JP2001250683A - Complex substrate, thin film light emission element using it, and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a complex substrate comprising a substrate/an electrode/a dielectric layer having a thick-film dielectric layer which is formed by using a sol-gel solution which can form a thick film having a flat and smooth surface without cracking in high concentration, its manufacturing method, and an EL element using it. SOLUTION: In the manufacturing method of the complex substrate which has a substrate having an electric insulation characteristic and an electrode and an insulator layer which are formed by the thick-film method on the substrate one by one, the manufacturing method of the complex substrate is obtained in which the thin film insulator layer is formed on the above insulator layer after applying the sol-gel solution in which a metal compound is dissolved in diol group (OH(CH2)nO) as a solvent, and, after drying, calcinaed. The complex substrate and the EL element using the complex substrate are included.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composite substrate having a dielectric and an electrode, an electroluminescent device (EL device) using the composite substrate, and a method of manufacturing the same.

[0002]

2. Description of the Related Art A phenomenon in which a substance emits light by the application of an electric field is called electroluminescence (EL), and an element using this phenomenon has been put to practical use as a backlight of a liquid crystal display (LCD) or a watch.

An EL element has a structure in which a powdered phosphor is dispersed in an organic substance or an enamel and electrodes are provided on the upper and lower sides, and between an electrode and two thin film insulators on an electrically insulating substrate. There is a thin-film element using a thin-film phosphor formed to be sandwiched between the thin-film phosphors. Further, there are a DC voltage driving type and an AC voltage driving type depending on the driving method. Distributed EL
The element has been known for a long time and has an advantage that it can be easily manufactured, but its use is limited because of its low luminance and short life. On the other hand, the thin-film EL device has characteristics of high luminance and long life, and has greatly expanded the practical range of the EL device.

Conventionally, in a thin film type EL device, a blue plate glass used for a liquid crystal display or a PDP is used as a substrate, an electrode in contact with the substrate is a transparent electrode such as ITO, and light generated by a phosphor is emitted from the substrate. The method of taking out from the mainstream was mainstream. As a phosphor material, ZnS to which Mn exhibiting yellow-orange emission has been added has been mainly used from the viewpoint of ease of film formation and emission characteristics. In order to manufacture a color display, it is essential to use a phosphor material that emits light in three primary colors of red, green and blue. These materials include ZnS to which SrS or Tm to which Ce emitting blue light is added, ZnS or CaS to which Sm to which red light emitting Sm is added, and ZnS or Ce to which green light emitting Tb is added.
CaS to which is added is a candidate, and research is continuing. But so far, the emission brightness,
There are problems in terms of luminous efficiency and color purity, and they have not been put to practical use.

[0005] As means for solving these problems, it is known that a method of forming a film at a high temperature and a heat treatment at a high temperature after the film formation are promising. When such a method is used, it is impossible to use a soda lime glass as a substrate from the viewpoint of heat resistance. The use of heat-resistant quartz substrates is also being considered, but quartz substrates are very expensive,
It is not suitable for applications requiring a large area such as displays.

In recent years, as described in JP-A-7-50197 and JP-B-7-44072, an electrically insulating ceramic substrate is used as a substrate, and instead of the thin film insulator below the phosphor, Development of devices using thick film dielectrics was reported.

FIG. 2 shows the basic structure of this device. The EL device shown in FIG. 2 has a structure in which a lower electrode 12, a thick-film dielectric layer 13, a light-emitting layer 14, a thin-film insulator layer 15, and an upper electrode 16 are sequentially formed on a substrate 11 made of ceramic or the like. I have. As described above, unlike the conventional structure, the transparent electrode is provided on the upper portion in order to extract the light emitted from the phosphor from the upper portion on the side opposite to the substrate.

In this device, the thick-film dielectric has a thickness of several tens μm, which is several hundred to several thousand times the thickness of the thin-film insulator. Therefore, there is an advantage that dielectric breakdown due to a pinhole or the like is small, and high reliability and high production yield can be obtained.

[0009] The voltage drop across the phosphor layer due to the use of a thick dielectric is overcome by using a high dielectric constant material as the dielectric layer. Further, by using the ceramic substrate and the thick film dielectric, the heat treatment temperature can be increased. As a result, it has become possible to form a light-emitting material exhibiting high light-emitting characteristics, which was conventionally impossible due to the presence of crystal defects.

However, the light-emitting layer formed on the thick-film dielectric has a thickness of about several hundred nm, and has a thickness of only about 1/100 of that of the thick-film dielectric. For this reason, the surface of the thick-film dielectric layer must be smooth at a level equal to or less than the thickness of the light-emitting layer, but the surface of the dielectric layer manufactured in the normal thick-film process must be sufficiently smooth. Was difficult.

If the surface of the dielectric layer is not smooth, a light emitting layer formed thereon cannot be formed uniformly, or a peeling phenomenon occurs between the dielectric layer and the light emitting layer. There was fear. For this reason, in the conventional process, it was necessary to remove large irregularities by polishing or the like, and to remove fine irregularities by a sol-gel process.

However, in the case where the surface is smoothed in the sol-gel process, if a sol-gel solution used for forming a normal dielectric thin film is used, the film thickness formed by one coating is reduced in order to prevent cracks. It was limited, and it was necessary to apply many times to sufficiently smooth the surface of the thick film dielectric.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thick film having a smooth surface by using a sol-gel solution having a high concentration and capable of forming a thick film without generating cracks. Composite substrate comprising substrate / electrode / dielectric layer having dielectric layer, method of manufacturing the same, and EL using the same
It is to provide an element.

[0014]

That is, the above object is achieved by the following constitutions. (1) A method for producing a composite substrate having an electrically insulating substrate and an electrode and an insulator layer formed on the substrate by a thick-film method and sequentially including an electrode and an insulator layer, wherein a metal compound is formed on the insulator layer.
A method for producing a composite substrate in which a sol-gel solution prepared by dissolving in a diol (OH (CH ₂ ) _n OH) as a solvent is applied, dried, and then fired to form a thin-film insulator layer. (2) The solvent is propanediol (OH (C
H _{2) 3} OH) in which the production method of the composite substrate according to (1). (3) At least one of the metal compounds is acetylacetonate (M (CH ₃ COCHCOCH ₃ ) _n : M is a metal element), or acetylacetone (CH ₃ COCH ₂ COCH ₃ ) is reacted with the metal compound. The method for producing a composite substrate according to the above (1) or (2), wherein the composite substrate is acetylacetonated. (4) The metal compound is (Pb _x La _1-x ) (Z
r _y , Ti _1-y ) O ₃ (where 0 ≦ x, y ≦ 1), the method for manufacturing a composite substrate according to any one of the above (1) to (3). (5) The method for producing a composite substrate according to any one of (1) to (4), wherein the drying temperature of the sol-gel solution is 350 ° C. or higher. (6) A composite substrate obtained by any one of the above (1) to (5). (7) The composite substrate according to (6), wherein the functional thin film is formed on the insulator layer. (8) An EL device having at least a light-emitting layer and a transparent electrode on the composite substrate according to (6) or (7). (9) The EL device according to (8), further including a thin film insulating layer between the light emitting layer and the transparent electrode.

[0015]

In the present invention, the above-mentioned sol-gel solution is applied onto a thick-film dielectric layer, dried and baked to form a substrate / electrode / dielectric layer having a thick-film dielectric layer with a smooth surface. A composite substrate can be made. When an EL element is manufactured using a composite substrate having such a smooth surface, a light-emitting layer formed thereon can be uniformly formed without peeling or the like. As a result, an EL element having excellent light-emitting characteristics and reliability can be obtained.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION
What is claimed is: 1. A method for producing a composite substrate, comprising: a substrate having electrical insulation; and an electrode and an insulator layer sequentially formed on the substrate by a thick film method, comprising: a metal compound on the insulator layer; A sol-gel solution prepared by dissolving in (OH (CH ₂ ) _n OH) is applied, dried, and fired to form a thin-film insulator layer.

As described above, a diol (OH (CH ₂ ) _n OH) is used as a solvent for a sol-gel, and a gold compound is dissolved therein, whereby a thick coating film can be obtained. The insulating layer of the substrate can be easily planarized.

Hereinafter, a specific configuration of the present invention will be described. Figure
FIG. 1 shows a cross-sectional view of an EL device using a composite substrate provided with electrodes and an insulator layer according to the present invention.

The composite substrate is an electrically insulating ceramic substrate 1
A multilayer ceramic comprising a thick-film electrode 5 formed in a predetermined pattern, an insulator layer 2 formed thereon by a thick-film method, and a thin-film insulator layer 3 formed by a sol-gel method It is a structure.

An EL device using a composite substrate has a basic structure comprising a thin-film light-emitting layer 4, an upper thin-film insulator layer 5, and an upper transparent electrode 7 formed on the composite substrate by vacuum evaporation, sputtering, CVD, or the like. have. Further, a single insulating structure in which the upper thin film insulator layer is omitted may be adopted.

The composite substrate of the present invention is characterized in that the surface is smooth by forming a thin-film insulator layer on a thick-film dielectric layer using a sol-gel solution using diols as a solvent. .

The high-concentration sol-gel solution used for forming the thin-film insulator layer includes diols such as propanediol (O
It is produced by dissolving a metal compound in a solvent of H (CH ₂ ) _n OH). As a metal compound raw material, metal alkoxide is often used for preparing a sol-gel solution, but since metal alkoxide is easily hydrolyzed, when preparing a high-concentration solution, acetylacetate is used to prevent precipitation and precipitation of the raw material and solidification of the solution. It is preferable to use nate compounds and derivatives thereof.

This solvent is preferably propanediol (OH (CH ₂ ) ₃ OH). Further, at least one of the metal compounds is acetylacetonate (M (CH ₃ COCHCOCH ₃ ) _n : M
Is preferably a metal element), or acetylacetonate formed by reacting a metal compound with acetylacetone (CH ₃ COCH ₂ COCH ₃ ). M above
Ba, Ti, Zr, Mg as the metal element represented by
And the like.

As the metal compound to be dissolved in such a sol-gel solution, a known metal compound used in a sol-gel solution can be used. Specifically, (Pb _x L
_{a 1-x) (Zr y} , Ti 1-y) O 3 ( provided that 0 ≦ x, y ≦
1), BaTiO ₃ , Pb (Mg _1/3 Nb _2/3 ) O ₃ , P
_{b (Fe 2/3 W 1/3) O} 3 or the like can be mentioned, among others _{(Pb x La 1-x)} (Zr y, Ti 1-y) O 3 ( where 0
≦ x, y ≦ 1) is preferred. These metal compounds are used in an amount of 0.1 to 5.0 mol, especially 0.5 to 5.0 mol, in 1000 ml of a solvent.
It is preferable to contain 1.0 mol.

The sol-gel solution thus prepared is applied on the insulator layer, preferably by spin coating or dip coating. Next, the composite substrate to which the sol-gel solution has been applied is dried and further baked. Sol-
In order to suppress the occurrence of cracks on the surface of the thin-film insulator layer manufactured by the gel method, it is preferable to perform drying at 350 ° C., and more preferably at 400 ° C. or higher.

In order to obtain a smooth surface of the thin film insulator layer, the steps of coating / drying / firing the sol-gel solution may be repeated several times, preferably 2 to 5 times. Alternatively, baking may be performed after repeating application / drying of the solution. Alternatively, a sol-gel solution may be applied on the composite substrate before firing, and the electrodes, the thick dielectric layer and the thin insulating layer may be fired simultaneously.

The drying conditions are preferably at 400 ° C. or higher for about 1 to 10 minutes, and the firing conditions are preferably at 500 to 900 ° C. for about 5 to 30 minutes.

The above composite substrate precursor can be produced by a usual thick film method. That is, for example, Al ₂ O ₃
Paste made by mixing a binder and a solvent with a conductive powder such as Pd or Ag / Pd on a ceramic substrate having electrical insulation such as glass or crystallized glass, into a predetermined pattern by a screen printing method or the like. Print. Next, an insulating paste prepared by mixing a binder and a solvent on a powdery insulating material is printed thereon as described above. Alternatively, a green sheet may be formed by casting a film of an insulator paste, and the green sheet may be laminated on the electrode. Further, an electrode may be printed on a green sheet of an insulator and laminated on a substrate.

The composite green obtained as described above is fired at a temperature suitable for the electrodes and the dielectric layers. When a noble metal such as Pd, Pt, Au, or Ag or an alloy thereof is used as the electrode, it can be fired in the air. When a dielectric material prepared to have reduction resistance is used, firing can be performed in a reducing atmosphere, so that a base metal such as Ni or an alloy thereof can be used as the internal electrode. The thickness of the electrode is usually 2-3 μm. The thickness of the dielectric layer needs to be 2 to 3 μm or more due to manufacturing problems. If the thickness is too large, not only the capacity is reduced and the applied voltage to the light emitting layer is reduced, but when the display element is formed due to the spread of the internal electric field, an image may blur or crosstalk may occur. .

The substrate used in the present invention has an insulating property.
And the insulating layer (dielectric layer) and electrode layer
If the required strength can be maintained without contamination
It is not particularly limited. As a specific material
Is alumina (Al_TwoO_Three), Quartz glass (SiO_Two ),
Magnesia (MgO), forsterite (2MgO.
SiO_Two), Steatite (MgO.SiO)_Two), Murai
(3Al_TwoO_Three・ 2SiO _Two), Berylia (BeO),
Zirconia (ZrO_Two ), Aluminum nitride (Al
N), silicon nitride (SiN), silicon carbide (SiC)
+ BeO) and the like.
In addition, Ba-based, Sr-based, and Pb-based perovskites
In this case, the same composition as the insulating layer can be used.
Can be used. Of these, alumina-based
Plate is preferred and beryllia or nitrogen if thermal conductivity is required.
Aluminum chloride, silicon carbide and the like are preferable. Substrate material
When the same composition as the insulating layer is used, the difference in thermal expansion
This is preferable because no warping or peeling phenomenon occurs.

The sintering temperature for forming these substrates is 8
00 ° C. or higher, especially 800 ° C. to 1500 ° C., and even 12 ° C.
It is about 00 ° C to 1400 ° C.

The substrate may contain a glass material for the purpose of lowering the firing temperature. In particular,
PbO, B ₂ O ₃ , SiO ₂ , CaO, MgO, TiO
₂ , one or more of ZrO ₂ . The glass content of the substrate material is about 20 to 30 wt%.

When preparing a paste for a substrate, the paste may have an organic binder. The organic binder is not particularly limited, and may be any of those commonly used as binders for ceramic materials.
What is necessary is just to select and use suitably. Examples of such an organic binder include ethyl cellulose, acrylic resin, and butyral resin, and examples of the solvent include α-terpineol, butyl carbitol, and kerosene. The content of the organic binder and the solvent in the paste is not particularly limited, and may be a commonly used amount, for example, about 1 to 5% by weight of the organic binder and about 10 to 50% by weight of the solvent.

Further, the paste for a substrate may contain additives such as various dispersants, plasticizers and insulators, if necessary. The total content of these is preferably 1% by weight or less.

The thickness of the substrate is usually about 1 to 5 mm, preferably about 1 to 3 mm.

When firing in a reducing atmosphere, a base metal can be used as an electrode material. Preferably,
1 of Mn, Fe, Co, Ni, Cu, Si, W, Mo, etc.
Using two or more species or Ni-Cu, Ni-M
Any of n, Ni-Cr, Ni-Co and Ni-Al alloys, more preferably Ni, Cu and Ni-Cu alloys.

When firing in an oxidizing atmosphere, a metal which does not become an oxide in the oxidizing atmosphere is preferable. Specifically, Ag, Au, Pt, Rh, Ru, Ir, Ir,
One or more of Pb and Pd;
g, Pd and Ag-Pd alloys are preferred.

The electrode layer may contain a glass frit. Adhesion with a base substrate can be improved. When the glass frit is fired in a neutral or reducing atmosphere, a glass frit that does not lose its properties even in such an atmosphere is preferable.

The composition is not particularly limited as long as such conditions are satisfied. For example, silicate glass (SiO ₂ : 20 to 80 wt%, Na ₂ O: 80)
２０20 wt%), borosilicate glass (B ₂ O ₃ : 5-50 w
_{t%, SiO 2: 5~70wt%} , PbO: 1~10wt
_{%, K 2 O: 1~15wt%} ), alumina silicate glass _{(Al 2 O 3: 1~30wt%} , SiO 2: 10~60wt
_{%, Na 2 O: 5~15wt%} , CaO: 1~20wt%,
B ₂ O _3: 5~30wt%) of the glass frit is selected from may be used one or two or more. If necessary, CaO: 0.01 to 50% by weight, SrO: 0.
01 to 70 wt%, BaO: 0.01 to 50 wt%, Mg
O: 0.01 to 5 wt%, ZnO: 0.01 to 70 wt%,
_{PbO: 0.01~5wt%, Na 2 O} : 0.01~10
_{wt%, K 2 O: 0.01~10wt} %, MnO 2: 0.0
One or more additives such as 1 to 20 wt% may be mixed and used so as to have a predetermined composition ratio. The content of glass relative to the metal component is not particularly limited, but usually,
It is about 0.5 to 20% by weight, preferably about 1 to 10% by weight. The total content of the above additives in the glass,
When the glass component is 100, the content is preferably 50% by weight or less.

When preparing the paste for the electrode layer, it may have an organic binder. The organic binder is the same as the above-mentioned substrate. Further, additives such as various dispersants, plasticizers, and insulators may be contained in the electrode layer paste as needed. Their total content is
It is preferably at most 1 wt%.

The thickness of the electrode layer is usually 0.5 to 5
μm, preferably about 1 to 3 μm.

As an insulator material constituting the insulator layer,
There is no particular limitation, and various insulator materials may be used. For example, a titanium oxide-based oxide, a titanate-based composite oxide, or a mixture thereof is preferable.

As the titanium oxide, nickel oxide (NiO), copper oxide (CuO), manganese oxide (Mn ₃ O ₄ ), alumina (Al ₂ O ₃ ), magnesium oxide (MgO), silicon oxide ( SiO ₂ ) etc.
Titanium oxide (TiO ₂ ) containing about 001 to 30% by mass and the like and titanate-based composite oxides include barium titanate (BaTiO ₃ ). The Ba / Ti atomic ratio of barium titanate is preferably about 0.95 to 1.20.

The titanate-based composite oxide (BaTiO ₃ ) includes magnesium oxide (MgO) and manganese oxide (Mn).
₃ O ₄ ), tungsten oxide (WO ₃ ), calcium oxide (CaO), zirconium oxide (ZrO ₂ ), niobium oxide (Nb ₂ O ₅ ), cobalt oxide (Co ₃ O ₄ ), yttrium oxide (Y ₂ O ₃₎ ), And barium oxide (Ba)
O) one or two or more selected from a total of 0.00
About 1 to 30 wt% may be contained. In order to adjust the firing temperature and the coefficient of linear expansion, etc., SiO ₂ ,
MO (where M is one or more elements selected from Mg, Ca, Sr and Ba), Li ₂ O, B ₂ O ₃
At least one selected from the group consisting of:
The thickness of the insulator layer is not particularly limited, but is usually 5 to 100.
It is about 0 μm, especially about 5 to 50 μm, and more preferably about 10 to 50 μm.

The insulating layer may be formed of a dielectric material. In particular, when the composite substrate is applied to a thin film EL device, a dielectric material is preferable. The dielectric material is not particularly limited, and various dielectric materials may be used.
For example, the above-mentioned titanium oxide-based, titanate-based composite oxide, or a mixture thereof is preferable.

The titanium oxide is the same as described above. In order to adjust the firing temperature and the coefficient of linear expansion, for example, SiO ₂ and MO (where M is one or more elements selected from Mg, Ca, Sr and Ba) as subcomponents,
It may contain at least one selected from Li ₂ O and B ₂ O ₃ .

Particularly preferred dielectric materials include the following. The dielectric layer (insulating layer) contains barium titanate as a main component, magnesium oxide, manganese oxide, at least one selected from barium oxide and calcium oxide as subcomponents, and silicon oxide. When barium titanate was converted to BaTiO ₃ , magnesium oxide to MgO, manganese oxide to MnO, barium oxide to BaO, calcium oxide to CaO, and silicon oxide to SiO ₂ , each compound in the dielectric layer was converted. Is a ratio of 100 moles of BaTiO ₃ to M
gO: 0.1-3 mol, preferably 0.5-1.5 mol, MnO: 0.05-1.0 mol, preferably 0.2
~ 0.4 mol, BaO + CaO: 2-12 mol, SiO
₂ : 2 to 12 mol.

The ratio of (BaO + CaO) / SiO ₂ is not particularly limited, but is usually preferably from 0.9 to 1.1. BaO, CaO and SiO ₂ are (Ba _x Ca
_1-x O) _y · SiO ₂ may be included. In this case, in order to obtain a dense sintered body, 0.3 ≦ x ≦ 0.
7, it is preferable that 0.95 ≦ y ≦ 1.05.
The content of (Ba _x Ca _1-x O) _y · SiO ₂ is BaT
iO _3, the total of MgO and MnO, preferably 1 to 10 wt%, more preferably 4-6 wt%.
The oxidation state of each oxide is not particularly limited as long as the content of the metal element constituting each oxide is within the above range.

It is preferable that the dielectric layer contains, as an auxiliary component, 1 mol or less of yttrium oxide in terms of Y ₂ O ₃ with respect to 100 mol of barium titanate in terms of BaTiO ₃ . Although there is no particular lower limit for the Y ₂ O ₃ content,
In order to realize a sufficient effect, the content is preferably 0.1 mol or more. When yttrium oxide is contained, (Ba
_x Ca _1-x O) _y · SiO ₂ content is BaTi
O _3, MgO, preferably 1 to 10% by weight relative to the sum of MnO and Y ₂ O _3, more preferably 4-6 wt%.

The reasons for limiting the contents of the respective subcomponents are as follows.

When the content of magnesium oxide is less than the above range, the temperature characteristics of the capacity cannot be set in a desired range. When the content of magnesium oxide exceeds the above range, the sinterability rapidly deteriorates, the densification becomes insufficient, and
The R accelerated life is reduced, and a high relative dielectric constant cannot be obtained.

If the manganese oxide content is less than the above range, good reduction resistance cannot be obtained, the IR accelerated life becomes insufficient, and it becomes difficult to reduce the loss tan δ. If the manganese oxide content exceeds the above range, it is difficult to reduce the change over time of the capacity when a DC electric field is applied.

BaO + CaO, SiO ₂ , (Ba _x C
If the content of a _1-x O) _y · SiO ₂ is too small, the change with time in the capacity when a DC electric field is applied becomes large, and the IR accelerated life becomes insufficient. If the content is too large, the relative dielectric constant will drop sharply.

Yttrium oxide has the effect of improving the IR accelerated life. If the content of yttrium oxide exceeds the above range, the capacitance may decrease, and the sinterability may decrease, resulting in insufficient densification.

Further, the dielectric layer may contain aluminum oxide. Aluminum oxide has the effect of enabling sintering at relatively low temperatures. The content of aluminum oxide in terms of Al ₂ O ₃ is preferably 1% by weight or less of the whole dielectric material. If the content of aluminum oxide is too large, sintering is adversely affected.

The preferred thickness of one dielectric layer is:
100 μm or less, especially 50 μm or less, furthermore 2 to 20
Make it about μm.

When the paste for the insulating layer is prepared, the paste may have an organic binder. The organic binder is the same as the above-mentioned substrate. Furthermore, additives such as various dispersants, plasticizers, and insulators may be contained in the insulating layer paste as needed. Their total content is
It is preferably at most 1 wt%.

The sintering temperature of the substrate and the dielectric layer is as follows:
It is preferable that the temperature is higher than the sintering temperature of the thin film dielectric layer, and it is particularly preferable that the temperature be equal to or higher than the temperature obtained by adding 50 ° C. to the sintering temperature. The upper limit is not particularly limited, but is usually about 1500 ° C.

In the present invention, it is preferable to apply a pressure treatment to the composite substrate precursor to smooth the surface. As a method of pressurization, a method of pressing a composite substrate using a large area mold, a method of strongly pressing a roll against a thick insulating layer on the composite substrate, and moving the composite substrate with rotation of the roll are considered. Can be The pressure is preferably about 10 to 500 ton / m ² .

When preparing the electrode or the insulator paste, it is effective to use a thermoplastic resin as a binder and to heat a pressing die or roll during pressing.

In this case, in order to prevent the insulator green from adhering and adhering to the mold or the roll, it is preferable to apply pressure through a resin film having a release material between the mold or the roll and the insulator green. .

As such a resin film, tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PE)
N), syndioctatic polysterene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr), polysulfone (PSF), polyestersulfone (PES), polyetherimide (PEI), cyclic polyolefin , Brominated phenoxy, etc., and a PET film is particularly preferable.

As the release material, for example, a silicone-based material such as a material mainly composed of dimethyl silicone can be used. The release material is usually applied on the resin film.

When a mold or a roll is heated, the temperature of the mold or the roll varies depending on the kind of the binder used, particularly the melting point, the glass transition point, the kind of the thermoplastic resin, and the like.
It is about 50 to 200 ° C. If the heating temperature is too low, a sufficient smoothing effect cannot be obtained. If the heating temperature is too high, the binder may be partially decomposed, or the insulating green may adhere to a mold, a roll, or a resin film.

The surface roughness Ra of the obtained composite substrate green insulator layer is preferably 0.1 μm or less. Such surface roughness can be achieved by adjusting the surface roughness of the mold. Further, it can be easily achieved by applying pressure through a resin film having a flat surface.

The composite substrate of the present invention is manufactured by laminating an insulating layer precursor, an electrode layer precursor, and a substrate precursor by a usual printing method or a sheet method using a paste, and firing this.

The conditions for the binder removal treatment performed before firing are as follows:
Although it may be a usual one, when baking is performed in a reducing atmosphere, it is particularly preferable to perform baking under the following conditions.

Heating rate: 5 to 500 ° C./hour, especially 10
-400 ° C / hour Holding temperature: 200-400 ° C, especially 250-300 ° C Temperature holding time: 0.5-24 hours, especially 5-20 hours Atmosphere: in air

The atmosphere during firing is the same as that in the electrode layer paste.
It may be determined appropriately according to the type of the conductive material, but it may be determined in a reducing atmosphere.
When firing in an atmosphere, the firing atmosphere is N_TwoWith the main component
And H _Two1-10%, and steaming at 10-35 ° C
H obtained by atmospheric pressure_TwoA mixture of O gas is preferred
New And the oxygen partial pressure is 10^-8-10^-12Pressure
Preferably. When the oxygen partial pressure is less than the above range,
Abnormal sintering of the conductive material of the electrode layer
There is. When the oxygen partial pressure exceeds the above range, the electrode
The layers tend to oxidize. Perform firing in an oxidizing atmosphere
In this case, normal firing in the atmosphere may be performed.

The holding temperature at the time of firing may be appropriately determined according to the type of the insulator layer, and is usually 800 to 1400 ° C.
It is about. If the holding temperature is lower than the above range, the densification is insufficient, and if the holding temperature is higher than the above range, the electrode layer is easily broken. The temperature holding time during firing is 0.05 to
8 hours, preferably 0.1 to 3 hours.

When firing in a reducing atmosphere, the composite substrate is preferably annealed if necessary. Annealing is a process for reoxidizing the insulator layer, which can significantly increase the IR accelerated life.

The oxygen partial pressure in the annealing atmosphere is preferably 10 ⁻⁶ atm or more, particularly preferably 10 ⁻⁶ to 10 ⁻⁸ atm. When the oxygen partial pressure is less than the above range, it is difficult to reoxidize the insulator layer or the dielectric layer, and when the oxygen partial pressure exceeds the above range, the internal conductor tends to be oxidized.

The holding temperature at the time of annealing is preferably 1100 ° C. or lower, more preferably 1000 to 1100 ° C.
If the holding temperature is less than the above range, the oxidation of the insulator layer or the dielectric layer tends to be insufficient and the life tends to be short,
When the ratio exceeds the above range, the electrode layer is oxidized, and not only the current capacity is reduced, but also the electrode layer reacts with the insulator base and the dielectric base, and the life tends to be shortened.

The annealing step may be constituted only by raising and lowering the temperature. In this case, the temperature holding time is zero, and the holding temperature is synonymous with the maximum temperature. Further, the temperature holding time is preferably 0 to 20 hours, particularly preferably 2 to 10 hours.
It is preferable to use a humidified H ₂ gas or the like as the atmosphere gas.

In each of the above-described steps of binder removal, firing, and annealing, a wetter or the like may be used to humidify N ₂ , H ₂ , a mixed gas, or the like. In this case, the water temperature is preferably about 5 to 75 ° C.

The binder removing step, the firing step, and the annealing step may be performed continuously or independently.

In the case where these steps are continuously performed, after removing the binder, the atmosphere is changed without cooling, and then the temperature is raised to the holding temperature for firing, firing is performed, and then cooling is performed. It is preferable to perform the annealing while changing the atmosphere when the temperature reaches.

In the case where these steps are performed independently, in the binder removal processing step, the temperature is raised to a predetermined holding temperature, held for a predetermined time, and then lowered to room temperature. At that time, the atmosphere for removing the binder is the same as in the case where the process is performed continuously.
Further, in the annealing step, the temperature is raised to a predetermined holding temperature,
After holding for a predetermined time, the temperature is lowered to room temperature. The annealing atmosphere at that time is the same as in the case of performing the annealing continuously. Further, the binder removal step and the firing step may be performed continuously, and only the annealing step may be performed independently. Only the binder removal step may be performed independently, and the firing step and the annealing step may be performed continuously. You may do so. As described above, a composite substrate can be obtained.

The composite substrate of the present invention can be made into a thin film EL device by forming a functional film such as a light emitting layer, another insulating layer, another electrode layer, etc. thereon. In particular, a thin film EL device having good characteristics can be obtained by using a dielectric material for the insulating layer of the composite substrate of the present invention. Since the composite substrate of the present invention is a sintered material, it is also suitable for a thin film EL device in which a heat treatment is performed after forming a light emitting layer which is a functional film.

In order to obtain a thin film EL device using the composite substrate of the present invention, a light emitting layer / another insulating layer (a dielectric layer) / another electrode layer is formed on an insulating layer (a dielectric layer) in this order. I just need.

Examples of the material for the light emitting layer include the materials described in “Technical Trends of Recent Display, Monthly Display '98 April”, Tasaku Tanaka, pp. 1-10. Specifically, as a material for obtaining red light emission, such as ZnS and Mn / CdSSe, as a material for obtaining green light emission, such as ZnS: TbOF and ZnS: Tb, and as a material for obtaining blue light emission, such as SrS: Ce, (Sr
S: Ce / ZnS) n, Ca ₂ Ga ₂ S ₄ : Ce, Sr ₂ G
a ₂ S ₄ : Ce and the like.

In order to obtain white light emission, Sr
S: Ce / ZnS: Mn and the like are known.

Of these, the IDW (Internati
onal Display Workshop) '97 X.Wu "Multicolor Thin-Fi
Particularly favorable results can be obtained by applying the present invention to an EL having a blue SrS: Ce light emitting layer, which is discussed in "lm Ceramic Hybrid EL Displays" p593 to 596.

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 50 nm.
It is about 0 nm.

As a method for forming the light emitting layer, a vapor phase deposition method can be used. 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 these, a chemical vapor deposition method such as a CVD method is preferable.

Further, as described in the above-mentioned IDW, when a light emitting layer of SrS: Ce is formed, H ₂ is preferably used.
When formed by an electron beam evaporation method in an S atmosphere, a high-purity light-emitting layer can be obtained.

After the formation of the light emitting layer, a heat treatment is preferably performed.
U. Heat treatment is performed on the electrode layer, insulating layer, and light emitting layer from the substrate side.
It may be performed after lamination, or from the substrate side, electrode layer, insulation
Layer, light emitting layer, insulating layer, or electrode layer formed on it
The cap annealing may be performed later. Usually, capani
It is preferable to use the rule method. Heat treatment temperature is preferred
600 to the sintering temperature of the substrate, more preferably 600
~ 1300 ° C, especially about 800 ~ 1200 ° C, processing time
Is about 10 to 600 minutes, especially about 30 to 180 minutes.
The atmosphere during the annealing process is N_Two, Ar, He
Or N_TwoO inside _TwoIs preferably 0.1% or less.

The insulating layer formed on the light emitting layer has a resistivity of 10 ⁸ Ω · cm or more, particularly 10 ¹⁰ to 10 ¹⁸ Ω · cm.
cm is preferred. 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 of this insulating layer, for example, silicon oxide (SiO ₂ ), silicon nitride (SiN), tantalum oxide (Ta ₂ O ₅ ), strontium titanate (S
rTiO ₃ ), yttrium oxide (Y ₂ O ₃ ), barium titanate (BaTiO ₃ ), lead titanate (PbTi
O ₃ ), zirconia (ZrO ₂ ), silicon oxynitride (SiON), alumina (Al ₂ O ₃ ), lead niobate (PbNb ₂ O ₆ ), and the like.

The method for forming the insulating layer with these materials is the same as that for the light emitting layer. In this case, the thickness of the insulating layer is preferably 50 to 1000 nm, particularly 100
About 500 nm.

In the EL device of the present invention, not only a single light-emitting layer but also a plurality of light-emitting layers may be stacked in the thickness direction.
It is also possible to adopt a configuration in which different types of light emitting layers (pixels) are combined in a matrix and arranged two-dimensionally.

In the thin-film EL device of the present invention, by using a substrate material obtained by firing, a light-emitting layer capable of emitting high-luminance blue light can be easily obtained, and the surface of the insulating layer on which the light-emitting layer is laminated. Is smooth, so that a high-performance, high-definition color display can be formed. Further, the manufacturing process is relatively easy, and the manufacturing cost can be kept low. Since efficient blue light emission with high luminance can be obtained, a white light emitting element may be combined with a color filter.

As the color filter film, a color filter used in a liquid crystal display or the like may be used, but the characteristics of the color filter are adjusted according to the light emitted from the EL element to optimize the extraction efficiency and the color purity. do it.

When a color filter capable of cutting off short-wavelength external light that is absorbed by the EL element material or the fluorescence conversion layer is used, the light resistance of the element and the display contrast are improved.

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

The fluorescence conversion filter film absorbs EL light and emits light from the phosphor in the fluorescence conversion film, thereby performing color conversion of the emission color. It is formed from 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 desirable that the fluorescent material has strong absorption in the EL emission wavelength region. In practice, laser dyes and the like are suitable, and rhodamine compounds, perylene compounds, cyanine compounds, phthalocyanine compounds (including subphthalocyanines, etc.) naphthalimide compounds, condensed ring hydrocarbon compounds, condensed heterocyclic compounds A styryl compound, a coumarin compound or 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.

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.

The thin film EL device of the present invention is usually driven by a pulse or an alternating current, and the applied voltage is about 50 to 300 V.

In the above example, a thin-film EL device is described as an application example of the composite substrate. However, the composite substrate of the present invention is not limited to such applications, and can be applied to various electronic materials and the like. It is. For example, application to a thin film / thick film hybrid high frequency coil element or the like is possible.

[0102]

Examples of the present invention will be described below. The EL structure used in the following examples has a structure in which a light emitting layer, an upper insulating film, and an upper electrode are sequentially laminated on the surface of an insulating layer of a composite substrate by a thin film method.

<Example 1> A paste prepared by mixing a binder (ethyl cellulose) and a solvent (terpineol) with Ag-Ti powder was spread on a 99.5% Al ₂ O ₃ substrate with a width of 1.5 mm and a gap. A pattern was printed on a 1.5 mm stripe and dried at 110 ° C. for several minutes. The dielectric paste is made of Pb (Mg _1/3 Nb) having an average particle size of 1 μm.
_2/3) O ₃ was prepared by mixing -PbTiO ₃ and (PMN-PT) powder raw material in a binder (acrylic resin) solvent (methylene chloride + acetone).

The dielectric paste was repeatedly printed and dried ten times on the substrate on which the above-mentioned electrode pattern was printed. The thickness of the obtained dielectric layer green was about 80 μm.
Thereafter, the PET film coated with silicon is placed on the dielectric precursor, and 500 ton /
It was heated and pressed at a pressure of m ² for 10 minutes. Next, this was fired in the air at 900 ° C. for 30 minutes. The thickness of the thick film dielectric layer after firing was 55 μm.

A sol-gel solution for forming a thin-film insulator layer was prepared as follows. That is, first, lead acetate is heated to 60 ° C.
For 12 hours or more in a reduced pressure atmosphere. The dehydrated lead acetate was melted by mixing with 1,3-propanediol at 120 ° C. for 2 hours.

Separately from this solution, a 1-propanol solution of zirconium tetranormal propoxide was mixed with acetylacetone at 120 ° C. for 30 minutes. To this mixed solution were added titanium diisopropoxide bisacetylacetonate and 1,3-propanediol, and further added
Mixing was performed at 2 ° C. for 2 hours. The resulting solution and the above-mentioned lead acetate solution were mixed at 80 ° C. for 5 hours. 1-propanol was added to adjust the concentration of the prepared solution.

The sol-gel solution thus prepared was passed through a 0.2-micron filter to remove precipitates and the like, and then 1500 rp was deposited on the thick dielectric of the composite substrate.
m for 1 minute. The composite substrate spin-coated with the solution was placed on a hot plate maintained at 120 ° C. for 3 minutes to dry the solution. After that, the composite substrate is heated to 600 ° C.
And baked for 15 minutes. Spin coating / drying / firing was repeated three times. Thus, a composite substrate was obtained.

<Example 2> In Example 1, drying after applying the sol-gel solution was performed at 350 ° C. Otherwise in the same manner as in Example 1, a composite substrate was obtained.

<Example 3> In Example 1, drying after applying the sol-gel solution was performed at 420 ° C. Otherwise in the same manner as in Example 1, a composite substrate was obtained.

Example 4 In Example 3, when preparing an acetic acid solution, dehydrated lanthanum oxide was added to 1,3-propanediol together with lead acetate. The solution is Pb / La
/ Zr / Ti ratio is 1.14 / 0.06 / 0.53 /
It was adjusted to be 0.47. The concentration of the solution was adjusted so that (Pb + La) in 1,000 ml of the solution was 0.8 mol. Otherwise in the same manner as in Example 1, a composite substrate was obtained.

In each of the above embodiments, the surface roughness of the dielectric was measured at 0.1 mm / sec by using a tally step.
The measurement was performed by moving an 8 mm probe. In addition, an upper electrode was formed on the dielectric layer in order to measure the electrical characteristics of the dielectric layer. The upper electrode is printed and dried with the electrode paste in a 1.5 mm width, 1.5 mm gap stripe pattern perpendicular to the electrode pattern on the substrate, and then at 850 ° C. for 15 minutes. It was formed by firing.

The dielectric characteristics were measured at 1 kHz using an LCR meter.
Was measured at the following frequency. The insulation resistance was determined by measuring a current value after applying a voltage of 25 V for 15 seconds and holding for 1 minute. Further, the voltage applied to the sample was increased at a rate of 100 V / sec, and a voltage value at which a current of 0.1 mA or more flowed was defined as a breakdown voltage. The surface roughness and electrical properties were measured three times at different locations per sample,
The average value was taken as the measured value.

The EL element is a composite substrate without an upper electrode, and is heated at 250 ° C. and doped with Mn-doped ZnS.
Using a target, a ZnS fluorescent thin film is formed by a sputtering method so as to have a thickness of 0.7 μm.
For 10 minutes. Next, Si ₃ N _{4 is used} as a second insulating layer.
An electroluminescent device was obtained by sequentially forming a thin film and an ITO thin film as a second electrode by a sputtering method. Luminescent properties are printed and fired electrodes of the obtained device structure,
The wiring was drawn out from the ITO transparent electrode, and an electric field of 1 kHz pulse width of 50 μs was applied to measure.

The electrical characteristics of the dielectric layers on the composite substrates produced as described above and the composite substrates produced using these composite substrates
Table 1 shows the emission characteristics of the EL element. For comparison, the characteristics of the composite substrate without the thin film dielectric layer are also shown.

[0115]

[Table 1]

[0116]

As described above, according to the present invention, a thick film having a smooth surface can be obtained by using a sol-gel solution having a high concentration and a large thickness without cracks. A composite substrate including a substrate having a dielectric layer / electrode / dielectric layer, a method for manufacturing the same, and an EL element using the same can be provided.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view showing a basic configuration of a thin film EL device of the present invention.

FIG. 2 is a partial cross-sectional view showing the structure of a conventional thin film EL device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Lower electrode layer 3 Lower insulating layer 4 Light emitting layer 5 Upper insulating layer 6 Upper electrode layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C04B 41/87 C04B 41/87 B 41/89 41/89 Z H05B 33/02 H05B 33/02 (72) Inventor Atsushi Hagiwara 1-13-1 Nihonbashi, Chuo-ku, Tokyo TDK Corporation (72) Inventor Masaru Takayama 1-13-1 Nihonbashi, Chuo-ku, Tokyo Fterm in TDK Corporation 3K007 AB15 AB18 CA02 CB01 DA05 DB02 EA02 EC01 FA01 4G031 AA09 AA11 AA12 AA32 BA09 CA08 GA02 GA04 GA06 4G052 DA02 DA08 DB12 DC06 4G055 AA08 AC01 AC09 BA35 BA38 BA40 BA42

Claims (9)

[Claims] 1. A method of manufacturing a composite substrate having an electrically insulating substrate and an electrode and an insulator layer formed on the substrate by a thick film method in sequence, comprising: a metal compound on the insulator layer; diols as solvents _{(OH (CH 2) n OH} ) sol was prepared by dissolving - gel solution coating, after drying, the manufacturing method of the composite substrate to sintering to form a thin film insulator layer. 2. The method according to claim 1, wherein the solvent is propanediol (OH
_{2. The} method according to claim 1, wherein (CH ₂ ) ₃ OH). 3. The method according to claim 1, wherein at least one of the metal compounds is acetylacetonate (M (CH ₃ COCHCOCH ₃ )).
_n : wherein M is a metal element, or acetylacetonate by reacting a metal compound with acetylacetone (CH ₃ COCH ₂ COCH ₃ ). 4. The method according to claim 1, wherein the metal compound is (Pb_xLa_1-x)
(Zr_y, Ti_1-y) O _Three (Where 0 ≦ x, y ≦ 1)
A method for manufacturing a composite substrate according to claim 1. 5. The drying temperature of the sol-gel solution is 35.
The method for producing a composite substrate according to claim 1, wherein the temperature is 0 ° C. or higher. 6. A composite substrate obtained by the method according to claim 1. 7. The composite substrate according to claim 6, wherein a functional thin film is formed on the insulator layer. 8. An EL device having at least a light emitting layer and a transparent electrode on the composite substrate according to claim 6. 9. The EL device according to claim 8, further comprising a thin film insulating layer between the light emitting layer and the transparent electrode.