The light emitting layer, the hole injection / transport layer, and the electron injection / transport layer can be formed as a uniform thin film.
It is preferable to use a vacuum deposition method. When vacuum deposition is used, the amorphous state or the crystal grain size is 0.2 μm
The following homogeneous thin film is obtained. If the crystal grain size exceeds 0.2 μm, the light emission becomes non-uniform, the driving voltage of the device must be increased, and the charge injection efficiency is significantly reduced.

The conditions for vacuum deposition are not particularly limited.
The degree of vacuum is 0 ^-4 Pa or less, and the deposition rate is 0.01 to 1 nm.
/ Sec. Further, it is preferable to form each layer continuously in a vacuum. If they are formed continuously in a vacuum, impurities can be prevented from adsorbing at the interface between the layers, so that high characteristics can be obtained. Further, the driving voltage of the element can be reduced, and the occurrence and growth of dark spots can be suppressed.

In the case where a plurality of compounds are contained in one layer when a vacuum evaporation method is used for forming each of these layers, it is preferable to co-deposit each boat containing the compounds by individually controlling the temperature.

In the present invention, each organic layer may be formed by a coating method. By forming the organic layer by a coating method, an element can be formed more easily, thereby improving production efficiency and reducing the price of the element. In particular, using a microgravure method or the like, the film thickness is thin and about 30 to 1
The R, G, and B light emitting layers of 00 nm are separately applied in a stripe pattern of about 100 μm width at a pitch of 100 μm, and the base material is printed using the above-mentioned flexible barrier film in a roll-to-roll manner. A method using control is preferred.

Examples of known polymer light emitting materials for organic EL used in the light emitting layer include polymer compounds such as polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives. Specifically, poly (2-decyloxy-1,4-phenylene) (DO-PPP), poly [2,
5-bis [2- (N, N, N-triethylammonium) ethoxy] -1,4-phenylene-alto-1,4
-Phenylene] dibromide (PPP-NEt3 +), poly [2- (2'-ethylhexyloxy) -5-methoxy-1,4-phenylenevinylene] (MEH-PP
V), poly (5-methoxy- (2-propanoxysulfonide) -1,4-phenylenevinylene) (MPS-P
PV), poly [2,5-bis (hexyloxy-1,4)
-Phenylene)-(1-cyanovinylene)] (CN-P
PV), poly [2- (2'-ethylhexyloxy)-
5-methoxy-1,4-phenylene- (1-cyanovinylene)] (MEH-CN-PPV) and poly (dioctylfluorene) (PDF).

Alternatively, as a precursor of a known polymer light emitting material for an organic EL, for example, poly (p-phenylene)
A precursor (Pre-PPP), a poly (p-phenylenevinylene) precursor (Pre-PPV), a poly (p-naphthalenevinylene) precursor (Pre-PNV), or the like can be used.

A known low molecular light emitting material for organic EL and a known polymer material such as polycarbonate (PC),
Polymethyl methacrylate (PMMA), polycarbazole (PVCz), or the like may be used as a mixture.

Further, if necessary, additives for adjusting the viscosity may be used. In particular, when the light-emitting layer and the hole injection layer are formed by uniform thin-film printing of 100 nm or less, it is necessary to dilute the light-emitting polymer to an extremely low concentration, to prevent the flow of the transfer pattern, and to transfer from the plate to the substrate. In order to improve the properties, a small amount of a thickener or a gelling agent that increases the viscosity or the elastic modulus of the solution without affecting the light emitting characteristics of the organic EL may be used as an additive.

As the well-known polymer charge transporting materials, examples of hole transporting materials include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, and phenylenediamines. Derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, polysilanes Compounds, poly (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, polythiophene derivatives , Polyphenylene derivatives, polyphenylene vinylene derivatives, polythiophene derivatives as the electron transporting materials such as polymer compounds such as polyfluorene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polymer compounds such as polyfluorene derivatives, and the like.

Examples of the solvent used for forming these polymer materials by the coating method include ethylene glycol, propylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol moethyl ether, triethylene glycol monomethyl ether, Triethylene glycol moethyl ether, glycerin, N, N-dimethylformamide, N-methyl-2-pyrrolidone, cyclohexanone,
Examples thereof include 1-propanol, octane, nonane, decane, xylene, diethylbenzene, trimethylbenzene, nitrobenzene and the like.

It is preferable that the above-mentioned organic materials are dissolved in the above-mentioned coating solvent so that the respective concentrations become 0.1 to 5% (mass percentage). Regarding the application, an application method using any solution such as a spin coating method, a spray coating method, a dip coating method, a flexographic method, or the like can be used. After the application, the element may be heated with a hot plate or the like for drying the solvent. The heating is preferably performed at a temperature equal to or lower than Tg (glass transition temperature) of the organic EL material, usually at a temperature of about 50 to 80 ° C., and is preferably dried under reduced pressure or an inert atmosphere.

The thickness per organic layer is preferably from 0.5 to 1000 nm, more preferably from 10 to 500 nm, according to the coating method. In the case of using an evaporation method such as a vacuum evaporation method, the thickness is about 1 to 500 nm.

The material of the positive electrode (hole injection electrode) is preferably a material capable of efficiently injecting holes into a hole injection layer or the like, and is preferably a substance having a work function of 4.5 eV to 5.5 eV. Specifically, tin-doped indium oxide (IT
O), zinc-doped indium oxide (IZO), indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), and zinc oxide (ZnO) are preferable. These oxides may deviate somewhat from their stoichiometric composition. The mixing ratio of SnO ₂ with respect to In ₂ O ₃ is 1 to 20 mass%, more preferably 5 to 12 wt%. The mixing ratio of ZnO to In ₂ O ₃ in IZO is usually about 12 to 32% by mass.

The hole injection electrode may contain silicon oxide (SiO ₂ ) to adjust the work function.
The content of silicon oxide (SiO ₂ ) is preferably about 0.5 to 10% by mol ratio of SiO _{2 to} ITO. S
The inclusion of iO ₂ increases the work function of ITO.

The electrode on the side from which light is extracted has an emission wavelength band,
The light transmittance is usually 400 to 700 nm, particularly preferably 50% or more, more preferably 80% or more, and particularly preferably 90% or more for each emitted light. If the transmittance is too low, the light emission itself from the light emitting layer is attenuated, and it becomes difficult to obtain the luminance required for the light emitting element.

The thickness of the electrode is 50 to 500 nm, especially 50 to 500 nm.
The range of -300 nm is preferred. The upper limit is not particularly limited. However, if the thickness is too large, there is a fear that the transmittance is reduced or the layer is peeled off. If the thickness is too small, a sufficient effect cannot be obtained, and there is a problem in film strength at the time of production and the like.

As the negative electrode, the following can be used as necessary as an electrode having an electron injecting property. For example, K, Li, Na, Mg, La, Ce, Ca, Sr,
A metal element such as Ba, Sn, Zn, Zr, or a binary or ternary alloy system containing them for improving stability, for example, Ag.Mg (Ag: 0.1 to 50 at%);
Al.Li (Li: 0.01 to 14 at%), In.Mg
(Mg: 50-80 at%), Al.Ca (Ca: 0.0
1 to 20 at%).

Further, these alkali metal monovalent ions (eg, Li, Na, K), alkaline earth metal divalent ions (eg, Pt, Zn), and trivalent ions (eg, Al,
In) may form a relatively stable complex with an oxygen complex (eg, acetylacetone, acetic acid, oxalic acid, etc.), and dissolve and apply the complex in a solution to form a thin cathode.

The thickness of the negative electrode thin film may be a certain thickness or more for sufficiently injecting electrons, and may be 0.1 nm or more, preferably 0.5 nm or more, particularly 1 nm or more. Also,
Although there is no particular upper limit, the film thickness is usually 1 to 50.
It may be about 0 nm.

Further, in order to prevent deterioration of the organic layers and electrodes of the device, it is preferable to seal the device with a sealing plate or the like. The sealing plate adheres and seals the sealing plate using an adhesive resin layer in order to prevent moisture from entering. The sealing gas is A
An inert gas such as r, He, N ₂ or the like is preferable. Further, the moisture content of the sealing gas is preferably 100 ppm or less, more preferably 10 ppm or less, and particularly preferably 1 ppm or less. Although there is no particular lower limit for the water content, it is usually about 0.1 ppm.

The material of the sealing plate is preferably the same as the material of the base material described above. The height of the sealing plate may be adjusted by using a spacer and held at a desired height. Examples of the material of the spacer include resin beads, silica beads, glass beads, and glass fibers, and glass beads are particularly preferable.

When a recess is formed in the sealing plate,
The preferred size of the spacer may be in the above range, but is particularly preferably in the range of 2 to 8 μm.

Furthermore, a desiccant, preferably C
aH ₂ may be sealed.

The adhesive is not particularly limited as long as it can maintain stable adhesive strength and has good airtightness, but it is preferable to use a cationic curing type ultraviolet curing epoxy resin adhesive. .

[Inorganic EL Element] The light emitting element structure is as follows.
It may be an inorganic EL structure. An inorganic EL element usually has a structure in which an inorganic light emitting layer is arranged between a pair of electrodes. If necessary, an insulating layer and a dielectric layer may be provided between the light emitting layer and the electrode.

Materials used for the light emitting layer of the inorganic EL (electroluminescence) element include ZnS and Mn / CdSSe as materials for obtaining red light emission, ZnS: TbOF, ZnS: Tb and the like for green light emission.
As a material for obtaining blue light emission, SrS: Ce, (S
rS: Ce / ZnS) n, GaCa ₂ S ₄ : Ce, SrG
a ₂ S ₄ : Ce and the like. Further, SrS: Ce / ZnS: Mn and the like are known as ones that obtain white light emission.

Usually, an EL phosphor thin film has a luminescent center added to a base material. The emission center may be added with an existing transition metal or rare earth in an existing amount. For example, rare earths such as Ce and Eu, Cr, Fe, Co, Ni, Cu, Bi, Ag
Is added to the raw material in the form of metal or sulfide. Since the amount of addition differs depending on the raw material and the thin film to be formed, the composition of the raw material is adjusted so that the thin film has an existing addition amount.

As a method for forming an EL phosphor thin film from these materials, existing methods such as a vapor deposition method, a sputtering method, a CVD method, a sol-gel method, and a printing and baking method may be used.

The thickness of the light emitting layer is not particularly limited, but if it is too thick, the driving voltage increases, and if it is too thin, the luminous efficiency decreases. Specifically, although it depends on the fluorescent material, it is preferably 100 to 1000 nm, particularly 150 to 70 nm.
It is about 0 nm.

In order to obtain a high-luminance sulfide phosphor thin film,
If necessary, it is preferable to form a sulfide phosphor having a composition to be formed at a high temperature of 600 ° C. or higher, or to anneal at a high temperature of 600 ° C. or higher. In particular, a high-temperature process is effective for obtaining a high-luminance blue phosphor.

The substrate of the inorganic EL device is not particularly limited, but is preferably a substrate that can withstand the above heat treatment temperature.

The heat-resistant temperature or melting point that can withstand the above temperature is 600 ° C. or more, preferably 700 ° C. or more, particularly 800 ° C.
The substrate described above is not particularly limited as long as it has an insulating property and can maintain a predetermined strength without contaminating an electrode layer and the like formed thereon. Specifically, alumina (Al ₂ O ₃ ), forsterite (2Mg)
O · SiO _2), steatite (MgO · SiO _2), mullite _{(3Al 2 O 3 · 2SiO 2} ), beryllia (Be
O), aluminum nitride (AlN), silicon nitride (S
iN) and a ceramic substrate such as silicon carbide (SiC + BeO). All of these heat resistant temperatures are 1000 ° C. or higher. Among these, an alumina substrate is particularly preferable, and when thermal conductivity is required, beryllia, aluminum nitride, silicon carbide and the like are preferable.

In addition, quartz, heat-resistant glass,
A thermally oxidized silicon wafer or the like can also be used.

The electrode layer formed on at least the substrate side and exposed to the high temperature of the heat treatment together with the light emitting layer preferably has silicon as a main component. This silicon electrode layer is made of polycrystalline silicon (p-Si),
It may be amorphous (α-Si) or, if necessary, single crystal silicon.

The electrode layer is doped with impurities in order to secure conductivity, in addition to silicon as a main component. The dopant used as the impurity only needs to be able to secure predetermined conductivity, and a normal dopant used for a silicon semiconductor can be used. In particular,
Examples thereof include B, P, As, Sb, and Al. Among them, B, P, As, Sb, and Al are particularly preferable.
The concentration of the dopant is preferably about 0.001 to 5 at%.

The electrode layer is obtained by doping the above-mentioned impurity into silicon as a main component, imparting conductivity, and functions as an electrode. The preferable resistivity of the electrode layer is preferably 1 Ω · cm or less, particularly 0.003 to 0.1 Ω · cm, in order to efficiently apply an electric field to the light emitting layer. The thickness of the electrode layer is preferably 50 to 2000 nm, particularly 100
About 1000 nm.

For the formation of the electrode layer, a vapor deposition method can be used. In the case where a single crystal substrate is used, the substrate can be formed by a known method, and an already formed substrate may be purchased. Examples of the vapor deposition method include a physical vapor deposition method such as a sputtering method and a vapor deposition method, and a chemical vapor deposition method such as a CVD method. Among them CV
Chemical vapor deposition such as Method D is preferred.

In order to form a Si layer by the CVD method, first, silane (SiH ₄ ), silicon chloride or the like is used as a silicon source as a raw material gas, and another element, specifically, the above dopant is added to silicon as required. When including
The chloride, hydride, organic matter, etc. are used as a source.

As the silicon source, silicon fluoride such as SiF ₄ , silicon chloride such as SiCl ₄ , SiH ₄ , S
i ₂ H ₆ , Si ₃ H ₈ , SiH ₃ Cl, SiH ₂ Cl ₂ , S
Examples include silanes such as iHCl ₃ and SiCl ₄ .

As dopants, B, P, As, S
There is no particular limitation as long as b and Al elements can be added. For example, arsines such as AsH ₃ , PH
Phosphine such as _3, phosphoric acid compounds such as POCl _3,
Diboranes such as B ₂ H ₆ , Al (CH ₃ ) ₃ , B (C
H ₃ ) _{3 and the} like are preferred. These reactive gases may be used alone or in combination of two or more. When two or more reactive gases are used in combination, the mixing ratio is arbitrary.

The carrier gas is H ₂ , H
e, Ar, etc. may be used. The reaction temperature is 500
The temperature may be set to about 1000 ° C.

As the chemical vapor deposition method, plasma CVD, normal pressure CVD or the like may be used in addition to the normal low pressure CVD method. Further, the mixing ratio between the carrier gas and the source, the flow rate, and the like may be adjusted to optimal values according to the resistance value of the thin film silicon layer.

In addition to the above-mentioned CVD method, a silicon layer can be formed by an EB vapor deposition method or an RF sputtering method as a physical vapor deposition method.

In addition to the above, a commonly used metal electrode such as platinum, tantalum, nickel, chromium, and titanium may be used.

The other electrode layer is preferably a transparent substrate having a light-transmitting property in a predetermined emission wavelength range in order to extract emitted light. In this case, it is particularly preferable to use a transparent electrode such as ZnO or ITO. ITO is usually In
_{Although 2} O ₃ and SnO are contained in a stoichiometric composition, the amount of O may slightly deviate from this.

The thin-film EL device has an insulating layer between the electrode layer and the fluorescent thin film (light-emitting layer). This insulating layer
Preferably, it is formed of an oxide of the above-mentioned electrode material constituent material. As a method for forming an oxide of an electrode constituent material, a gas containing oxygen such as O ₂ gas may be introduced when forming the electrode. in this way,
When forming an electrode material, a film can be continuously formed from the electrode only by introducing a gas containing oxygen, and the manufacturing process can be simplified.

Further, a thermal oxidation method used in a semiconductor manufacturing process may be used. As the thermal oxidation method, any of a dry O ₂ oxidation method, a wet O ₂ oxidation method, and a steam oxidation method may be used. When the dry O ₂ oxidation method is used, Pb, HCl, Cl ₂ , C ₂ HCl ₃
May be mixed.

The thickness of the insulating layer using such an electrode constituting material is preferably 20 to 500 nm, particularly preferably 50 to 500 nm.
It is about 300 nm.

The insulating layer may be different from the oxide constituting the electrode. In particular, the insulating layer on the side of the other electrode (formed above the light emitting layer) that is not heat-treated is formed separately from the electrode forming step. In this case, the resistivity of the insulating layer is 10 ⁸ Ω · cm or more, particularly 10 ¹⁰ to 10 ¹⁸
It is about Ω · cm. Further, it is preferable that the substance has a relatively high dielectric constant, and the dielectric constant ε thereof is preferably about 3 to 1000.

As the constituent material when the insulating layer is formed separately from the electrodes, for example, silicon oxide (SiO ₂ ), silicon nitride (SiN), tantalum oxide (Ta ₂ O ₅ ), strontium titanate (SrTiO ₃ ), yttrium oxide (Y ₂ O _3), barium titanate (BaTiO _3), lead titanate (PbTiO _3), zirconia (Zr ₂ O _3),
Silicon oxynitride (SiON), alumina (Al ₂ O ₃ ), lead niobate (PbNbO ₃ ), and the like can be given. In addition, in order to secure light transmittance, Si
A transparent ceramic layer containing O ₂ , BaO, B ₂ O ₃ , Al ₂ O ₃ , CaO or the like may be used. The method for forming the insulating layer with these materials is the same as the method for forming the electrode. In this case, the thickness of the insulating layer is preferably 50 to 10
00 nm, especially about 100 to 500 nm.

Further, after forming an insulating layer of an electrode constituting material as necessary, the insulating layer may be further formed double using another material.

[0176]

Next, the present invention will be described more specifically with reference to examples and comparative examples.

Example 1-1 As shown in FIG. 1, the base material 1 was colorless having a thickness of 200 μm, had a total light transmittance of 90% or more, and had a heat resistance of Tg: 230 ° C. A polyethersulfone resin sheet (FS-5300, manufactured by Sumitomo Bakelite Co., Ltd.) was used. The both surfaces of the substrate 1 were modified with polysilazane partially methyl-modified [hydrogen 1 in the structure.
[0at% substituted product] in dibutyl ether (DBE) 20% by mass (L710, manufactured by Tonen Corp., containing Pd catalyst) is coated on both sides by a dip coating method, dried by heating, and then bubbled in pure water. Air (humidified air)
While supplying to a clean oven maintained at 00 ° C., heat in the oven for 2 hours to perform steam oxidation, and then perform a heat treatment at 230 ° C. for 1 hour in an air atmosphere to obtain a dense thickness on both surfaces of the substrate. A flexible transparent substrate having a silica layer containing a minute methyl group of about 1.2 μm was obtained.

Next, on this substrate, as a blue transmission layer, a green transmission layer, and a red transmission layer, a color filter manufactured by Fuji Hunt Co., Ltd., and the cut light was green light of a wavelength of 560 nm or more and 480 nm or less. The filter layer 2 was patterned using light having a wavelength of 490 nm or more, blue light having a wavelength of 490 nm or more, and red light having a wavelength of 580 nm or less.

Next, a xylene solution of the same perhydropolysilazane (Mn = 1000) as described above (concentration: 20 wt%:
The coating solution of Tonen Corp. L710, a product containing several tens of pounds of a Pd catalyst) is coated with a thin layer coater such as a spin coater, a die coater, a flexo coater, or a gravure coater to form a pattern of the color filter. After coating with a spin coater so that a thickness of about 0.5 μm is obtained on the substrate,
As in the case of the above substrate, bubbling air in water was supplied, and heating and steam oxidation were performed at 200 ° C. for 30 minutes to 1 hour in a clean oven. Next, the substrate was oxidized and dehydrated by heating at 230 ° C. for 1 hour on a hot plate. that time,
Because of the Pd catalyst, perhydropolysilazane is converted to a silica film by this heating and steam oxidation,
The barrier layer 3 having a dense silica film is heated continuously at 230 ° C. as it is to completely remove moisture and has a dense silica film.
A μm thick silica film was formed.

Further, ashing was performed with oxygen plasma (output of 2 kW, substrate temperature of 200 ° C.) for 10 minutes. By this treatment, the surface of the barrier layer also serving as the overcoat of the color filter was further cleaned, and a more even and complete a-SiO ₂ passivation layer 3 was formed.

Next, an ITO transparent electrode (hole injection electrode)
Was formed and patterned so as to form pixels of 64 dots × 7 lines (100 × 100 μm per pixel) with a film thickness of 85 nm. Then, the substrate on which the patterned hole injection electrode was formed was subjected to ultrasonic cleaning using a neutral detergent, acetone and ethanol, pulled up from boiling ethanol, and dried. Thereafter, UV / O ₃ cleaning was performed.

[0182] Then, the substrate was transferred to the deposition chamber, and fixed to a substrate holder of a vacuum deposition apparatus, the inside of the tank 1 × 10 ^-4 Pa
The pressure was reduced to the following. Then, poly (thiophene-2,5-diyl) having a thickness of 10 nm was used as a hole injection layer, and TPD was doped with rubrene at a ratio of 1% by mass as a hole transport layer and a yellow light emitting layer. A film was formed to a thickness. The concentration of rubrene is preferably about 0.1 to 10% by mass, and light is emitted with high efficiency at this concentration. The concentration may be determined from the color balance of the luminescent color, and depends on the light intensity and the wavelength spectrum of the blue luminescent layer to be formed thereafter. Further, as a blue light emitting layer, 4'-bis [(1,2,2-triphenyl) ethenyl] biphenyl was simulated at 50 nm, and as an electron transport layer, Alq3 was simulated at 10 nm.

Next, AlLi (Li: 7 at%) was added to 1 nm
And an Al electrode layer was formed to a thickness of 200 nm to form the organic EL element 4. Before sealing as an organic EL display, a desiccant (CaH ₂ ) was mixed with silicon rubber and immobilized by mixing (not shown), and finally a 100 μm-thick PCTFE film (used in Example 2) The film 5 was coated with EVA on ETFE without using a UV absorber) to obtain an organic EL display. This PCTFE film is superior to ETFE in terms of water absorption and water vapor transmission.

As a comparative sample, a 200 μm thick
m, colorless and has a total light transmittance of 90% or more.
g: Polyethersulfone resin (PES) sheet having heat resistance of 230 ° C. (manufactured by Sumitomo Bakelite Co., Ltd., FS
-5300) as a substrate, a color filter is directly provided thereon, and an organic resin overcoat material containing an acrylic resin, a reactive acrylic monomer, a photosensitizer, and a polymerization catalyst is applied thereon to a thickness of 5 μm, and UV Exposure 400mj / cm ²
UV curing, and then heat cured by heating to 150 ° C,
A sample (sample #A) in which a flattening layer was formed by an overcoat layer and no barrier layer was formed.

When a direct current voltage was applied to each of the organic EL color displays produced in this manner and the organic EL color displays were continuously driven at a constant current density of 50 mA / cm ² , the luminance half-life of the inventive sample was 400 hours or more. On the other hand, the comparison sample #A took less than 50 hours. In addition, even a very small minute dark spot was observed in the sample of the present invention, even after 400 hours or more. On the other hand, in Comparative Sample #A, a large number of dark spots having a large diameter of about 100 μm or more were observed within 50 hours.

From these results, it can be seen that the provision of the barrier layer of the present invention has a life equivalent to or longer than that of a display in which a conventional overcoat layer and a barrier layer are provided. Note that substantially the same results were obtained when the color filter layer and the fluorescence conversion filter layer were used in combination.

Note that the obtained organic EL display is
It was lighter than those using a conventional glass substrate and a sealing glass substrate including a comparative sample, and did not cause damage such as breaking of the panel against impact. Thereby, it turned out that it is especially effective as a display for portable devices.

Example 1-2 A Corning 7059 glass substrate was washed as a substrate, immersed in a 0.3% aqueous solution of Shin-Etsu Silicone KBM603, washed with water, and subjected to silane coupling treatment. A baking treatment was performed at 1 ° C. for 1 hour.

Next, a red transer film manufactured by Fuji Photo Film Co., Ltd. was laminated on the substrate at 130 ° C., at a lamination pressure of 2 MPa, and at a lamination speed of 1.4 m / min. Thereafter, the base film of the transer film was peeled off, masked with a red mask, and subjected to collective exposure using a super-high pressure mercury lamp to a predetermined integrated light quantity (50 to 100 mj / cm ² ).

Next, a red pixel is formed by a process using a predetermined developing solution and a developing material, and the red pixel is formed by the above-mentioned ultra-high pressure mercury lamp.
With a light exposure of 0 mj / cm ² , post-exposure was performed on both sides of the back surface of the glass substrate and the pixel formation surface.
The resultant was baked at 120 ° C. for 120 minutes to produce a red pixel color filter.

Further, the same operation as described above was carried out using green and blue transer films to produce red, green and blue filters for high definition full color. If necessary, a black transer film may be laminated on the above R, G, B color filters, using an ultra-high pressure mercury lamp (using a wavelength cut filter at 365 nm), and increasing the integrated light amount to 50 to 100 mj / cm ^2. As
When exposure is performed from the glass substrate side on the back surface of the R, G, and B color filters, the RGB pixels serve as a mask, the back surface is exposed, and a black matrix may be formed by the same operation as the filter.

Next, a polysilazane partially methyl-modified product [the hydrogen substitution rate in the structure was 10 at.
%] Xylene solution (Pd catalyst-containing product)
Coated in the same manner as in Example 1 using a spin coater, and subjected to steam oxidation and baking, a 0.4 μm-thick silica film having a high light transmittance and heat resistance, a very flat and dense layer containing a small amount of methyl groups. I got

Further, 20% by weight of [-(SiH ₂ -NH) _m- ] polysilazane having no methyl group on the silica film
A xylene solution was applied by a spin coater, and subjected to steam oxidation and baking under the same conditions as described above to obtain a 0.4 μm-thick high light transmittance, heat resistance, extremely flat and dense silica film.

Next, in the same manner as in Example 1-1, oxygen plasma ashing, a hole injection layer, a light emitting layer, and other constituent layers were laminated by a dry process to obtain an organic EL device.

Here, the silica film obtained from polysilazane containing no methyl group is extremely dense as an amorphous inorganic silica film and is the best as a water vapor, oxygen gas and barrier film, but has a thickness of 0.6 μm. Then, cracks may occur. On the other hand, the partially methylated polysilazane-modified pair does not crack even when the film thickness exceeds 1.0 μm, and is extremely effective for flattening the surface of the underlying full-color filter and obtaining an excellent EL device. . That is, the smoothness (Rmax measured by AFM
(20 nm or less). For this reason, when the extremely thin organic EL light-emitting layer, ITO transparent electrode thin film, etc. formed on the top are formed in a vacuum process, the flat uniformity is maintained, and the "dark spot" of the organic EL display caused by local unevenness. This was effective in preventing "screen color unevenness".

The inorganic amorphous silica film is extremely excellent as a gas passivation film,
In the high-temperature holding test for the accelerated life degradation evaluation of the display, the generation of the above "dark spots" and the growth of minute dark spots were suppressed, and the "color unevenness of the screen" was generated.

[Embodiment 1-3] As shown in FIG.
An alumina substrate was used as 11. On this substrate 11,
Al electrode 12 is formed with a thickness of 200 nm by RF sputtering.
Done. Next, the SiO _Two : BaO: B_TwoO_Three : Al_TwoO
_Three : CaO in a mass ratio of 45: 30: 12: 1, respectively.
Input power by RF sputtering using a target
Power 1.5kw, O_TwoUnder the conditions of 2% and 0.4 Pa, the film thickness is 100 n
m, crystallized by annealing at 220 ° C. for 4 hours,
A lower insulating layer 13 of a glass ceramic film was formed.

Further, the substrate temperature was set to 200 ° C., and EB
A ZnS: Mn phosphor thin film (light emitting layer) 14 having a thickness of 600 nm was formed by a vapor deposition method, and annealed at 600 ° C. in a vacuum for 10 minutes. Next, the substrate temperature was set to 550 ° C., and ZnS and Sr
S was mixed at a molar ratio of 1: 3, and Ce ₂ S ₃ was further converted to Sr.
A SrS: Ce phosphor thin film having a thickness of 600 nm is formed by RF magnetron sputtering using Ar gas using a target in which Ce: 0.2 mol% is added to S and ZnS is mixed with 33.3% of the base material composition. 14 was formed.

Next, in the same manner as described above, the upper insulating layer 15 made of a glass ceramic film is formed on the SrS: Ce phosphor thin film 1.
4 was formed to a thickness of 100 nm.

Further, using an ITO oxide target, R
Substrate temperature 25 by F magnetron sputtering
At 0 ° C., a 200 nm-thick ITO transparent electrode 16 was formed in a predetermined pattern to form an EL element.

Using xylene sufficiently dehydrated with molecular weight, a 20 wt% polysilazane solution was applied with a precision die coater (CAP coater, manufactured by Hirano Techsheet Co., Ltd.), and heated on a hot plate at 100 ° C. under N ₂ atmosphere. After drying, it was pre-baked and baked at 900 ° C. for 30 minutes in a vacuum heating furnace maintained at a degree of vacuum of 0.001 Pa to form a SiN _x insulating layer 17.

Next, when the thickness of the SiN _x insulating layer is 20
Since it is a thin film having a thickness of 0 nm, a 30% by mass solution of a polysilazane partially methylated modified product [substituted with 10 at% of hydrogen in the structure] in xylene (Pd catalyst-containing product) is applied in the same manner as in Example 1 using a die coater. And after pre-baking,
Bake for 2.5 hours (only heating, no humidification)
The silica layer 17 containing a minute methyl group was formed.

Then, in the same manner as in Example 1-2, an R, G, B transer film manufactured by Fuji Photo Film Co., Ltd. is pasted on a glass sealing plate (7059 substrate manufactured by Corning), exposed, and baked. Thus, a color filter 19 was produced.

Further, a T-die extruded film (thickness: 100 μm) 18 of a low melting point thermoplastic fluororesin Dyneon (manufactured by Sumitomo 3M) THV-400 was attached to a color filter 19 of a sealing plate and a methyl group of the EL element. At 150 ° C. and 1 ° C. with a vacuum laminator.
After a time treatment, a full-color inorganic EL device as shown in FIG. 2 was obtained.

By extracting the electrodes from the Al electrode and the ITO transparent electrode using a probe electrode in a vacuum from the obtained structure and applying a sine wave AC electric field of 1 KHz, predetermined light emission can be obtained with good reproducibility. Was.

Example 2-1 7059 manufactured by Corning Incorporated
On a glass substrate, as a blue transmission layer, a green transmission layer, and a red transmission layer, with a color filter manufactured by Fuji Hunt Co., the cut light is green light having a wavelength of 560 nm or more and light having a wavelength of 480 nm or less, and blue is Light of wavelength 490nm or more, red is 58
Patterns were formed using light having a wavelength of 0 nm or less.

Next, perhydropolysilazane (Mn = 1)
000) xylene solution (concentration: 20 wt%: L110 manufactured by Tonen Co., Ltd., containing several tens of pounds of Pd catalyst) for a thin layer such as a spin coater, a die coater, a flexo coater, and a gravure coater. The color filter is applied on the substrate on which the pattern is formed by a coater to a thickness of 1.5 μm in a wet film thickness, dried with hot air, and dried.
Annealed at 0 ° C. for 30 minutes to 1 hour. Next, this substrate was continuously heated and oxidized with steam at 90 ° C. and 80% RH for 3 hours. At this time, since the Pd catalyst is contained, the perhydropolysilazane is converted to a silica film by this heating and steam oxidation, and is continuously heated at 110 ° C.
Then, water was completely removed to form a 1.0 μm-thick silica film as a barrier layer having a silica film.

Further, ashing was performed with oxygen plasma (2 kW output, substrate temperature 200 ° C.) for 10 minutes. By this treatment, the surface of the barrier layer also serving as the overcoat of the color filter was further cleaned, and a flatter and more complete a-SiO ₂ passivation layer was formed.

Next, an ITO transparent electrode (hole injection electrode)
Was formed and patterned so as to form pixels of 64 dots × 7 lines (100 × 100 μm per pixel) with a film thickness of 85 nm. Then, the substrate on which the patterned hole injection electrode was formed was subjected to ultrasonic cleaning using a neutral detergent, acetone and ethanol, pulled up from boiling ethanol, and dried. Thereafter, UV / O ₃ cleaning was performed.

Next, the substrate was moved to a film forming chamber, fixed to a substrate holder of a vacuum evaporation apparatus, and the pressure in the tank was reduced to 1 × 10 ⁻⁴ Pa or less. Then, poly (thiophene-2,5-diyl) having a thickness of 10 nm is used as a hole injection layer, and TPD is doped with rubrene at a ratio of 1% by weight as a hole transport layer and a yellow light emitting layer. A thick film was formed.
The concentration of rubrene is preferably about 0.1 to 10% by weight, and light is emitted with high efficiency at this concentration. The concentration may be determined from the color balance of the luminescent color, and depends on the light intensity and the wavelength spectrum of the blue luminescent layer to be formed thereafter. Further, 4'-bis [(1,2,2-triphenyl) ethenyl] biphenyl is also used as a blue light emitting layer at 50 nm, and Alq3 as an electron transport layer.
Was simulated by 10 nm.

Next, AlLi (Li: 7 at%) was added to 1 nm
To form an Al electrode layer having a thickness of 200 nm. Finally, glass sealing was performed to obtain an organic EL display.

As a comparative sample, an acrylic resin was applied to a thickness of 5 μm on a color filter,
A sample (sample #A) was formed by heating to 0 ° C. and thermosetting to form an overcoat layer and no barrier layer.

When a direct current voltage was applied to each of the organic EL color displays produced in this manner and the organic EL color displays were continuously driven at a constant current density of 50 mA / cm ² , the luminance half-life of the inventive sample was 500 hours or more. On the other hand, the comparison sample #A took less than 50 hours. From these results, it can be seen that the provision of the barrier layer of the present invention has a life equal to or longer than that of a display in which a conventional overcoat layer and a barrier layer are provided. In addition,
Substantially equivalent results were obtained when the color filter layer and the fluorescence conversion filter layer were used in combination.

Example 2-2 A color filter layer was formed on a glass substrate in the same manner as in Example 2-1.

Next, a xylene solution of organic polysilazane (concentration: 20 wt.%) In which hydrogen of NH ₂ group of perhydropolysilazane (# L110) used in Example 2-1 was replaced by CH ₃ .
%: Manufactured by Tonen Co., Ltd.) by a spin coater to a wet film thickness of 1.5 μm on a substrate on which the color filter has been patterned, and dried with hot air at 180 ° C. Annealed for 30 minutes.

Next, in the same manner as in Example 2-1, peroxysilazane (D820: manufactured by Tonen Corp .: molecular weight Mn = 70)
0, trimethylamine 5 wt% is added as a catalyst) by a spin coater to a wet film thickness of 1.5 μm.
m, dried with hot air, and annealed at 180 ° C. for 30 minutes.

Next, the substrate was continuously heated at 90 ° C. and 80%
Heated steam oxidation under RH atmosphere conditions for 3 hours, converted to a silica film, and continuously heated at 110 ° C. as it was to completely remove water and form a 0.8 μm thick second barrier layer having a silica film. A silica film was formed.

Further, ashing was performed for 10 minutes with oxygen plasma (output of 2 kW, substrate temperature of 200 ° C.). By this treatment, the surface of the barrier layer also serving as the overcoat of the color filter was further cleaned, and a flatter and more complete a-SiO ₂ passivation layer was formed.

Since the obtained organic / inorganic (SiO ₂ ) hybrid barrier layer containing a methyl group consisting of organic polysilazane as the first layer intervenes in the obtained passivation film having a two-layer structure, the passivation film of Example 2-1 is different from that of Example 2-1. "Affinity" and "adhesion" with the patterned color filter surface were further improved.

However, when the passivation film is composed of only the first layer, the peeling material (organic strong alkali / NMP) for removing the residue of the positive resist used when forming the color filter is obtained in the humidification chemical resistance acceleration test. It was confirmed that the barrier layer was eroded by the use of a solvent and the second layer composed of dense SiO ₂ was functioning very effectively.

Further, instead of the first barrier layer of this embodiment, a photopolymerization initiator exemplified as the organic-inorganic hybrid resin layer (1) is contained, and perhydropolysilazane and a UV-crosslinkable acrylate derivative are used. In the case of using the transparent cured product made of the mixture or the films similarly exemplified in (2) and (3), the humidified chemical resistance accelerated test showed a tendency to be affected by the heat-peelable material. For this reason, when used for an EL element, the second dense SiO ₂ layer of the present embodiment is indispensable for blocking moisture, O ₂ gas, and other outgas from the color filter to the organic layer and the electrodes. It turned out to be.

Next, in the same manner as in Example 2-1, ITO
The transparent electrode was patterned to form a hole injection layer, a hole transport layer, an electron injection / transport / emission layer, and an AlLi / Al electrode layer. Finally, glass sealing was performed to obtain an organic EL display (sample 2).

When a direct current voltage was applied to each of the organic EL color displays produced in this manner and the organic EL color displays were continuously driven at a constant current density of 50 mA / cm ² , the luminance half time was 500.
It was more than an hour. From these results, it can be seen that the provision of the barrier layer of the present invention has a life equal to or longer than that of a display in which a conventional overcoat layer and a barrier layer are provided.

Example 2-3 A high frequency ion plating apparatus equipped with a mask alignment system was preliminarily baked at 200 ° C. for 2 hours.
A 59 glass substrate was inserted. After that, RF power 200W
Was applied to a coil in the ion plating to generate argon plasma, and the substrate surface was washed by ion bombardment.

Next, the organic coloring pigment was placed in a graphite cell, and the organic pigment was sublimated under a vacuum of about 1.33 × 10 ⁻⁶ Pa (10 ⁻⁴ Torr) to form a color filter film. At this time, when the sublimated organic pigment passes through the plasma, it may collide with the plasma gas and activate the organic pigment surface. , A good film including adhesion to the substrate and flatness was obtained.

The red R, blue B, and green G organic pigments used include “prevention of rough surface flatness due to crystal growth after film formation on a glass substrate”, “color tone performance as a color filter”, The following organic pigments were used as organic pigments which easily satisfy the “heat resistance to substrate heating (about 250 ° C. or higher)” and are easy to deposit. Note that the heat resistance is mainly for thermal annealing performed to improve the crystallinity and lower the resistance of the ITO transparent electrode film formed on the filter layer.

R: Diketopyrrolopyrrole red G: Tetramethoxyvanadyl phthalocyanine B: Monochloro-Cu-phthalocyanine The R, G, B filter layers were each patterned using a Ni metal mask.

The color filter thus obtained is a thin film having a thickness of 0.3 to 0.7 μm, is flat with little variation in thickness, exhibits sufficient chromaticity, and has excellent light transmittance. A filter was obtained.

Next, in the same manner as in Example 2-1, a xylene solution of perhydropolysilazane (L110 manufactured by Tonen Corp.)
Was diluted with dibutyl ether, overcoated with a thin film coating apparatus (CAP coater) manufactured by Hirano Technoseed Co., Ltd., humidified and heated under the same conditions as in Example 2-1 to 1.5 μm. the a-SiO ₂ layer having a thickness formed on the filter layer.

Further, ashing was performed with oxygen plasma in the same manner as in Example 2-1 to form a more complete a-SiO2 passivation layer on the surface of the SiO2 layer. Thickness variation is also R
a It was flat within 30 nm.

Next, in the same manner as in Example 2-1, ITO
The transparent electrode was patterned to form a hole injection layer, a hole transport layer / light emitting layer, a light emitting layer, an electron injection / transport, and an AlLi / Al electrode layer. Finally, glass sealing was performed to obtain an organic EL display (sample 3).

A direct current voltage was applied to each of the organic EL color displays produced in this manner, and the organic EL color displays were continuously driven at a constant current density of 50 mA / cm ^2.
It was more than an hour. From these results, it can be seen that the provision of the barrier layer of the present invention has a life equal to or longer than that of a display in which a conventional overcoat layer and a barrier layer are provided. In addition, a color filter layer,
Approximately the same results were obtained when the fluorescent conversion filter layer was used in combination.

[Example 2-4] Instead of the glass substrate used in Example 2-1, a colorless, transparent material having a total light transmittance of 90% or more and a heat resistance of Tg: 288 ° C was used. Arylate resin casting film (Unitika Ltd.)
MF-2000).

The film was baked at 200 ° C. for 1 hour to remove outgas components such as low molecular weight components and moisture in the film. The color filter layer was patterned in the same manner as in Example 1.

Next, as the overcoat layer of the color filter layer, a zirconia chemically modified polysilsesquioxane polymer having the following structure (ZRS ^™ , manufactured by Catalyst Chemical Industry Co., Ltd.) having the following structure was applied to the first layer by 2.5 μm. Then 240
The composition was thermoset at 30 ° C. for 30 minutes.

[0236]

Embedded image

Next, a coating solution of a xylene solution of perhydropolysilazane (L110 manufactured by Tonen KK) was diluted with dibutyl ether in the same manner as in Example 2-1 and the first layer was coated with a spin coater. The film was applied to a thickness of 1.5 μm on a wet film, dried with hot air, and then annealed at 180 ° C. for 30 minutes. Next, this substrate is continuously
The mixture was heated and steam-oxidized at 0 ° C. and 80% RH for 3 hours.

Next, in the same manner as in Example 2-1, ITO
The transparent electrode was patterned to form a hole injection layer, a hole transport layer / light emitting layer, a light emitting layer, an electron injection / transport, and an AlLi / Al electrode layer. Finally, glass sealing was performed to obtain an organic EL display (sample 4).

A direct current voltage was applied to each of the organic EL color displays thus produced, and the organic EL color displays were continuously driven at a constant current density of 50 mA / cm ^2.
It was more than an hour. From these results, it can be seen that the provision of the barrier layer of the present invention has a life equal to or longer than that of a display in which a conventional overcoat layer and a barrier layer are provided.

This sample is lightweight because the substrate is plastic, does not have the risk of brittle fracture like glass, and has some flexibility in the form of a film-like organic EL.
The display was obtained.

[Example 3-1] As shown in FIG. 3, a Teijin optically conductive film Eclear HT comprising a substrate 31 with a polycarbonate resin base sandwiched between gas barrier layers on both sides and an ITO transparent electrode thin film provided on one side thereof. -6
0 (optically isotropic polycarbonate film) was scrub-washed with a neutral detergent. Then heat and dry well,
This ITO film was used as the hole injection electrode layer 32. This IT
The surface resistance of the O film was 60Ω / □.

After the surface of the substrate on which the ITO electrode layer 32 and the like had been formed was washed with UV / O ₃ , a resist was applied and patterned into 1 mm pitch stripes by a photolithographic method.

Next, a hole transport layer 33 was formed. The hole transport layer is formed by dissolving poly (3,4-ethylenedioxythiophene) (poly (3,4-ethylenedioxithin) in a toluene solvent.
iophene) / polystylene sulphonate) PEDOT / P
A solution in which 1.5 mass% of SS was dissolved was formed to a thickness of 40 nm by spin coating.

Next, as the light emitting layer 34, a precursor methanol solution (coating solution) made of polyphenylene vinylene (PPV) Cambridge Display Technology LDT having a polymer concentration of 1 g per 10 to 25 g of methanol.
Was uniformly spin-coated on the substrate on which the above-mentioned PEDOT was formed.

Further, as an electron injecting and transporting layer, the substrate was transferred to a vacuum evaporation apparatus, and a film of LiF was formed to a thickness of 6 nm, and subsequently, a film of metal Ca was formed to a thickness of 6 nm. Thereafter, Al was deposited to a thickness of 200 nm to form a negative electrode 36.

A 30% NV-containing xylene-dissolved polysilazane solution L110 (manufactured by Tonen KK) containing a Pd catalyst was mixed with Al
The above-mentioned module, in which the lead wire is soldered to the electrode and ITO electrode, is applied to a thickness of 1.2 μm by three-dimensional spray coating using precision spray coating manufactured by EV Groop US Inc or Nordson, and immediately dried and baked did. As a result, the precursor polymer was converted into an EL light-emitting characteristic PPV film (thickness: 200 to 300 nm).

Thus, the SiO _x N _y (O / (O + N) atomic ratio of 70 was obtained by the polysilazane dip coating.
%) Flexible organic EL sealed to a thickness of 1 μm
An element was obtained.

When an electric field was applied to the obtained sample of the organic EL device in the air, it showed diode characteristics.
When the TO side was biased to the plus side and the LiF / Ca / Al electrode side to the minus side, the current increased as the voltage increased, and clear light emission was observed in a normal room. In addition, no leakage current and no light emission from other than the selected electrode line were observed. The device was placed in an atmosphere at 80 ° C. for 1 hour.
No deterioration in luminance was observed even after the accelerated deterioration test for 00 hours, and the occurrence of dark spots was not confirmed.

Example 3-2 As shown in FIG. 4, an amorphous silicon layer was formed on a 1737 heat-resistant alkali-free glass substrate 41 made by Corning by a CVD method. This amorphous silicon layer is solid-phase grown by heat and laser annealing to form an active layer (polysilicon layer), and further, SiO _{2 serving as a} gate oxide film thereon
The layer was formed by, for example, a plasma CVD method. This S
A Mo—Si ₂ layer serving as a gate electrode is formed on the iO ₂ layer,
It was performed by a sputtering method. Then, the Mo—Si ₂ layer and the SiO ₂ layer formed above were patterned by, for example, dry etching to obtain a gate electrode and a gate oxide film.

Then, using the gate electrode as a mask, an N-type impurity: P was doped by ion doping in portions to be the source / drain regions of the silicon active layer.

Next, this was heated at about 550 ° C. for 10 hours in a nitrogen atmosphere to activate the dopant. Further, hydrogenation was performed by heat treatment at about 400 ° C. for 30 minutes in a hydrogen atmosphere to reduce the defect state density of the semiconductor.

The first substrate serving as an insulating layer is formed on the entire substrate.
The SiO ₂ layer was about thick 8000Å molding. The first SiO ₂ film 43 serving as the insulating layer was etched to form a contact hole. Next, Al was deposited as a drain and source wiring electrode to form a TFT array 42.

Next, an ITO 44 serving as a hole injection electrode was formed in a region where the organic EL element was to be formed, and was connected to a wiring electrode. After patterning the ITO 44, the second SiO ₂ layer 45 is coated to a thickness of
And patterned.

Further, on this second SiO ₂ layer 45,
As an element isolation structure, polyimide was formed to a thickness of about 1 to 2 μm, and was patterned to form an isolation partition 46.

Next, a hole transport layer 47 was formed. The hole transport layer 47 is formed by adding PEDOT / PS to a toluene solvent.
S dissolved at 1.5% by mass and spin-coated
It was formed to a thickness of 0 nm.

The substrate coated with PEDOT / PSS is
Vacuum drying was performed at 80 ° C. for 1 hour, and thereafter, three types of polyfluorene light emitting layers 48 corresponding to each of the RGB emission colors using xylene as a solvent were respectively applied. At this time, the film thickness was 700 nm. Furthermore, vacuum drying at 80 ° C.
It went for 0 minutes.

Next, the substrate was transferred to a vacuum evaporation apparatus, and LiF was formed into a film having a thickness of 5 nm as the inorganic electron injection layer 49. Subsequently, Al was evaporated to a thickness of 200 nm to form a cathode 50.
Protective film 51 was formed on the electron injection electrode in the same manner as in Example 3-1.
Was formed. Finally, glass sealing was performed to obtain an organic EL device.

When an electric field was applied to the obtained sample of the organic EL device in the air, each pixel showed diode characteristics. When the ITO side was biased positive and the LiF / Al electrode side was biased negative, the current was: It increased with an increase in voltage, and clear light emission was observed from each pixel in a normal room. In addition, no leakage current and no light emission from other than the selected electrode line were observed.

[0259]

As described above, according to the present invention, translucency,
Heat resistance, passivation properties (gas barrier properties, oligomer ejection prevention properties, reduction of outgassing), water absorption (wet) resistance,
Substrate with excellent productivity such as chemical deterioration stability, dimensional form stability, surface anti-reflection property, electrical insulation, ultraviolet light deterioration resistance, and weather resistance, and film formation under normal pressure. An object of the present invention is to provide a light-emitting element having a protective member, thereby providing a light-emitting element which is highly reliable, easy to manufacture, and inexpensive.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a basic structure of an organic EL device which is a light emitting device of the present invention.

FIG. 2 is a schematic cross-sectional view showing a basic structure of an inorganic EL element which is a light emitting element of the present invention.

FIG. 3 is a schematic cross-sectional view showing a basic structure of an organic EL device which is a light emitting device of the present invention manufactured in Example 3-1.

FIG. 4 is a schematic cross-sectional configuration diagram showing a basic configuration of an organic EL device which is a light emitting device of the present invention manufactured in Example 3-2.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material 2 Color filter 3 Silica film 4 Light emitting element structure (organic EL structure) 5 Sealing plate 11 Substrate 12 Lower electrode (Al electrode) 13 Lower insulating layer 14 Light emitting layer (two-layer structure) 15 Upper insulating layer 16 Upper electrode (transparent electrode) 17 Barrier layer (polysilazane layer, two-layer structure) 19 Color filter 20 Sealing plate

Continued on the front page F term (reference) 3K007 AB04 AB12 AB13 AB15 AB18 BA06 BB01 BB07 CA01 CA05 CA06 CB01 DA01 DA05 DB01 DB02 DB03 EA02 EB00 EB01 FA01

Claims (10)

[Claims] 1. A light-transmitting and heat-resistant base material, a light-transmitting lower electrode formed thereon, a light-emitting layer, and an upper electrode. A light-emitting element having a silica film and / or a silica-based film obtained by applying polysilazane on both the substrate side and the opposite side of the substrate and oxidizing the same. 2. The light emitting device according to claim 1, wherein said base material is formed of glass or a resin material. 3. The light-emitting device according to claim 1, wherein the silica film and / or the silica-based film is provided at least between the substrate and the light-emitting layer. 4. A TFT is formed on the base material,
The light emitting device according to claim 3, further comprising a light emitting layer on the TFT. 5. The light emitting device according to claim 1, wherein said silica film and / or silica-based film is provided on at least both sides of a substrate. 6. The light emitting device according to claim 1, wherein the silica film and / or the silica-based film is oxidized under heating and / or humidification. 7. The light emitting device according to claim 1, wherein said polysilazane and / or a modified product thereof has a structural unit represented by the following structural formula. Embedded image [R ¹ , R ² and R ³ represent an alkyl group. However,
At least one of R ¹ , R ² and R ³ is a hydrogen atom. ] 8. The light emitting device according to claim 7, wherein the alkyl group has a total carbon number of 6 or less. 9. The light emitting device according to claim 7, wherein the silica film and / or the silica-based film is a film in which polysilazane having a number average molecular weight of 100 to 50,000 and / or a modified product thereof is ceramicized. 10. The light emitting device according to claim 1, which is an EL device.