JP4656074B2 - Electro-optical device and method of manufacturing electro-optical device - Google Patents

Description

  The present invention relates to an electro-optical device, a film-like member suitable for the electro-optical device, a laminated film, a low refractive index film, a multilayer laminated film, and an electronic apparatus including the electro-optical device.

  An organic electroluminescence display device (electro-optical device) equipped with an organic electroluminescence element corresponding to each pixel is self-luminous with high brightness, can be driven at a low voltage, and has a high response speed. Therefore, it is expected to be a display device that will follow the liquid crystal display device in the future because the display device is excellent in display performance and the display device can be made thinner, lighter and consume less power.

  FIG. 16 is a cross-sectional view showing an example of a schematic organic electroluminescence display device. In this organic electroluminescence display device 100, an organic electroluminescence in which a light emitting layer 102 and a hole transport layer 103 are sandwiched between a metal electrode (cathode) 104 and a transparent electrode (anode) 105 on a glass substrate 101. An element 106 is formed. Although not shown, in the case of an active matrix type organic electroluminescence display device, a plurality of data lines and a plurality of scanning lines are actually arranged in a grid pattern, and are arranged in a matrix partitioned by these data lines and scanning lines. A driving transistor such as a switching transistor or a driving transistor and the organic electroluminescence element 106 are disposed for each pixel. When a drive signal is supplied via the data line or the scanning line, a current flows between the electrodes, the organic electroluminescence element 106 emits light, light is emitted to the outer surface side of the glass substrate 101, and the pixel is turned on. .

  By the way, although light emission occurs in all directions in the light emitting layer 102, light emitted at a wide angle (for example, a critical angle or more) is guided in the glass substrate 101 as shown in the schematic diagram of FIG. It cannot be taken out of the 101. That is, since the light extraction efficiency is poor, even if light is emitted by supplying a predetermined current to the light emitting layer 102, only a part of the light contributes to display, leading to a decrease in visibility.

  On the other hand, an organic electroluminescent element and an electrode sandwiching the organic electroluminescent element are deteriorated by a substance that causes element deterioration such as oxygen or water vapor (moisture). In a so-called active electro-optical device including an active element such as a transistor, the active element may be deteriorated when oxygen, water vapor (moisture), or various ion species reach the active element.

  The present invention has been made in view of such circumstances, and one object of the present invention is to improve the external extraction efficiency of light while maintaining sealing performance, and to achieve high visibility. Is to provide.

In order to solve the above problems, an electro-optical device according to the present invention includes a low refractive index layer having a lower refractive index than the substrate, a sealing layer provided on the low refractive index layer, on the substrate, A polymer layer provided on the sealing layer; and a light-emitting element provided on the polymer layer, wherein the light-emitting element includes a first electrode, a second electrode, and the first electrode and the first electrode. It has a light emitting layer arranged between two electrodes, and light emitted from the light emitting layer is emitted to the substrate side.
In the above electro-optical device, a resin layer is provided between the low refractive index layer and the sealing layer.
In the electro-optical device, a sealing member is provided on the light emitting element so as to cover the light emitting element.
In the electro-optical device, the thickness of the sealing layer is smaller than the wavelength of light emitted from the electro-optical element.
In the above electro-optical device, the thickness of the sealing layer is smaller than the wavelength of light emitted from the light emitting element.
In the above electro-optical device, the sealing layer includes at least one of ceramic, silicon nitride, silicon oxynitride, and silicon oxide.
In the above electro-optical device, the sealing layer contains at least one element selected from boron, carbon, nitrogen, aluminum, silicon, phosphorus, ytterbium, samarium, erbium, yttrium, gadolinium, dysprosium, and neodymium. It is characterized by.
In the above electro-optical device, at least one of the low refractive index layer and the sealing layer includes a desiccant or an adsorbent.
In the above electro-optical device, the low refractive index layer includes at least one material selected from aerogel, porous silica, and magnesium fluoride.
In the above electro-optical device, the refractive index of the low refractive index layer is 1.2 or less.
In the above electro-optical device, the low refractive index layer and the sealing layer transmit light.
In the above electro-optical device, the sealing layer suppresses the transmission of a substance.
In order to solve the above-described problem, an electro-optical device manufacturing method according to the present invention includes a first step of forming a low refractive layer having a lower refractive index than the substrate on the substrate, and the low refractive layer on the low refractive layer. A second step of forming a sealing layer, a third step of forming a polymer layer on the sealing layer, and a fourth step of forming a light emitting element on the polymer layer, The light emitting element includes a first electrode, a second electrode, and a light emitting layer disposed between the first electrode and the second electrode, and light emitted from the light emitting layer is emitted to the substrate side. It is characterized by doing.
In the method of manufacturing the electro-optical device, the first step includes a step of applying a wet gel and a drying step of drying the wet gel using a supercritical drying method. The resin is mixed.
The method of manufacturing the electro-optical device includes a step of forming a resin layer between the low refractive layer and the sealing layer.
The method of manufacturing the electro-optical device includes a step of providing a sealing member on the light emitting element so as to cover the light emitting element.
In the electro-optical device manufacturing method, the sealing thickness is smaller than the wavelength of light emitted from the electro-optical element.
In the electro-optical device manufacturing method, the sealing layer has a thickness smaller than a wavelength of light emitted from the light emitting element.
The method for manufacturing a film-shaped member according to the present invention is a method for manufacturing a film-shaped member including a first film and a second film that is an insulating film, and includes a first step of forming the first film. And a second step of forming the second film, wherein the first step includes a drying step using a supercritical drying method.
In the method for manufacturing a film-shaped member, the first film may be made of a low refractive index material.
In the method for manufacturing a film-like member, the second film may include at least one of ceramic, silicon nitride, silicon oxynitride, and silicon oxide.
In the method for manufacturing a film-shaped member, at least one of the first film and the second film may include at least one of a desiccant and an adsorbent.
In the method for manufacturing a film-shaped member, the second film is at least one selected from boron, carbon, nitrogen, aluminum, silicon, phosphorus, ytterbium, samarium, erbium, yttrium, gadolinium, dysprosium, and neodymium. You may make it contain an element.
In the method for manufacturing a film-shaped member, the first film may include at least one material selected from airgel, porous silica, and magnesium fluoride.
In the method for manufacturing a film-like member, the refractive index of the first film may be 1.2 or less.
In the method for manufacturing a film-like member, the first film may transmit light.
In the method for manufacturing a film-shaped member, the first step may further include an application step of applying a wet gel, and the wet gel may be dried in the drying step.
In the method for manufacturing a film-shaped member, the second film may suppress the permeation of a substance.
In the method for manufacturing a film-shaped member, the first film and the second film may both transmit light.
In the method for manufacturing a film-shaped member, the first film may be a SiO ₂ film.
In the method for manufacturing a film-shaped member, the first film may be formed on a substrate, and the refractive index of the first film may be lower than the refractive index of the substrate.
In the method for manufacturing a film-shaped member, the first film may be disposed between the second film and the substrate.
A method for manufacturing an electro-optical device according to the present invention, the method for manufacturing an electro-optical device including an electro-optical element, including the method for manufacturing a film-like member described above.
Another electro-optical device manufacturing method according to the present invention is a method for manufacturing an electro-optical device including a substrate, an electro-optical element, a first film, and a second film that is an insulating film. A first step of forming a film; and a second step of forming the second film, wherein the first step includes a drying step using a supercritical drying method. .
In the method for manufacturing the electro-optical device, the refractive index of the first film may be lower than the refractive index of the substrate.
In the method for manufacturing the electro-optical device, the second film may suppress transmission of a substance.
In the above method for manufacturing an electro-optical device, the second film may be disposed between the electro-optical element and the first film.
In order to solve the above problems, an electro-optical device of the present invention is an electro-optical device having a light-emitting element, including a sealing layer that blocks transmission of a substance, and a direction in which light emitted from the light-emitting element is extracted. A low refractive index layer is disposed on the substrate.
The sealing layer can be appropriately selected depending on the substance whose transmission should be suppressed. For example, ceramics, particularly silicon nitride, silicon oxynitride, silicon oxide, and the like are preferable for suppressing oxygen and water permeation. Moreover, what disperse | distributed at least one of the desiccant and the adsorption agent to the organic material or the inorganic material may be used. In order to suppress the penetration of metal ions, for example, it is preferable to add various elements to the insulating film.
Here, the refractive index of the low refractive index layer is preferably 1.5 or less, and more preferably 1.2 or less. In addition, when the member which makes an interface with air in the light extraction direction is provided, the refractive index of the low refractive index layer may be lower than that member.

  According to the present invention, since the light emitted from the light emitting layer passes through the low refractive index layer, reflection when the light is emitted into the air is reduced and the light extraction efficiency is improved. By disposing in the light extraction direction, it becomes possible to block deterioration factors of the light emitting element such as oxygen and water entering from the light extraction direction by the sealing layer.

  Examples of the low refractive index layer include a porous body that can transmit light, aerogel, porous silica, magnesium fluoride or a material containing the same, a gel in which fine particles of magnesium fluoride are dispersed, a fluorine-based polymer, or the like. Examples thereof include a material, a porous polymer having a branched structure such as a dendrimer, and a material containing at least one of inorganic fine particles and organic fine particles in a predetermined material.

  In the case where light is extracted from the side of a glass substrate that is generally used as a substrate for arranging a light emitting element, the refractive index of the glass is 1.54. Therefore, the low refractive index layer has a refractive index of about 1.5. It is desirable to set as follows. More preferably, it is 1.2 or less.

In the electro-optical device, an energization control unit that performs energization control of the light emitting element may be disposed on the substrate. In this case, the light emitted from the light-emitting element can be taken out from the substrate on which the energization control unit is disposed, and the light emitted from the light-emitting element is also emitted from the opposite side of the light-emitting element to the substrate. It can be taken out.
For example, a transistor or a diode can be used as the energization control unit. In particular, the thin film transistor is suitable for the energization control unit because it is light transmissive and can be formed on an inexpensive glass substrate.

  The electro-optical device of the present invention is an electro-optical device including a light-emitting element, and has a low refractive index in which at least one of a desiccant and an adsorbent is dispersed in a direction in which light emitted from the light-emitting element is extracted. It is characterized in that the layers are arranged.

  The electro-optical device includes a low refractive index layer in which a desiccant or an adsorbent is dispersed, so that the light extraction efficiency is high, and the transmission of substances that cause deterioration such as light-emitting elements and electrodes is suppressed. can do.

  In the above electro-optical device, the light-emitting element may be an organic electroluminescence element. Since the organic electroluminescence element may have a reduction in light emission efficiency and element lifetime due to contact with water, oxygen, or the like, deterioration of the element can be reduced by providing a sealing layer. In general, at least one of the electrodes sandwiching the organic electroluminescence is formed of a metal that easily deteriorates due to water, oxygen, or the like, so that deterioration of the electrode can be reduced.

  The film-like member of the present invention is characterized by having a low refractive index layer and a sealing layer that suppresses permeation of a substance. Here, the low refractive index layer means a layer having a refractive index of 1.5 or less. In particular, the refractive index of the low refractive index layer may be preferably 1.2 or less. For example, an element or device having an electro-optical function can be maintained for a long time by being covered with the film-like member of the present invention.

  In the film member, at least one of a desiccant and an adsorbent may be dispersed in at least one of the low refractive index and the sealing layer.

  The laminated film of the present invention is characterized by having a low refractive index layer and a sealing layer that suppresses permeation of a substance. Here, the low refractive index layer means a layer having a refractive index of 1.5 or less. In particular, the refractive index of the low refractive index layer may be preferably 1.2 or less. For example, an element or device having an electro-optical function can be maintained for a long time by being covered with the laminated film of the present invention.

  A porous body can be used as the low refractive index layer of the laminated film. Since the porous body has a high void ratio, the refractive index can be sufficiently lowered.

  As the low refractive index layer of the above laminated film, for example, aerogel, porous silica, magnesium fluoride or a material containing this, a gel in which fine particles of magnesium fluoride are dispersed, a fluorine-based polymer or a material containing this, Examples thereof include a porous polymer having a branched structure, and a material containing at least one of inorganic fine particles and organic fine particles in a predetermined material. That is, a material having a high void occupation ratio, a low density material, or a material having a low atomic refractive index or molecular refractive index can be employed.

  The low refractive index film of the present invention is characterized in that at least one of a desiccant and an adsorbent is dispersed in a low refractive index material.

  According to the present invention, the low refractive index film can suppress the permeation of the substance by dispersing the desiccant or the adsorbent in the low refractive index material. Therefore, the low refractive index film of the present invention is suitable for an electro-optical element and an electro-optical device.

  The multilayer laminated film of the present invention includes the laminated film and the low refractive index film. Permeation of a substance can be further suppressed by multilayering the film as in the present invention. In addition, it is possible to suppress the transmission of different substances in each of the plurality of sealing layers.

  Therefore, the multilayer laminated film of the present invention is suitable for an electro-optical element or an electro-optical device.

  An electro-optical device according to the present invention includes an electro-optical element and at least one of the laminated film, the low refractive index film, and the multilayer laminated film.

  According to the present invention, by providing the film, it is possible to improve the light extraction efficiency and prevent deterioration of various electro-optical elements and electro-optical devices.

The electro-optical device further includes an energization control unit that performs energization control of the electro-optical element, and a substrate that supports the energization control unit.
At least one of the laminated film, the low refractive index film, and the multilayer laminated film may be disposed on at least one main surface of the substrate. In such a case, the deterioration of the electro-optical device can be prevented by blocking or adsorbing a substance entering from the substrate side.

  At least one of the film member, the laminated film, the low refractive index film, and the multilayer laminated film may be arranged on the opposite side of the electro-optic element from the substrate. In such a case, a substance that enters from above the electro-optical element can be blocked or adsorbed, so that the electro-optical device can be prevented from deteriorating.

  For example, a transistor or a diode can be used as the energization control unit. In particular, the thin film transistor is suitable for the energization control unit because it can be formed on an inexpensive glass substrate having light transmittance.

  The electro-optic element may be an organic electroluminescence element.

  An electronic apparatus according to the present invention includes the electro-optical device according to the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the electronic device which is excellent in display quality and can hold | maintain a desired function for a long time is realizable.

<< First Embodiment >>
Hereinafter, the electro-optical device of the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view showing an example of a first embodiment of an organic electroluminescence display device which is an electro-optical device of the present invention.
In FIG. 1, an organic electroluminescence display device 1 includes a substrate (light transmission layer) 2 capable of transmitting light, and a pair of cathode (electrode) 7 and anode (electrode) 8 provided on one surface side of the substrate 2. An organic electroluminescent element (light emitting element) 9 comprising a light emitting layer 5 and a hole transport layer 6 made of a sandwiched organic electroluminescent material, and a low layer laminated between the substrate 1 and the organic electroluminescent element 9. A refractive index layer 3 and a sealing layer 4 are provided. The low refractive index layer 3 is provided closer to the substrate 2 than the sealing layer 4.

Here, the organic electroluminescence display device 1 shown in FIG. 1 has a form in which light emitted from the light emitting layer 5 is extracted from the substrate 2 side to the outside of the device, and the forming material of the substrate 2 is transparent or semi-transparent capable of transmitting light. Transparent materials such as transparent glass, quartz, sapphire, or transparent synthetic resins such as polyester, polyacrylate, polycarbonate, polyether ketone, and the like can be given. In particular, an inexpensive soda glass is preferably used as a material for forming the substrate 2.
On the other hand, in the form of taking out light emission from the opposite side of the substrate, the substrate may be opaque, in which case, ceramic such as alumina, metal sheet such as stainless steel subjected to insulation treatment such as surface oxidation, A thermosetting resin, a thermoplastic resin, or the like can be used.

  The anode 8 is a transparent electrode made of indium tin oxide (ITO) or the like, and can transmit light. The hole transport layer 6 is made of, for example, a triphenylamine derivative (TPD), a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, or the like. Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, JP-A-3-37992, and JP-A-3-152184. Examples described in the publication are exemplified, but a triphenyldiamine derivative is preferable, and 4,4′-bis (N (3-methylphenyl) -N-phenylamino) biphenyl is particularly preferable. Polymeric materials such as polyethylene dioxythiophene or a mixture of polyethylene dioxythiophene and polystyrene sulfonic acid can also be used.

  Note that a hole injection layer may be formed instead of the hole transport layer, and both the hole injection layer and the hole transport layer may be formed. In this case, as a material for forming the hole injection layer, for example, copper phthalocyanine (CuPc), polytetravinylthiophene polyphenylene vinylene, 1,1-bis- (4-N, N-ditolylaminophenyl) cyclohexane , Tris (8-hydroxyquinolinol) aluminum and the like, and copper phthalocyanine (CuPc) is particularly preferable.

As a material for forming the light emitting layer 5, low molecular organic light emitting dyes and polymer light emitting materials, that is, light emitting materials such as various fluorescent materials and phosphorescent materials, and organic electroluminescent materials such as Alq ₃ (aluminum chelate complexes) can be used. It is. Among the conjugated polymers that serve as the light-emitting substance, those containing an arylene vinylene or polyfluorene structure are particularly preferable. Examples of the low-molecular light emitters include naphthalene derivatives, anthracene derivatives, perylene derivatives, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroquinoline and its metal complexes, aromatic amines, tetraphenylcyclo Pentadiene derivatives and the like, or known ones described in JP-A-57-51781 and 59-194393 can be used. The cathode 7 is a metal electrode made of aluminum (Al), magnesium (Mg), gold (Au), silver (Ag), or the like. Moreover, what laminated | stacked these metals can also be used as a cathode.

  An electron transport layer or an electron injection layer can be provided between the cathode 7 and the light emitting layer 5. The material for forming the electron transport layer is not particularly limited, and is an oxadiazole derivative, anthraquinodimethane and its derivative, benzoquinone and its derivative, naphthoquinone and its derivative, anthraquinone and its derivative, tetracyanoanthraquinodimethane And derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like. Specifically, as with the material for forming the hole transport layer, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-209888 are disclosed. And the like described in JP-A-3-379992 and 3-152184, particularly 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4. -Oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum are preferred.

The low refractive index layer 3 is a layer having a light transmission refractive index lower than that of the substrate 2 and is made of silica aerogel. Silica aerogel is a light-transmitting porous material having a uniform ultrafine structure obtained by supercritical drying of a wet gel formed by a sol-gel reaction of silicon alkoxide. Silica airgel is a material composed of fine SiO ₂ particles of several tens of nanometers, with the voids occupying 90% or more of the volume, and the remainder agglomerated in a dendritic manner. The refractive index is 1.2 or less. Further, the refractive index can be adjusted by changing the porosity. Here, the refractive index of glass, which is the material of the substrate 2, is 1.54, and the refractive index of quartz is 1.45.

  Silica airgel is manufactured through a step of producing a wet gel by a sol-gel method, a step of aging the wet gel, and a supercritical drying step of drying the wet gel by a supercritical drying method to obtain an airgel. The supercritical drying method is a method suitable for drying a gel material without contracting the gel by replacing and removing the liquid in the jelly-like gel material consisting of a solid phase and a liquid phase with a supercritical fluid. Thus, an airgel having a high porosity can be obtained.

The low refractive index layer 3 may be a porous SiO ₂ film instead of the silica airgel layer using the supercritical drying method. This SiO ₂ film is formed by a plasma CVD method (plasma chemical vapor deposition method), and SiH ₄ and N ₂ O are used as reaction gases. Furthermore, on this SiO ₂ film, a SiO ₂ film having a porosity. This SiO ₂ film is formed by an atmospheric pressure CVD method (atmospheric pressure chemical vapor deposition method), and a reactive gas containing TEOS (tetraethoxysilane), O ₂ (oxygen), and a low concentration of O ₃ (ozone) is used. Use. Here, the low concentration of O ₃ means a concentration of O ₃ lower than the concentration necessary for the oxidation of TEOS.

  The sealing layer 4 blocks air from entering the organic electroluminescence element 9 including the electrodes 7 and 8 from the outside on the substrate 2 side. Can be transmitted. As a material constituting the sealing layer 4, for example, a transparent material such as ceramic, silicon nitride, silicon oxynitride, or silicon oxide is used, and among these, silicon oxynitride is preferable from the viewpoints of transparency and gas barrier properties. Metal ions may cause deterioration of the device. In such a case, for example, boron, carbon, nitrogen, aluminum, silicon, phosphorus, ytterbium, samarium, erbium, yttrium, gadolinium, dysprosium, neodymium, etc. An insulating film containing at least one element selected from these elements can also be used as the sealing layer 4. For example, at least one selected from desiccants or adsorbents such as magnesium oxide, magnesium carbonate, iron oxide, titanium oxide, bentonite, acid clay, montmorillonite, diatomaceous earth, activated alumina, silica alumina, zeolite, silica, zirconia, and barium oxide. Those containing one material can also be used as the sealing layer 4 because they adsorb or occlude oxygen and moisture. The thickness of the sealing layer 4 is preferably set so as to be smaller than the wavelength of light emitted from the light emitting layer 5 (for example, 0.1 μm).

  When the organic electroluminescence display device 1 is of an active matrix type, although not shown, a plurality of data lines and a plurality of scanning lines are arranged in a lattice pattern, and the matrix is divided into these data lines and scanning lines. For each pixel arranged in a shape, the organic electroluminescence element 9 is driven by a transistor such as a switching transistor or a driving transistor. When a drive signal is supplied via the data line or the scanning line, a current flows between the electrodes, the light emitting layer 5 of the organic electroluminescence element 9 emits light, and light is emitted to the outer surface side of the substrate 2. Lights up.

  Further, in the organic electroluminescence display device 1, the atmosphere enters the organic electroluminescence element 9 including the electrodes 7 and 8 on the surface opposite to the sealing layer 4 with the organic electroluminescence element 9 interposed therebetween. The sealing member 10 which interrupts | blocks is formed.

  When the organic electroluminescence display device 1 is manufactured, first, a wet gel, which is an airgel raw material, is coated on the substrate 2 and is supercritically dried to form the low refractive index layer 3. In general, aerogel has high hygroscopicity, and if it is desired to reduce hygroscopicity, the supergel drying may be performed after hydrophobizing the thin film of the wet gel formed by coating with hexamethyldisilazane or the like. . Next, a silicon nitride film is formed on the low refractive index layer 3 as the sealing layer 4 by plasma CVD. A buffer layer made of a resin or the like may be provided between the low refractive index layer and the sealing layer in order to improve adhesion. Then, the anode 8 is formed on the sealing layer 4 by sputtering, ion plating, vacuum deposition, or the like, and the hole transport layer 6, the light emitting layer 5, and the cathode 7 are sequentially deposited on the anode 8 and laminated. Thus, the organic electroluminescence display device 1 is manufactured.

  In the organic electroluminescence display device 1 configured as described above, the light emitted from the light emitting layer 5 passes through the transparent electrode 8 and enters the substrate 2 through the sealing layer 4 and the low refractive index layer 3. At this time, since the refractive index of the low refractive index layer 3 made of silica airgel is lower than that of the substrate 2 made of glass or quartz, light is incident on the high refractive index material from the low refractive index material. The light incident on the low-refractive index layer 3 at the above angle is refracted in a direction equal to or less than the critical angle at the interface with the substrate 2 and deviates from the total reflection condition in the substrate 2, thereby improving the light extraction efficiency. Can do.

  As described above, the light emitted from the light emitting layer 5 passes through the low refractive index layer 3 having a lower refractive index than that of the substrate 2 and then enters the substrate 2, so that the low refractive index layer 3 has an angle greater than the critical angle. The light incident on the substrate 2 is refracted in the direction of the critical angle or less at the interface with the substrate 2, deviates from the total reflection condition in the substrate 2, and is extracted outside. Thereby, the light extraction efficiency is improved and high visibility can be obtained. Further, even if the low refractive index layer 3 is made of a material having high air permeability such as silica airgel, the intrusion of air from the substrate 2 side is suppressed by the sealing layer 4. The electroluminescence element 9 is not exposed to the atmosphere and is prevented from being deteriorated. Therefore, the organic electroluminescence display device 1 can maintain good light emission characteristics. In addition, by providing the low refractive index layer 3 close to the substrate 2, reflection from the inside is suppressed even when external light is irradiated from the substrate 2 side, and high visibility of light from the organic electroluminescence element 9 is achieved. Can be maintained.

  In this embodiment, each layer including the low refractive index layer 3 and the sealing layer 4 is formed by sequentially laminating by a plasma CVD method, a sputtering method, or a vapor deposition method, but as shown in FIG. A film-like member (laminated film) 20 having the low refractive index layer 3 and the sealing layer 4 may be formed in advance, and this film-like member may be disposed between the substrate 2 and the anode 8.

  In this embodiment, the low refractive index layer 3 is provided on the substrate 2 and the sealing layer 4 is provided on the low refractive index layer 3. However, the sealing layer 4 is provided on the substrate 2 and sealed. The low refractive index layer 3 may be provided on the layer 4. Thus, the layer configuration between the anode 8 (organic electroluminescence element 9) and the substrate 2 may be substrate 2 / low refractive index layer 3 / sealing layer 4 / anode 8 or substrate 2 / sealing layer. 4 / low refractive index layer 3 / anode 8 may be used. Furthermore, a plurality of sealing layers may be provided such as substrate 2 / sealing layer 4 / low refractive index layer 3 / sealing layer 4 / anode 8 and sealing layer.

    A polymer layer may be interposed between the sealing layer (barrier layer) 4 and the anode 8 or between the low refractive index layer 3 and the sealing layer 4. As a material constituting the polymer layer, general hydrocarbon polymers such as polyethylene, polystyrene, and polypropylene can be used. Polymer fine particles synthesized by monomer polymerization reaction (for example, emulsion polymerization method) can also be used. A fluorine-containing polymer containing a fluorine atom can also be used. Examples of the monomer containing a fluorine atom used for synthesizing the fluorine-containing polymer include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1 , 3-dioxole), fluorinated alkyl esters of acrylic acid or methacrylic acid and fluorinated vinyl ethers. A copolymer of a monomer containing a fluorine atom and a monomer not containing a fluorine atom may be used. Examples of monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic esters (eg, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate). , Methacrylates (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate), styrenes (eg, styrene, vinyl toluene, α-methyl styrene), vinyl ethers (eg, methyl vinyl ether), vinyl esters ( Examples include vinyl acetate, vinyl propionate), acrylamides (eg, N-tert-butylacrylamide, N-cyclohexylacrylamide), methacrylamides and acrylonitriles.

When the low refractive index layer 3 is formed of silica aerogel, a wet gel is applied to the substrate 2 by spin coating or the like, followed by supercritical drying. However, a synthetic resin (organic substance) may be mixed in the wet gel. The synthetic resin in this case is preferably a synthetic resin having a heat denaturation temperature higher than the critical temperature of the supercritical fluid and capable of transmitting light. For example, when alcohol is used as a supercritical fluid, the heat denaturation temperature is higher than the critical temperature of alcohol, and synthetic resins capable of transmitting light include hydroxylpropyl cellulose (HPC), polyvinyl butyral (PVB), and ethyl cellulose (EC). (In addition, PVB and EC are soluble in alcohol and insoluble in water). When ether is used as the solvent, chlorine-based polyethylene or the like is preferably selected as the resin, and when CO ₂ is used as the solvent, HPC or the like is preferably selected.

The low refractive index layer 3 in the present embodiment is a silica airgel, but may be an airgel based on alumina as long as it is a porous body that can transmit light with a lower refractive index than the substrate 2. The porous body (aerogel) preferably has a density of 0.4 g / cm ³ or less.

  On the other hand, the low refractive index layer 3 may not be a porous body, and can transmit light such as an epoxy adhesive (refractive index: 1.42) or an acrylic adhesive (refractive index: 1.43). An adhesive made of a polymer material having a lower refractive index than that of the substrate 2 may be used. Even when these adhesives are used alone, the light extraction efficiency can be improved because the refractive index is lower than that of glass or quartz constituting the substrate 2. Moreover, when using these adhesives, the organic electroluminescent display apparatus 1 can be manufactured by bonding the board | substrate 2 and the sealing layer 4 together.

  Further, the low refractive index layer 3 may be porous silica, magnesium fluoride (refractive index: 1.38) or a material containing the same. The low refractive index layer 3 made of magnesium fluoride can be formed by sputtering. Alternatively, a gel in which fine particles of magnesium fluoride are dispersed may be used. Alternatively, it may be a fluorine-based polymer or a material containing the same, for example, a perfluoroalkyl-polyether, a perfluoroalkylamine, or a perfluoroalkyl-polyether-perfluoroalkylamine mixed film.

Furthermore, a predetermined polymer binder may be mixed with a soluble or dispersible low refractive index fluorocarbon compound.
As the polymer binder, polyvinyl alcohol, polyacrylic acid, polyvinyl pyrrolidone, polyvinyl sulfonic acid sodium salt, polyvinyl methyl ether, polyethylene glycol, poly α-trifluoromethyl acrylic acid, polyvinyl methyl ether-co-maleic anhydride, polyethylene glycol- Examples include co-propylene glycol and polymethacrylic acid.
Examples of the fluorocarbon compound include perfluorooctanoic acid-ammonium salt, perfluorooctanoic acid-tetramethylammonium salt, perfluoroalkylsulfonic acid ammonium salt of C-7 and C-10, and perfluorooctanoic acid ammonium salt of C-7 and C-10. Examples include tetramethylammonium fluoroalkylsulfonic acid salts, fluorinated alkyl quaternary ammonium iodides, perfluoroadipic acid, and quaternary ammonium salts of perfluoroadipic acid.

Furthermore, since a method of introducing voids as the low refractive index layer 3 is effective, in addition to the airgel, voids may be formed as microvoids between or within the fine particles. As the fine particles, inorganic fine particles or organic fine particles can be used for the low refractive index layer.
The inorganic fine particles are preferably amorphous. The inorganic fine particles are preferably made of a metal oxide, nitride, sulfide or halide, more preferably a metal oxide or metal halide, and most preferably a metal oxide or metal fluoride. . As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb and Ni are preferred, and Mg, Ca, B and Si are more preferred. An inorganic compound containing two kinds of metals may be used. A particularly preferred inorganic compound is silicon dioxide, ie silica.

  The microvoids in the inorganic fine particles can be formed, for example, by cross-linking silica molecules forming the particles. Crosslinking silica molecules reduces the volume and makes the particles porous. (Porous) inorganic fine particles having microvoids are described in the sol-gel method (described in JP-A Nos. 53-112732 and 57-9051) or the precipitation method (APPLIED OPTICS, 27, page 3356 (1988)). ) Can be directly synthesized as a dispersion. Further, the powder obtained by the drying / precipitation method can be mechanically pulverized to obtain a dispersion. Commercially available porous inorganic fine particles (for example, silicon dioxide sol) may be used. The inorganic fine particles having microvoids are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (eg, methanol, ethanol, isopropyl alcohol) and ketone (eg, methyl ethyl ketone, methyl isobutyl ketone) are preferable.

  The organic fine particles are also preferably amorphous. The organic fine particles are preferably polymer fine particles synthesized by polymerization reaction of monomers (for example, emulsion polymerization method). The organic fine particle polymer preferably contains a fluorine atom. Examples of the monomer containing a fluorine atom used for synthesizing the fluorine-containing polymer include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1 , 3-dioxole), fluorinated alkyl esters of acrylic acid or methacrylic acid and fluorinated vinyl ethers. A copolymer of a monomer containing a fluorine atom and a monomer not containing a fluorine atom may be used. Examples of monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic esters (eg, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate). , Methacrylates (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate), styrenes (eg, styrene, vinyl toluene, α-methyl styrene), vinyl ethers (eg, methyl vinyl ether), vinyl esters ( Examples include vinyl acetate, vinyl propionate), acrylamides (eg, N-tert-butylacrylamide, N-cyclohexylacrylamide), methacrylamides and acrylonitriles.

  The microvoids in the organic fine particles can be formed, for example, by crosslinking a polymer that forms the particles. Crosslinking the polymer reduces the volume and makes the particles porous. In order to crosslink the polymer forming the particles, it is preferable to use 20 mol% or more of the monomer for synthesizing the polymer as a polyfunctional monomer. The ratio of the polyfunctional monomer is more preferably 30 to 80 mol%, and most preferably 35 to 50 mol%. Examples of polyfunctional monomers include dienes (eg, butadiene, pentadiene), esters of polyhydric alcohols and acrylic acid (eg, ethylene glycol diacrylate, 1,4-cyclohexane diacrylate, dipentaerythritol hexaacrylate), Esters of polyhydric alcohol and methacrylic acid (eg, ethylene glycol dimethacrylate, 1,2,4-cyclohexanetetramethacrylate, pentaerythritol tetramethacrylate), divinyl compounds (eg, divinylcyclohexane, 1,4-divinylbenzene), divinyl Sulfones, bisacrylamides (eg, methylene bisacrylamide) and bismethacrylamides are included. Microvoids between particles can be formed by stacking at least two fine particles.

The low refractive index layer 3 may be made of a material having fine pores and fine inorganic particles. In this case, the low-refractive index layer 3 is formed by coating, and the fine pores are formed by performing an activated gas treatment after applying the layer, and the gas is released from the layer. Alternatively, the low refractive index layer 3 may be formed by mixing two or more types of ultrafine particles (for example, MgF ₂ and SiO ₂ ) and changing the mixing ratio in the film thickness direction. The refractive index changes by changing the mixing ratio. The ultrafine particles are bonded by SiO ₂ generated by the thermal decomposition of ethyl silicate. In the thermal decomposition of ethyl silicate, carbon dioxide and water vapor are also generated by combustion of the ethyl portion. Since carbon dioxide and water vapor are separated from the layer, a gap is formed between the ultrafine particles. Alternatively, the low refractive index layer 3 may be formed by containing inorganic fine powder made of porous silica and a binder, and voids are formed between the fine particles by stacking two or more fine particles made of a fluorine-containing polymer. The low refractive index layer 3 may be formed.

  Porosity can also be improved at the molecular structure level. For example, a low refractive index can be obtained by using a polymer having a branched structure such as a dendrimer.

  The low refractive index layer 3 is desirably set to have a refractive index of 1.5 or less, and more preferably 1.2 or less, using the above materials.

<< Second Embodiment >>
FIG. 3 shows a second embodiment of the organic electroluminescence display device of the present invention. In the description using FIG. 3, the description of the same or equivalent components as those in the first embodiment is omitted.
In FIG. 3, the organic electroluminescence display device 1 includes a substrate 2 capable of transmitting light, and a light emitting layer 5 and a hole transport layer 6 provided on one surface of the substrate 2 and sandwiched between a pair of electrodes 7 and 8. An organic electroluminescent element 9 provided, and a low refractive index layer (low refractive index film) 11 provided between the substrate 2 and the anode 8 of the organic electroluminescent element 9 and having a refractive index lower than that of the substrate 2 are provided. . In the low refractive index layer 11, at least one of a desiccant and an adsorbent is dispersed.
That is, in this embodiment, there is no sealing layer, and the low refractive index layer 11 according to this embodiment is obtained by dispersing a desiccant or an adsorbent in the material constituting the low refractive index layer described in the first embodiment. It is.

  The low refractive index layer 11 is obtained by mixing a powder desiccant with a synthetic resin that can transmit light and has a refractive index lower than that of the substrate 2 such as an acrylic resin or an epoxy resin. Since the powder of the desiccant is mixed in the synthetic resin, the moisture that permeates the low refractive index layer 11 can be reduced. As the resin, it is preferable to use a resin that is cured by mixing two liquids such as an epoxy resin or by ultraviolet irradiation. When there is no fear that the organic electroluminescence element 9 is deteriorated by heating, a type that is cured by heating may be used. The desiccant is mixed before the low refractive index layer 11 is cured, and can be evenly mixed into the low refractive index layer 11 when the resin is cured after sufficiently kneading. As the desiccant, a chemisorbable substance can be used. Examples of the chemisorbing desiccant include oxides of alkaline earth metals such as calcium oxide and barium oxide, halides of alkaline earth metals such as calcium chloride, and phosphorus pentoxide. In addition, for example, acid clay, montmorillonite, diatomaceous earth, activated alumina, silica alumina, zeolite, silica, zirconia and the like can be used.

  As described above, even if the main component of the low refractive index layer 11 is a highly breathable material such as a synthetic resin, a sealing function (barrier function) is formed in the low refractive index layer 11 by dispersing the desiccant particles. ). Therefore, intrusion of components such as oxygen and moisture from the substrate side 2 that cause deterioration of the element can be suppressed by the low refractive index layer 11, and good light emission characteristics can be maintained.

  Also in the present embodiment, the low refractive index layer 11 containing the desiccant is formed in advance as a film member (low refractive index film), and this film member is disposed between the substrate 2 and the anode 8. You may do it.

  Further, the multilayer film having the low refractive index layer and the sealing layer shown in the first embodiment and the low refractive index film in which the desiccant or the adsorbent dispersed in the second embodiment is combined to form a multilayer stack. Of course, it can be used as a film.

<< Third Embodiment >>
Next, as a third embodiment, a specific configuration example of the electro-optical device according to the invention will be described with reference to FIGS. 4, 5, and 6.
4 and 5 show an example in which the electro-optical device according to the present invention is applied to an active matrix display device using an organic electroluminescence element.

  As shown in FIG. 4 which is a circuit diagram, the organic electroluminescence display device S1 includes a plurality of scanning lines 131, a plurality of signal lines 132 extending in a direction intersecting with the scanning lines 131, and these. A plurality of common power supply lines 133 extending in parallel to the signal line 132 are respectively wired, and each pixel has a pixel (pixel area element) AR at each intersection of the scanning line 131 and the signal line 132. It is.

For the signal line 132, a data line driving circuit 90 including a shift register, a level shifter, a video line, and an analog switch is provided.
On the other hand, for the scanning line 131, a scanning line driving circuit 80 including a shift register and a level shifter is provided. Further, in each of the pixel regions AR, a first thin film transistor 22 to which a scanning signal is supplied to the gate electrode via the scanning line 131 and an image signal supplied from the signal line 132 via the first thin film transistor 22. Is electrically connected to the common power supply line 133 through the second thin film transistor 24, the second thin film transistor 24 to which the image signal held by the storage capacitor cap is supplied to the gate electrode, and the second thin film transistor 24. A pixel electrode 23 into which a driving current sometimes flows from the common power supply line 133 and a light emitting portion (light emitting layer) 60 sandwiched between the pixel electrode (anode) 23 and the counter electrode (cathode) 222 are provided.

  Under such a configuration, when the scanning line 131 is driven and the first thin film transistor 22 is turned on, the potential of the signal line 132 at that time is held in the holding capacitor cap, and according to the state of the holding capacitor cap. Thus, the conduction state of the second thin film transistor 24 is determined. Then, a current flows from the common power supply line 133 to the pixel electrode 23 through the channel of the second thin film transistor 24, and further, a current flows to the counter electrode 222 through the light emitting layer 60, whereby the light emitting layer 60 has an amount of current flowing therethrough. In response to the light emission.

  Here, the planar structure of each pixel AR is an enlarged plan view with the counter electrode and the organic electroluminescence element removed, as shown in FIG. 132, the common power supply line 133, the scanning line 131, and other pixel electrode scanning lines (not shown).

6 is a cross-sectional view taken along arrow AA in FIG. Here, the organic electroluminescence display device shown in FIG. 6 takes a form in which light is extracted from the side opposite to the substrate 2 side where a thin film transistor (TFT) is disposed.
As shown in FIG. 6, the organic electroluminescence display device S 1 includes a substrate 2, an anode (pixel electrode) 23 made of a transparent electrode material such as indium tin oxide (ITO), and holes from the anode 23. Are provided on the upper surface of the light emitting layer 60, a light emitting layer (organic electroluminescent layer, electrooptical element) 60 containing an organic electroluminescent material that is one of the electrooptical materials, and a light emitting layer 60. From the electron transport layer 50 and at least one of metals such as aluminum (Al), magnesium (Mg), gold (Au), silver (Ag), and calcium (Ca) provided on the upper surface of the electron transport layer 50 A cathode (counter electrode) 222 formed on the substrate 2 and a thin film transistor as an energization control unit for controlling whether or not to write a data signal to the pixel electrode 23 (Hereinafter referred to as “TFT”) 24. Further, the laminated film 20 including the low refractive index layer 3 and the sealing layer 4 is provided on the upper layer of the cathode 222, that is, on the side from which the light from the light emitting layer 60 is extracted. In FIG. 6, the low refractive index layer 3 is arranged on the upper layer of the cathode 222 and the sealing layer 4 is arranged on the uppermost layer. However, the sealing layer 4 is arranged on the upper layer of the cathode 222, The low refractive index layer 3 may be disposed on the upper layer of the sealing layer 4. Alternatively, a passivation film, a protective film, or a planarizing film made of an organic material or an inorganic material may be formed on the cathode 222, and the low refractive index layer 3 or the sealing layer 4 may be provided thereon. The TFT 24 operates based on an operation command signal from the scanning line driving circuit 80 and the data line driving circuit 90 and performs energization control to the pixel electrode 23.

The TFT 24 is provided on the surface of the substrate 2 via a base protective layer 281 mainly composed of SiO ₂ . The TFT 24 includes a silicon layer 241 formed on the base protective layer 281, a gate insulating layer 282 provided on the base protective layer 281 so as to cover the silicon layer 241, and an upper surface of the gate insulating layer 282. A gate electrode 242 provided in a portion facing the silicon layer 241; a first interlayer insulating layer 283 provided above the gate insulating layer 282 so as to cover the gate electrode 242; a gate insulating layer 282 and a first interlayer insulating layer A source electrode 243 connected to the silicon layer 241 through a contact hole opened over the layer 283, and a position facing the source electrode 243 with the gate electrode 242 interposed therebetween. The gate insulating layer 282 and the first interlayer insulating layer 283 are provided. A drain electrode 244 connected to the silicon layer 241 through a contact hole opened over the And a second interlayer insulating layer 284 provided on an upper layer of the first interlayer insulating layer 283 to cover the source electrode 243 and drain electrode 244.

  The pixel electrode 23 is disposed on the upper surface of the second interlayer insulating layer 284, and the pixel electrode 23 and the drain electrode 244 are connected through a contact hole 23 a provided in the second interlayer insulating layer 284. Further, a third insulating layer (bank layer) 221 made of a synthetic resin or the like is provided between a portion of the surface of the second interlayer insulating layer 284 other than the portion where the organic electroluminescence element is provided and the cathode 222. ing.

  Note that a region of the silicon layer 241 that overlaps with the gate electrode 242 with the gate insulating layer 282 interposed therebetween is a channel region. In the silicon layer 241, a source region is provided on the source side of the channel region, and a drain region is provided on the drain side of the channel region. Among these, the source region is connected to the source electrode 243 through a contact hole that opens over the gate insulating layer 282 and the first interlayer insulating layer 283. On the other hand, the drain region is connected to the drain electrode 244 made of the same layer as the source electrode 243 through a contact hole that extends through the gate insulating layer 282 and the first interlayer insulating layer 283. The pixel electrode 23 is connected to the drain region of the silicon layer 241 through the drain electrode 244.

  In this example, since the emitted light is extracted from the side opposite to the substrate 2 on which the TFT 24 is provided, the substrate 2 may be opaque. In this case, a ceramic sheet such as alumina or a metal sheet such as stainless steel is used. An insulating treatment such as surface oxidation, a thermosetting resin, a thermoplastic resin, or the like can be used.

On the other hand, the organic electroluminescence element can be configured to take out light emitted from the light emitting layer from the substrate side on which the TFT is provided, as will be described later. In the case where the emitted light is extracted from the substrate side, transparent or translucent materials such as glass, quartz, and resin are used as the substrate material, but particularly inexpensive soda glass is preferably used. When soda glass is used, it is preferable to apply silica coating to the soda glass because it has an effect of protecting the soda glass that is weak against acid-alkali and further has an effect of improving the flatness of the substrate.
In addition, a color filter film, a color conversion film containing a luminescent substance, or a dielectric reflection film may be disposed on the substrate to control the emission color.

  When forming the base protective layer 281, the base protective layer 281 has a thickness of about 200 to 500 nm by forming a film on the substrate 2 by plasma CVD using TEOS (tetraethoxysilane) or oxygen gas as a raw material. A silicon oxide film is formed.

When forming the silicon layer 241, first, the temperature of the substrate 2 is set to about 350 ° C., and an amorphous silicon layer having a thickness of about 30 to 70 nm is formed on the surface of the base protective film 281 by plasma CVD or ICVD. Form. Next, a crystallization process is performed on the amorphous silicon layer by a laser annealing method, a rapid heating method, a solid phase growth method, or the like to crystallize the amorphous silicon layer into a polysilicon layer. In the laser annealing method, for example, a line beam having a beam length of 400 mm is used with an excimer laser, and the output intensity is set to 200 mJ / cm ² , for example. With respect to the line beam, the line beam is scanned so that a portion corresponding to 90% of the peak value of the laser intensity in the short dimension direction overlaps each region. Next, the polysilicon layer is patterned by a photolithography method to form an island-shaped silicon layer 241.

  Note that the silicon layer 241 serves as the channel region and the source / drain region of the second thin film transistor 24 shown in FIG. 4, but the channel region and the source / drain region of the first thin film transistor 22 at different cross-sectional positions. A semiconductor film is also formed. That is, the two types of transistors 22 and 24 are formed at the same time, but are manufactured in the same procedure. Therefore, in the following description, only the second thin film transistor 24 will be described with respect to the transistor, and the first thin film transistor 22 will be Description is omitted.

When forming the gate insulating layer 282, a silicon oxide film having a thickness of about 60 to 150 nm is formed on the surface of the silicon layer 241 by using a plasma CVD method using TEOS or oxygen gas as a raw material. Alternatively, a gate insulating layer 282 made of a nitride film is formed. The gate insulating layer 282 may be a porous silicon oxide film (SiO ₂ film). The gate insulating layer 282 made of a porous SiO ₂ film is formed by CVD (chemical vapor deposition) using Si ₂ H ₆ and O ₃ as reaction gases. Using these reaction gases, high SiO ₂ particles in the gas phase is formed, a large SiO ₂ of the particles are deposited on the silicon layer 241 and protective underlayer 281. Therefore, the gate insulating layer 282 has a large number of voids in the layer and becomes a porous body. The gate insulating layer 282 has a low dielectric constant by becoming a porous body.

Note that the surface of the gate insulating layer 282 may be subjected to H (hydrogen) plasma treatment. Thereby, dangling bonds in Si—O bonds on the surface of the voids are replaced with Si—H bonds, and the moisture absorption resistance of the film is improved. Then, another SiO ₂ layer may be provided on the surface of the plasma-treated gate insulating layer 282. By doing so, an insulating layer having a dielectric constant can be formed.
In addition to Si ₂ H ₆ + O ₃ , the reaction gas for forming the gate insulating layer 282 by the CVD method may be Si ₂ H ₆ + O ₂ , Si ₃ H ₈ + O ₃ , or Si ₃ H ₈ + O _2. Good. Furthermore, in addition to the above reaction gas, a reaction gas containing B (boron) or a reaction gas containing F (fluorine) may be used.

Furthermore, when forming the gate insulating layer 282 is a porous material, and the SiO ₂ film having a porosity, by laminating a SiO ₂ film formed by normal pressure chemical vapor deposition, the film quality The gate insulating layer 282 as a stable porous body can also be formed. These films can be laminated by generating plasma intermittently or periodically in an atmosphere of SiH ₄ and O ₂ under reduced pressure. Specifically, the gate insulating layer 282 contains the substrate 2 in a predetermined chamber, and keeps the substrate 2 at, for example, 400 ° C., and uses SiH ₄ and O ₂ as reaction gases, and supplies an RF voltage (high frequency voltage) to the chamber. It is formed by applying. During film formation, the SiH ₄ flow rate and the O ₂ flow rate are constant, whereas the RF voltage is applied to the chamber at a cycle of 10 seconds. As a result, plasma is generated and extinguished at a cycle of 10 seconds. In this manner, by using time-varying plasma, a process using low-pressure CVD and a process using plasma CVD under reduced pressure can be repeatedly performed in one chamber. Then, by repeating the low pressure CVD and the plasma CVD under the reduced pressure, a SiO ₂ film having a large number of voids in the film is formed. That is, the gate insulating layer 282 is porous.

  The gate electrode 242 is formed by forming a conductive film containing a metal such as aluminum, tantalum, molybdenum, titanium, or tungsten over the gate insulating layer 282 by sputtering and then patterning the conductive film.

  In order to form the source region and the drain region in the silicon layer 241, after forming the gate electrode 242, the gate electrode 242 is used as a patterning mask, and phosphorus ions are implanted in this state. As a result, high-concentration impurities are introduced in a self-aligned manner with respect to the gate electrode 242, so that a source region and a drain region are formed in the silicon layer 241. Note that a portion where no impurity is introduced becomes a channel region.

  The first interlayer insulating layer 283 is composed of a silicon oxide film or a nitride film, a porous silicon oxide film, etc., like the gate insulating layer 282, and is formed of the gate insulating layer 282 in the same procedure as the method for forming the gate insulating layer 282. It is formed in the upper layer.

  In order to form the source electrode 243 and the drain electrode 244, first, contact holes corresponding to the source electrode and the drain electrode are formed by patterning the first interlayer insulating layer 283 using a photolithography method. Next, a conductive layer made of a metal such as aluminum, chromium, or tantalum is formed so as to cover the first interlayer insulating layer 283, and then a region in which the source electrode and the drain electrode are to be formed is covered. The source electrode 243 and the drain electrode 244 are formed by providing a patterning mask and patterning the conductive layer.

  Like the first interlayer insulating layer 283, the second interlayer insulating layer 284 is composed of a silicon oxide film or a nitride film, a porous silicon oxide film, and the like. The second interlayer insulating layer 284 is formed in the same procedure as the method for forming the first interlayer insulating layer 283. It is formed in the upper layer of one interlayer insulating layer 283. Here, when the second interlayer insulating layer 284 is formed, a contact hole 23 a is formed in a portion corresponding to the drain electrode 244 in the second interlayer insulating layer 284.

The anode 23 connected to the organic electroluminescence element is made of transparent electrode material such as SnO ₂ doped with ITO or fluorine, ZnO or polyamine, and is connected to the drain electrode 244 of the TFT 24 through the contact hole 23a. . In order to form the anode 23, a film made of the transparent electrode material is formed on the upper surface of the second interlayer insulating layer 284, and this film is patterned.

  The third insulating layer 221 is made of a synthetic resin such as an acrylic resin or a polyimide resin. The third insulating layer 221 is formed after the anode 23 is formed. As a specific method for forming the third insulating layer 221, for example, an insulating layer is formed by applying a resist such as acrylic resin or polyimide resin melted in a solvent by spin coating, dip coating, or the like. The constituent material of the insulating layer may be any material as long as it does not dissolve in the ink solvent described below and can be easily patterned by etching or the like. Further, the insulating layer is simultaneously etched by a photolithography technique or the like to form the opening 221a, whereby the third insulating layer 221 having the opening 221a is formed.

Here, a region showing ink affinity and a region showing ink repellency are formed on the surface of the third insulating layer 221. In the present embodiment, each region is formed by a plasma treatment process. Specifically, the plasma treatment process includes a preliminary heating process, an ink repellency process for making the wall surface of the opening 221a and the electrode surface of the pixel electrode 23 ink-philic, and an upper surface of the third insulating layer 221 having ink repellency. It has an ink repellent process and a cooling process.
That is, the base material (the substrate 2 including the third insulating layer and the like) is heated to a predetermined temperature (for example, about 70 to 80 soils), and then plasma treatment using oxygen as a reactive gas in an atmospheric atmosphere (O ₂ Plasma processing). Subsequently, a plasma treatment (CF ₄ plasma treatment) using methane tetrafluoride as a reactive gas in an air atmosphere as an ink repellent process is performed, and the substrate heated for the plasma treatment is cooled to room temperature. Ink affinity and ink repellency are imparted to predetermined locations. The electrode surface of the pixel electrode 23 is also somewhat affected by this CF ₄ plasma treatment. However, since ITO or the like, which is the material of the pixel electrode 23, has a poor affinity for fluorine, the hydroxyl group imparted in the ink-philic step is used. Is not substituted with a fluorine group, and ink affinity is maintained.

  The hole transport layer 70 is formed on the upper surface of the anode 23. Here, the material for forming the hole transport layer 70 is not particularly limited, and known materials can be used, and examples thereof include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives. Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, JP-A-3-37992, and JP-A-3-152184. Examples described in the publication are exemplified, but a triphenyldiamine derivative is preferable, and 4,4′-bis (N (3-methylphenyl) -N-phenylamino) biphenyl is particularly preferable.

  Note that a hole injection layer may be formed instead of the hole transport layer, and both the hole injection layer and the hole transport layer may be formed. In this case, as a material for forming the hole injection layer, for example, copper phthalocyanine (CuPc), polytetravinylthiophene polyphenylene vinylene, 1,1-bis- (4-N, N-ditolylaminophenyl) cyclohexane , Tris (8-hydroxyquinolinol) aluminum and the like, and copper phthalocyanine (CuPc) is particularly preferable.

  When the hole injection / transport layer 70 is formed, an ink jet method can be used. That is, after discharging the composition ink containing the hole injection / transport layer material described above onto the electrode surface of the anode 23, the hole injection / transport layer 70 is formed on the electrode 23 by performing a drying process and a heat treatment. Is done. After the hole injection / transport layer forming step, in order to prevent oxidation of the hole injection / transport layer 70 and the light emitting layer (organic electroluminescence layer) 60, an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere is used. Preferably it is done. For example, an inkjet head (not shown) is filled with a composition ink containing a hole injection / transport layer material, and the ejection nozzle of the inkjet head is made to face the electrode surface of the anode 23, and the inkjet head and the base material (substrate 2) While the ink is relatively moved, ink droplets whose liquid amount per droplet is controlled are ejected from the ejection nozzle onto the electrode surface. Next, the hole injection / transport layer 70 is formed by drying the ejected ink droplets to evaporate the polar solvent contained in the composition ink.

  In addition, as a composition ink, what melt | dissolved the mixture of polythiophene derivatives, such as polyethylene dioxythiophene, polystyrene sulfonic acid, etc. in polar solvents, such as isopropyl alcohol, can be used, for example. Here, the ejected ink droplet spreads on the electrode surface of the anode 23 that has been subjected to the affinity ink treatment, and fills the vicinity of the bottom of the opening 221a. On the other hand, ink droplets are repelled and do not adhere to the upper surface of the third insulating layer 221 that has been subjected to ink repellent treatment. Therefore, even if the ink droplet is deviated from the predetermined ejection position and ejected onto the upper surface of the third insulating layer 221, the upper surface does not get wet with the ink droplet, and the repelled ink droplet is opened to the third insulating layer 221. It is supposed to roll into the portion 221a.

  The light emitting layer 60 is formed on the upper surface of the hole injection / transport layer 70. The material for forming the light emitting layer 60 is not particularly limited, and low molecular organic light emitting dyes and polymer light emitting materials, that is, light emitting materials composed of various fluorescent materials and phosphorescent materials can be used. Among conjugated polymers that serve as luminescent materials, those containing an arylene vinylene structure are particularly preferred. Examples of the low-molecular phosphors include naphthalene derivatives, anthracene derivatives, perylene derivatives, polymethine series, xanthene series, coumarin series, cyanine series pigments, 8-hydroquinoline and its metal complexes, aromatic amines, tetraphenylcyclo Pentadiene derivatives and the like, or known ones described in JP-A-57-51781 and 59-194393 can be used.

In the case of using a polymeric fluorescent substance as a material for forming the light emitting layer 60, a polymer having a fluorescent group in the side chain can be used, but preferably includes a conjugated structure in the main chain, and in particular, polythiophene, Poly-p-phenylene, polyarylene vinylene, polyfluorene and derivatives thereof are preferred. Of these, polyarylene vinylene and its derivatives are preferred. The polyarylene vinylene and its derivatives are polymers containing 50 mol% or more of the repeating units represented by the following chemical formula (1) based on the total repeating units. Although it depends on the structure of the repeating unit, it is more preferable that the repeating unit represented by the chemical formula (1) is 70% or more of the entire repeating unit.
-Ar-CR = CR'- (1)
[Wherein Ar is an arylene group or heterocyclic compound group having 4 to 20 carbon atoms involved in the conjugated bond, R and R ′ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms. , A group selected from the group consisting of an aryl group having 6 to 20 carbon atoms, a heterocyclic compound having 4 to 20 carbon atoms, and a cyano group. ]

  The polymeric fluorescent substance includes an aromatic compound group or a derivative thereof, a heterocyclic compound group or a derivative thereof, and a group obtained by combining them as a repeating unit other than the repeating unit represented by the chemical formula (1). May be. In addition, the repeating unit represented by the chemical formula (1) and other repeating units may be linked by a non-conjugated unit having an ether group, an ester group, an amide group, an imide group, or the like, Non-conjugated moieties may be included.

  In the polymer fluorescent substance, Ar in the chemical formula (1) is an arylene group or a heterocyclic compound group having 4 to 20 carbon atoms involved in the conjugated bond, and is represented by the following chemical formula (2). Examples include an aromatic compound group or a derivative group thereof, a heterocyclic compound group or a derivative group thereof, and a group obtained by combining them.

（Ｒ１〜Ｒ９２は、それぞれ独立に、水素、炭素数１〜２０のアルキル基、アルコキシ基およびアルキルチオ基；炭素数６〜１８のアリール基およびアリールオキシ基；ならびに炭素数４〜１４の複素環化合物基からなる群から選ばれた基である。）

(R1 to R92 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group and an alkylthio group; an aryl group and aryloxy group having 6 to 18 carbon atoms; and a heterocyclic compound having 4 to 14 carbon atoms. A group selected from the group consisting of groups.)

  Among these, phenylene group, substituted phenylene group, biphenylene group, substituted biphenylene group, naphthalenediyl group, substituted naphthalenediyl group, anthracene-9,10-diyl group, substituted anthracene-9,10-diyl group, pyridine-2, 5-diyl group, substituted pyridine-2,5-diyl group, thienylene group and substituted thienylene group are preferred. More preferred are a phenylene group, a biphenylene group, a naphthalenediyl group, a pyridine-2,5-diyl group, and a thienylene group.

  When R and R ′ in the chemical formula (1) are hydrogen or a substituent other than a cyano group, the alkyl group having 1 to 20 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Hexyl group, heptyl group, octyl group, decyl group, lauryl group and the like, and methyl group, ethyl group, pentyl group, hexyl group, heptyl group and octyl group are preferable. Examples of the aryl group include a phenyl group, a 4-C1-C12 alkoxyphenyl group (C1-C12 indicates that the number of carbon atoms is 1-12, and the same shall apply hereinafter), a 4-C1-C12 alkylphenyl group, 1 -A naphthyl group, 2-naphthyl group, etc. are illustrated.

  From the viewpoint of solvent solubility, Ar in the chemical formula (1) is one or more alkyl groups having 4 to 20 carbon atoms, alkoxy groups and alkylthio groups, aryl groups and aryloxy groups having 6 to 18 carbon atoms, and 4 to 4 carbon atoms. It preferably has a group selected from 14 heterocyclic compound groups.

  Examples of these substituents are as follows. Examples of the alkyl group having 4 to 20 carbon atoms include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and a lauryl group, and a pentyl group, a hexyl group, a heptyl group, and an octyl group are preferable. Examples of the alkoxy group having 4 to 20 carbon atoms include a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, a lauryloxy group, and the like, such as a pentyloxy group and a hexyloxy group. , A heptyloxy group and an octyloxy group are preferable. Examples of the alkylthio group having 4 to 20 carbon atoms include a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group, a decyloxy group, and a laurylthio group, and a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group are preferable. Examples of the aryl group include a phenyl group, a 4-C1-C12 alkoxyphenyl group, a 4-C1-C12 alkylphenyl group, a 1-naphthyl group, and a 2-naphthyl group. A phenoxy group is illustrated as an aryloxy group. Examples of the heterocyclic compound group include a 2-thienyl group, 2-pyrrolyl group, 2-furyl group, 2-, 3- or 4-pyridyl group. The number of these substituents varies depending on the molecular weight of the polymeric fluorescent substance and the constitution of the repeating unit, but from the viewpoint of obtaining a highly soluble polymeric fluorescent substance, these substituents are one or more per 600 molecular weight. It is more preferable.

  The polymeric fluorescent substance may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. . From the viewpoint of obtaining a polymer fluorescent substance having a high fluorescence quantum yield, a random copolymer having a block property and a block or graft copolymer are preferable to a complete random copolymer. Moreover, since the organic electroluminescent element formed here utilizes fluorescence from a thin film, the polymer fluorescent substance having fluorescence in a solid state is used.

When a solvent is used for the polymeric fluorescent substance, preferred examples include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene and the like. Although depending on the structure and molecular weight of the polymeric fluorescent substance, it can usually be dissolved in these solvents in an amount of 0.1 wt% or more.
Moreover, as said polymeric fluorescent substance, it is preferable that molecular weight is 10 < ³ > -10 < ⁷ > in polystyrene conversion, Their polymerization degree changes also with a repeating structure and its ratio. In general, the total number of repeating structures is preferably 4 to 10000, more preferably 5 to 3000, and particularly preferably 10 to 2000 from the viewpoint of film formability.

  The method for synthesizing such a polymeric fluorescent substance is not particularly limited. For example, a dialdehyde compound in which two aldehyde groups are bonded to an arylene group, a compound in which two halogenated methyl groups are bonded to an arylene group, and triphenyl A Wittig reaction from a diphosphonium salt obtained from phosphine is exemplified. As another synthesis method, a dehydrohalogenation method from a compound in which two halogenated methyl groups are bonded to an arylene group is exemplified. Further, a sulfonium salt decomposition method for obtaining the polymeric fluorescent substance by heat treatment from an intermediate obtained by polymerizing a sulfonium salt of a compound having two halogenated methyl groups bonded to an arylene group with an alkali is exemplified. In any of the synthesis methods, a compound having a skeleton other than an arylene group is added as a monomer, and by changing the abundance ratio, the structure of the repeating unit contained in the generated polymeric fluorescent substance can be changed. The repeating unit represented by (1) may be added and adjusted so as to be 50 mol% or more and copolymerized. Among these, the method by Wittig reaction is preferable in terms of reaction control and yield.

More specifically, a method for synthesizing an arylene vinylene copolymer, which is one example of the polymeric fluorescent substance, will be described. For example, when obtaining a polymeric fluorescent substance by Wittig reaction, for example, first, a bis (halogenated methyl) compound, more specifically, for example, 2,5-dioctyloxy-p-xylylene dibromide is converted to N, N- A phosphonium salt is synthesized by reacting with triphenylphosphine in a dimethylformamide solvent, and this is condensed with a dialdehyde compound, more specifically, for example, terephthalaldehyde using, for example, lithium ethoxide in ethyl alcohol. By the Wittig reaction, a polymeric fluorescent substance containing a phenylene vinylene group and a 2,5-dioctyloxy-p-phenylene vinylene group is obtained. At this time, in order to obtain a copolymer, two or more kinds of diphosphonium salts and / or two or more kinds of dialdehyde compounds may be reacted.
When these polymeric fluorescent substances are used as the material for forming the light emitting layer, the purity affects the light emission characteristics, and therefore it is desirable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography after synthesis.

Further, as the material for forming the light emitting layer made of the above-described polymeric fluorescent material, light emitting layer forming materials of three colors of red, green, and blue are used for full color display, each of which is a predetermined patterning device (inkjet device). ) To the pixel AR at a preset position and patterned.
Note that as the light-emitting substance, a host material added with a guest material can be used.

As such a light emitting material, for example, a high molecular organic compound or a low molecular weight material as a host material, or a fluorescent dye or a phosphorescent material for changing the light emitting characteristics of a light emitting layer obtained as a guest material is used. Preferably used.
As the polymer organic compound, in the case of a material having low solubility, for example, after a precursor is applied, the polymer organic compound becomes a conjugated polymer organic electroluminescence layer by being heated and cured as shown in the following chemical formula (3). Some can produce a light emitting layer. For example, in the case of a sulfonium salt as a precursor, there are those in which a sulfonium group is eliminated by heat treatment to become a conjugated polymer organic compound.
In addition, some highly soluble materials can be used as a light emitting layer by applying the material as it is and then removing the solvent.

  The polymer organic compound is solid and has strong fluorescence, and can form a uniform solid ultrathin film. In addition, it has high forming ability and high adhesion to the ITO electrode, and further, after solidification, forms a strong conjugated polymer film.

As such a high molecular organic compound, for example, polyarylene vinylene is preferable. Since polyarylene vinylene is soluble in an aqueous solvent or an organic solvent, it can be easily prepared into a coating solution when applied to the second substrate 11, and can be polymerized under certain conditions. A high-quality thin film can be obtained.
Examples of such polyarylene vinylene include PPV (poly (para-phenylene vinylene)), MO-PPV (poly (2,5-dimethoxy-1,4-phenylene vinylene)), CN-PPV (poly (2,5 -Bishexyloxy-1,4-phenylene- (1-cyanovinylene))), MEH-PPV (poly [2-methoxy-5- (2′-ethylhexyloxy)]-para-phenylenevinylene), etc. , Poly (alkylthiophene) such as PTV (poly (2,5-thienylenevinylene)), PFV (poly (2,5-furylenevinylene)), poly (paraphenylene), polyalkylfluorene, and the like. Among them, those composed of precursors of PPV or PPV derivatives as shown in chemical formula (4), and polymers as shown in chemical formula (5) Rukirufluorene (specifically, a polyalkylfluorene copolymer as shown in chemical formula (6)) is particularly preferred.
Since PPV or the like is a conductive polymer having strong fluorescence and π electrons forming a double bond being nonpolarized on the polymer chain, a high-performance organic electroluminescence device can be obtained.

In addition to the PPV thin film, a high molecular organic compound or a low molecular material capable of forming a light emitting layer, that is, a material used as a host material in this example is, for example, an aluminum quinolinol complex (Alq3), distyryl biphenyl, a chemical formula ( 7) BeBq2, Zn (OXZ) ₂ , and TPD, ALO, DPVBi, and other commonly used ones, pyrazoline dimer, quinolidinecarboxylic acid, benzopyrylium perchlorate, benzopyra Noquinolidine, rubrene, phenanthroline europium complex, and the like can be mentioned, and a composition for an organic electroluminescence device containing one or more of these can be used.

  On the other hand, examples of the guest material added to such a host material include fluorescent dyes and phosphorescent substances as described above. In particular, the fluorescent dye can change the light emission characteristics of the light emitting layer, and is effective, for example, as a means for improving the light emission efficiency of the light emitting layer or changing the light absorption maximum wavelength (light emission color). That is, the fluorescent dye can be used not only as a light emitting layer material but also as a dye material having a light emitting function itself. For example, the energy of exciton generated by carrier recombination on a conjugated polymer organic compound molecule can be transferred onto the fluorescent dye molecule. In this case, since light emission occurs only from fluorescent dye molecules having high fluorescence quantum efficiency, the current quantum efficiency of the light emitting layer is also increased. Therefore, by adding a fluorescent dye to the material for forming the light emitting layer, the emission spectrum of the light emitting layer simultaneously becomes that of the fluorescent molecule, which is effective as a means for changing the emission color.

The current quantum efficiency here is a scale for considering the light emission performance based on the light emission function, and is defined by the following equation.
ηE = energy of emitted photons / input electric energy And, by converting the light absorption maximum wavelength by doping with a fluorescent dye, it is possible to emit, for example, three primary colors of red, blue and green, resulting in a full color display It becomes possible.
Furthermore, the luminous efficiency of the electroluminescence element can be significantly improved by doping with a fluorescent dye.

  As the fluorescent dye, in the case of forming a light emitting layer that emits red colored light, it is preferable to use the laser dye DCM-1, rhodamine or rhodamine derivative, penylene, or the like. A light emitting layer can be formed by doping a host material such as PPV with these fluorescent dyes. However, since many of these fluorescent dyes are water-soluble, they are added to a sulfonium salt that is a water-soluble PPV precursor. Doping and then heat treatment makes it possible to form a more uniform light emitting layer. Specific examples of such fluorescent dyes include rhodamine B, rhodamine B base, rhodamine 6G, rhodamine 101 perchlorate and the like, and a mixture of two or more thereof may be used.

  Moreover, when forming the light emitting layer which emits green colored light, it is preferable to use quinacridone, rubrene, DCJT and derivatives thereof. For these fluorescent dyes, a light emitting layer can be formed by doping a host material such as PPV as in the case of the above fluorescent dyes. However, since these fluorescent dyes are often water-soluble, they are water-soluble. If a sulfonium salt, which is a PPV precursor, is doped and then heat-treated, a more uniform light emitting layer can be formed.

  Furthermore, when forming a light emitting layer that emits blue colored light, it is preferable to use distyrylbiphenyl and its derivatives. For these fluorescent dyes, a light emitting layer can be formed by doping a host material such as PPV as in the case of the above fluorescent dyes. However, since these fluorescent dyes are often water-soluble, they are water-soluble. If a sulfonium salt, which is a PPV precursor, is doped and then heat-treated, a more uniform light emitting layer can be formed.

  In addition, examples of other fluorescent dyes having blue colored light include coumarin and derivatives thereof. These fluorescent dyes are compatible with PPV and can easily form a light emitting layer. Among these, particularly, coumarin is insoluble in a solvent itself, but there are some which become soluble in a solvent by increasing the solubility by appropriately selecting a substituent. Specific examples of such fluorescent dyes include coumarin-1, coumarin-6, coumarin-7, coumarin 120, coumarin 138, coumarin 152, coumarin 153, coumarin 311, coumarin 314, coumarin 334, coumarin 337, coumarin 343 and the like. Is mentioned.

Furthermore, examples of the fluorescent dye having another blue colored light include tetraphenylbutadiene (TPB) or a TPB derivative, DPVBi, and the like. These fluorescent dyes are soluble in an aqueous solution in the same manner as the red fluorescent dye and the like, have good compatibility with PPV, and can easily form a light emitting layer.
About the above fluorescent dye, only 1 type may be used for each color, and 2 or more types may be mixed and used for it.
In addition, as such a fluorescent dye, those shown in chemical formula (8), those shown in chemical formula (9), and those shown in chemical formula (10) are used.

  About these fluorescent dyes, it is preferable to add 0.5-10 wt% by the method mentioned later with respect to the host material consisting of the said conjugated polymer organic compound etc., and adding 1.0-5.0 wt%. More preferred. If the amount of fluorescent dye added is too large, it will be difficult to maintain the weather resistance and durability of the light-emitting layer obtained. On the other hand, if the amount added is too small, the effects of adding the fluorescent dye as described above will be sufficiently obtained. Because there is no.

In addition, Ir (ppy) ₃ , Pt (thpy) ₂ , PtOEP, or the like represented by the chemical formula (11) is preferably used as a phosphorescent material as a guest material added to the host material.

Note that when the phosphor represented by the chemical formula (11) is used as a guest material, CBP, DCTA, TCPB, or the above-described DPVBi, Alq3 shown in the chemical formula (12) is particularly preferably used as the host material.
Further, both the fluorescent dye and the phosphor may be added to the host material as a guest material.

  When the light emitting layer 60 is formed of such a host / guest luminescent material, for example, a plurality of material supply systems such as nozzles are formed in advance in a patterning device (inkjet device), and the host material and guest are formed from these nozzles. By simultaneously discharging the materials at a preset amount ratio, the light emitting layer 60 can be formed of a light emitting material in which a desired amount of guest material is added to the host material.

  The light emitting layer 60 is formed by the same procedure as the method for forming the hole injection / transport layer 70. That is, after the composition ink containing the light emitting layer material is ejected onto the upper surface of the hole injection / transport layer 70 by an ink jet method, the inside of the opening 221a formed in the third insulating layer 221 is performed by performing drying treatment and heat treatment. The light emitting layer 60 is formed on the hole injection / transport layer 70. This light emitting layer forming step is also performed in an inert gas atmosphere as described above. Since the ejected composition ink is repelled in the ink-repellent-treated region, even if the ink droplet deviates from a predetermined ejection position, the repelled ink droplet rolls into the opening 221a of the third insulating layer 221.

  The electron transport layer 50 is formed on the upper surface of the light emitting layer 60. The electron transport layer 50 is also formed by the ink jet method in the same manner as the method for forming the light emitting layer 60. The material for forming the electron transport layer 50 is not particularly limited, and is an oxadiazole derivative, anthraquinodimethane and its derivative, benzoquinone and its derivative, naphthoquinone and its derivative, anthraquinone and its derivative, tetracyanoanthraquinodi. Examples include methane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, and the like. Specifically, as with the material for forming the hole transport layer, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-209888 are disclosed. And the like described in JP-A-3-379992 and 3-152184, particularly 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4. -Oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum are preferred.

  In addition, the hole injection / transport layer 70 forming material and the electron transport layer 50 forming material described above may be mixed with the light emitting layer 60 forming material and used as the light emitting layer forming material. Although the amount of the injection / transport layer forming material and the electron transport layer forming material used varies depending on the type of compound used, etc., it is appropriately determined in consideration of the amount within a range that does not impair sufficient film formability and light emission characteristics. Is done. Usually, it is 1 to 40 weight% with respect to the light emitting layer forming material, More preferably, it is 2 to 30 weight%.

The cathode 222 is formed in the whole surface of the electron carrying layer 50 and the 3rd insulating layer 221, or stripe form. Of course, the cathode 222 may be formed of a single layer made of a single material such as Al, Mg, Li, or Ca, or an alloy material of Mg: Ag (10: 1 alloy). It may be formed as a layer (including an alloy). Specifically, a layered structure such as Li ₂ O (about 0.5 nm) / Al, LiF (about 0.5 nm) / Al, or MgF ₂ / Al can be used. The cathode 222 is a thin film made of the above-described metal and can transmit light.

  The low refractive index layer 3 and the sealing layer 4 are formed on the upper surface of the cathode 222. Since the forming material and forming method of the low refractive index layer 3 and the sealing layer 4 are the same as those in the first and second embodiments described above, description thereof is omitted.

  As described above, by applying the laminated film 20 of the present invention to a top emission type electro-optical device, the visibility can be greatly improved and the invasion of gas which causes the element deterioration can be prevented.

  Note that it is of course possible to apply the low refractive index film 11 containing the desiccant or the adsorbent described in the second embodiment instead of the laminated film 20 shown in FIG.

  In addition to the hole injection / transport layer 70, the light emitting layer 60, and the electron transport layer 50, a hole blocking layer is formed, for example, on the counter electrode 222 side of the light emitting layer 60, thereby extending the life of the light emitting layer 60. You may plan. As a material for forming such a hole blocking layer, for example, BCP represented by the chemical formula (13) and BAlq represented by the chemical formula (14) are used, but BAlq is preferable in terms of extending the life.

<< 4th Embodiment >>
Next, as a fourth embodiment of the present invention, a modification of the above-described third embodiment will be described with reference to FIG. Here, components that are the same as or equivalent to those in FIG.

The display device S2 shown in FIG. 7 is a top emission type organic electroluminescence display device, and light emitted from the light emitting layer 60 is extracted from the opposite side to the substrate 2 to the outside of the device. In the display device S <b> 2 according to the present embodiment, a polymer layer (light transmission layer) 21 capable of transmitting light is formed on the surface of the laminated film 20.
As a material for forming the polymer layer 21, In ₂ O ₃ , SnO ₃ , ITO, SiO ₂ , Al ₂ O ₃ , TiO ₂ , AlN, SiN, SiC, SiON, acrylic resin, epoxy resin, polyimide resin, or these A mixture is mentioned. Here, the transmission refractive index of the low refractive index layer 3 is set lower than the transmission refractive index of the polymer layer 21.

  As described above, in the top emission type organic electroluminescence display device, the polymer layer 21 may be provided on the light extraction side.

<< 5th Embodiment >>
Next, as a fifth embodiment of the present invention, a modification of the fourth embodiment will be described with reference to FIG.
The display device S3 shown in FIG. 8 is a top emission type organic electroluminescence display device. This display device S3 is provided in the upper layer of the cathode 222, and is a laminated film comprising a protective layer 51 for protecting the cathode 222, and the low refractive index layer 3 and the sealing layer 4 provided in the upper layer of the protective layer 51. 20 and a sealing substrate 53 that is provided in the upper layer of the laminated film 20 and is bonded to the laminated film 20 through an adhesive layer 52.

The protective layer 51 is made of a material equivalent to the sealing layer 4 such as ceramic, silicon nitride, silicon oxynitride, or silicon oxide, and is formed on the surface of the cathode 222 by a plasma CVD method (plasma chemical vapor deposition method). The protective layer 51 can transmit light and has a lower refractive index than the adhesive layer 52 and the sealing substrate 53.
The adhesive layer (light transmission layer) 52 is made of a light transmissive material such as an epoxy resin or an acrylic resin. In addition, as the resin for the adhesive layer, it is preferable to use a resin that is cured by mixing two liquids such as an epoxy resin or by ultraviolet irradiation. When there is no fear that the organic electroluminescence element 9 is deteriorated by heating, a type that is cured by heating may be used.
The sealing substrate (light transmission layer) 53 has a barrier property and is made of a material that can transmit light. Examples of the material for forming the sealing substrate 53 include transparent materials such as ceramic, silicon nitride, silicon oxynitride, and silicon oxide, similarly to the sealing layer 4. Alternatively, instead of the sealing substrate 53 made of the above material, a protective sheet made of a predetermined synthetic resin may be used.

  As described above, it is possible to provide the protective layer 51 that protects the cathode 222 and the sealing substrate 53 that protects the entire display device S3 and prevents the invasion of gas that causes element deterioration. In this case, a sufficient barrier effect can be obtained in the display device S3. A sufficient barrier effect can be obtained by simply bonding the sealing substrate 53 and the laminated film 20 via the adhesive layer 52 without providing the protective layer 51.

  Further, the sealing substrate 53 described with reference to FIG. 8 may be provided on the polymer layer 21 described with reference to FIG.

<< 6th Embodiment >>
Next, a display device according to a sixth embodiment of the present invention will be described with reference to FIG. Here, in the following description, the same or equivalent components as those in the above-described embodiment are denoted by the same reference numerals, and the description thereof is simplified or omitted.
The display device S4 shown in FIG. 9 is a so-called back emission type organic electroluminescence display device that takes out light emitted from the light emitting layer 60 from the substrate 2 side where the TFT 24 is provided to the outside of the device.

  As shown in FIG. 9, the organic electroluminescence display device S4 includes a second interlayer insulating layer 284 provided under the anode 23 of the organic electroluminescence element and a lower layer of the second interlayer insulating layer 284, as in the above embodiment. A first interlayer insulating layer 283 provided on the gate insulating layer 283, a gate insulating layer 282 provided below the first interlayer insulating layer 283, and a base protective layer 281 provided below the gate insulating layer 282. ing. A laminated film 20 composed of the low refractive index layer 3 and the sealing layer 4 is provided between the base protective layer 281 and the substrate 2.

  Here, since the organic electroluminescence display device S4 shown in FIG. 9 is of a back emission type, the substrate 2 is made of a material that can transmit light. As a material for forming the substrate 2, as described above, glass, Transparent or translucent materials such as quartz and resin are used, but particularly inexpensive soda glass is preferably used.

  On the other hand, a sealing layer 54 that prevents intrusion of a substance (oxygen, moisture, etc.) due to element deterioration with respect to the EL element is formed on the cathode 222. As the sealing layer 54, a metal film (metal substrate) having a barrier property, a resin film, ceramic, silicon nitride, silicon oxynitride, silicon oxide, or the laminated film 20 or the low refractive index film 11 according to the present invention is used. Can be used.

  The second interlayer insulating layer 284, the first interlayer insulating layer 283, the gate insulating layer 282, and the like through which light emitted from the light emitting layer 60 passes are made of a material that can transmit light. Examples of the material for forming these insulating layers include silicon oxide films, porous polymers, and silica airgel.

  As described above, the laminated film 20 of the present invention can also be applied to a back emission type electro-optical device, and the visibility can be greatly improved while preventing the invasion of gas which causes the element deterioration.

  In the present embodiment, a reflective layer capable of reflecting light may be provided between the sealing layer 54 and the cathode 222. By providing the reflective layer, the light emitted from the light emitting layer 60 to the cathode 222 side is reflected by the reflective layer and proceeds to the substrate 2 side, so that the light extraction efficiency can be improved.

<< 7th Embodiment >>
Next, as a seventh embodiment of the present invention, a modification of the sixth embodiment will be described with reference to FIG.
A display device S5 shown in FIG. 10 is a back-emission type organic electroluminescence display device, and has a sealing layer 54 as the uppermost layer. A substrate 2 capable of transmitting light is provided below the base protective layer 281, a polymer layer 55 is provided below the substrate 2, and a sealing layer 4 and a low refractive index layer are provided below the polymer layer 55. 3 is provided, and a sealing substrate 53 is provided below the stacked film 20.

As a material for forming the polymer layer 55, as in the polymer layer 21 described in the fourth embodiment, In ₂ O ₃ , SnO ₃ , ITO, SiO ₂ , Al ₂ O ₃ , TiO ₂ , AlN, SiN, SiC, and SiON , Acrylic resin, epoxy resin, polyimide resin, or a mixture thereof. Alternatively, the polymer layer 55 may be formed of a low refractive index material equivalent to the low refractive index layer 3.

As described above, the layer configuration of the polymer layer, the low refractive index layer, and the sealing layer can be arbitrarily set, and high barrier properties can be realized.
FIG. 10 shows a back emission type organic electroluminescence display device. Of course, various layer configurations can be adopted in the top emission type organic electroluminescence display device S6 as shown in FIG. By doing so, even in a top emission type organic electroluminescence display device, a high barrier property can be realized, and element deterioration can be prevented. Here, the laminated film 20 including the low refractive index layer 3 and the sealing layer 4 is formed on the cathode 222. Note that the polymer layer 55 ′ shown in FIG. 11 does not need to have a low refractive index, and can be formed of a predetermined material having a high barrier property.

<< Eighth Embodiment >>
Next, an eighth embodiment of the present invention will be described with reference to FIG.
A display device S7 shown in FIG. 12 is a passive matrix organic electroluminescence display device, in which FIG. 12A is a plan view and FIG. 12B is a cross-sectional view taken along line BB in FIG. The passive matrix organic electroluminescence display device S7 includes a plurality of first bus wirings 300 provided on the substrate 121, and a plurality of second bus wirings 310 disposed on a walk orthogonal to the first bus wirings 300. Yes. In addition, an insulating film 320 made of, for example, SiO ₂ is disposed so as to surround a predetermined position where the light emitting element (organic electroluminescence element) 140 having the electron transport layer 141, the light emitting layer 142, and the hole transport layer 143 is disposed. It is installed.

  A protective layer 51 that protects the bus wiring 310 is provided above the bus wiring 310, a low refractive index layer 3 is provided above the protective layer 51, and a sealing layer is provided above the low refractive index layer 3. A layer 4 is provided, and a sealing substrate 53 is provided above the sealing layer 4 via an adhesive layer 52.

  As described above, the low refractive index layer 3 and the sealing layer 4 according to the present invention can be applied to a passive matrix organic electroluminescence display device, and the low refractive index layer 3 and the sealing layer 4 are provided. As a result, good visibility can be obtained while preventing intrusion of gas due to element degradation.

  In each of the above embodiments, a sealant or a synthetic resin can be provided on each layer (each film) or on the side of the substrate.

  In each of the above embodiments, an organic electroluminescence display device is taken as an example of an electro-optical device. However, the liquid crystal display device can also be applied to the laminated film 20 (low refractive index film 11) of the present invention in a plasma display device or the like. It is.

[Electronics]
Examples of electronic devices provided with the organic electroluminescence display device of the above embodiment will be described. FIG. 13 is a perspective view showing an example of a mobile phone. In FIG. 13, reference numeral 1000 denotes a mobile phone body, and reference numeral 1001 denotes a display unit using the organic electroluminescence display device.

  FIG. 14 is a perspective view showing an example of a wristwatch type electronic device. In FIG. 14, reference numeral 1100 indicates a watch body, and reference numeral 1101 indicates a display unit using the organic electroluminescence display device.

  FIG. 15 is a perspective view illustrating an example of a portable information processing apparatus such as a word processor or a personal computer. In FIG. 15, reference numeral 1200 denotes an information processing apparatus, reference numeral 1202 denotes an input unit such as a keyboard, reference numeral 1204 denotes an information processing apparatus body, and reference numeral 1206 denotes a display unit using the above organic electroluminescence display device.

  Since the electronic devices shown in FIGS. 13 to 15 include the organic electroluminescence display device according to the above-described embodiment, it is possible to realize an electronic device that has an organic electroluminescence display portion with a high display quality and a bright screen. it can.

  The technical scope of the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention, and the specific materials mentioned in the embodiment. The layer structure and the like are merely examples, and can be changed as appropriate.

  According to the electro-optical device of the present invention, the low refractive index layer having a refractive index lower than that of the light transmission layer and the sealing layer for blocking gas intrusion are provided between the light transmission layer and the light emitting element. The light extraction efficiency can be sufficiently improved by the refractive index layer, and high visibility can be obtained. In addition, since the light-emitting element can be prevented from being acted on by the sealing layer due to the element deterioration, good light-emitting characteristics can be maintained for a long time.

  In addition, according to the electro-optical device of the present invention, the low refractive index layer is provided with a low refractive index layer in which a desiccant or an adsorbent is dispersed between the light transmission layer and the light emitting element. Barrier function). Accordingly, gas intrusion from the light transmission layer side can be suppressed by the low refractive index layer, and the light emitting element can be prevented from being acted on by a substance caused by element deterioration, so that good light emission characteristics can be maintained for a long time. .

  According to the film-like member, laminated film, low refractive index film, and multilayer laminated film of the present invention, the light transmitted through the film is adjusted to a desired state, and unnecessary gas can be prevented from entering and exiting. When applied to an apparatus, good performance is exhibited.

  According to the electronic device of the present invention, it is possible to realize an electronic device having a display portion with a bright screen and excellent display quality.

1 is a schematic configuration diagram illustrating a first embodiment of an electro-optical device according to the invention. It is sectional drawing which shows the film-shaped member of this invention. FIG. 6 is a schematic configuration diagram illustrating a second embodiment of the electro-optical device according to the invention. It is a circuit diagram which shows an active matrix type organic electroluminescent display apparatus. FIG. 5 is an enlarged view showing a planar structure of a pixel portion in the display device of FIG. 4. FIG. 6 is a diagram illustrating a third embodiment of the electro-optical device according to the invention, and is a cross-sectional view taken along line AA in FIG. 5. FIG. 6 is a cross-sectional view illustrating a fourth embodiment of an electro-optical device according to the invention. FIG. 9 is a cross-sectional view illustrating a fifth embodiment of an electro-optical device according to the invention. FIG. 10 is a cross-sectional view illustrating a sixth embodiment of an electro-optical device according to the invention. FIG. 10 is a cross-sectional view illustrating a seventh embodiment of the electro-optical device according to the invention. 10 is another example related to the seventh embodiment of the electro-optical device of the invention. It is a figure which shows the passive matrix type organic electroluminescent display apparatus which concerns on 8th Embodiment of the electro-optical apparatus of this invention, Comprising: (a) is a top view, (b) is BB sectional drawing of (a). . FIG. 6 is a diagram illustrating an example of an electronic apparatus including the electro-optical device according to the invention. FIG. 6 is a diagram illustrating an example of an electronic apparatus including the electro-optical device according to the invention. FIG. 6 is a diagram illustrating an example of an electronic apparatus including the electro-optical device according to the invention. It is a schematic block diagram which shows an example of the conventional electro-optical apparatus. It is a figure for demonstrating a mode that the light from a light emitting layer is refracted by a board | substrate.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Organic electroluminescence display device (electro-optical device), 2 ... Substrate, 3, 11 ... Low refractive index layer, 4 ... Sealing layer, 5 ... Light emitting layer, 6 ... Hole transport layer, 7 ... Cathode (electrode) , 8 ... anode (electrode), 9 ... organic electroluminescence element (light emitting element), 11 ... low refractive index film, 20 ... laminated film.

Claims (16)

On the board
A low refractive index layer having a lower refractive index than the substrate;
A sealing layer provided on the low refractive index layer;
A polymer layer provided on the sealing layer;
A light emitting device provided on the polymer layer,
The light emitting element has a first electrode, a second electrode, and a light emitting layer disposed between the first electrode and the second electrode,
The light emitted from the light emitting layer is emitted to the substrate side. The electro-optical device according to claim 1, wherein a resin layer is provided between the low refractive index layer and the sealing layer.   The electro-optical device according to claim 1, wherein a sealing member is provided on the light emitting element so as to cover the light emitting element. The electro-optical device according to claim 1, wherein a thickness of the sealing layer is smaller than a wavelength of light emitted from the light emitting element. The sealing layer includes at least one of ceramic, silicon nitride, silicon oxynitride, and silicon oxide;
The electro-optical device according to claim 1.   The sealing layer contains at least one element selected from boron, carbon, nitrogen, aluminum, silicon, phosphorus, ytterbium, samarium, erbium, yttrium, gadolinium, dysprosium, and neodymium. The electro-optical device according to any one of 1 to 4.   The electro-optical device according to claim 1, wherein at least one of the low refractive index layer and the sealing layer contains a desiccant or an adsorbent.   The electro-optical device according to claim 1, wherein the low refractive index layer includes at least one material selected from airgel, porous silica, and magnesium fluoride. The electro-optical device according to claim 1, wherein a refractive index of the low refractive index layer is 1.2 or less.   The electro-optical device according to claim 1, wherein the low refractive index layer and the sealing layer transmit light.   The electro-optical device according to claim 1, wherein the sealing layer suppresses transmission of a substance. Forming a low refractive layer having a refractive index lower than that of the substrate on the substrate;
A second step of forming a sealing layer on the low refractive layer;
A third step of forming a polymer layer on the sealing layer;
A fourth step of forming a light emitting element on the polymer layer,
The light emitting element has a first electrode, a second electrode, and a light emitting layer disposed between the first electrode and the second electrode,
The light emitted from the light emitting layer is emitted to the substrate side. The first step includes a step of applying a wet gel, and a drying step of drying the wet gel using a supercritical drying method.
13. The method of manufacturing an electro-optical device according to claim 12, wherein the wet gel is mixed with a resin. The method of manufacturing an electro-optical device according to claim 12 or 13, characterized in that it comprises a step of forming a resin layer between the sealing layer and the low refractive layer. On the light emitting device, method of manufacturing an electro-optical device according to any one of claims 12 to 14, characterized in that it comprises the step of providing the sealing member so as to cover the light emitting element. The method of manufacturing an electro-optical device according to claim 12, wherein a thickness of the sealing layer is smaller than a wavelength of light emitted from the light emitting element.

Images