WO2006022273A2

WO2006022273A2 - Organic el element, organic el element protection film and method for manufacturing the organic el element protection film

Info

Publication number: WO2006022273A2
Application number: PCT/JP2005/015295
Authority: WO
Inventors: Makoto Tomoyori
Original assignee: Tohoku Device Co Ltd; Makoto Tomoyori
Priority date: 2004-08-24
Filing date: 2005-08-23
Publication date: 2006-03-02
Also published as: KR20070049223A; WO2006022273A3; JPWO2006022273A1

Abstract

An organic EL element, especially a top emission type, having an increased effective emission quantity per consumption power is provided by providing a protection film, which has a microlens array which can be integrally formed with a cap, can concentrate light emission from both planes of an organic EL layer on one plane and has a high transparency. The organic EL element includes the protection film; an organic EL light emitting diode (OLED) including a transparent electrode film, the organic EL layer and a counter electrode layer; a board whereupon the OLED is mounted; and the cap for covering the OLED. On the outer plane or inner plane of the cap or on the front side of the transparent electrode film, the microlens array made of, for instance, a silicone resin, is provided, preferably a light reflecting plane is provided on the board, and more preferably, the protection film includes a silica film and an organic fluorine polymeric film containing silicon.

Description

Specification

Organic EL device, protective film for organic EL device and method for producing the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to an organic EL element, and more particularly to an organic EL element that exhibits high light emission efficiency effectively in the case of a top emission type.

Background art

[0002] Organic-electric-luminescence elements (hereinafter referred to as “organic EL elements” for short) can form high-purity, high-quality multilayer films with a thickness of nm class due to recent advances in thin-film formation technology. It became possible to operate at a low voltage of about 5V.

In this way, organic EL elements are attracting attention as elements for next-generation display systems that have low power consumption, high quality, are thin, and can display curved surfaces.

[0003] In an organic EL element, a plurality of films having a predetermined organic molecular component force are stacked vertically to form an organic EL layer, and electrode layers are attached to both the upper and lower sides to form an OLED (organic light emitting diode), Apply a predetermined voltage or current through both electrodes to inject electrons and holes into the organic EL layer, and use the phenomenon of light emission when electrons and holes recombine.

Therefore, in order to guide the emitted light to the outside and perform the display function, at least one of the electrodes provided on the upper and lower sides must be transparent.

[0004] For this transparent electrode, ITO (Indium Tin Oxide) is widely used as a material that can achieve both electrical conductivity and transparency. Generally, annealing is required to lower the electrical resistance of ITO. In addition, polishing is necessary to increase the smoothness of the ITO surface (to reduce the roughness).

[0005] Since the organic EL layer is deteriorated when the temperature is increased during the annealing of the ITO, it is necessary to perform the formation of the ITO prior to the formation of the organic EL layer.

In other words, when ITO is formed first, the stacking order is [substrate—first electrode film (ITO) —organic EL layer—second electrode film (opaque electrode film)], and light is emitted from the substrate side (bottom emission). Therefore, the substrate must also be transparent, and a glass substrate is usually used.

[0006] However, the glass substrate has a poor thermal conductivity and the heat dissipation is insufficient for the heat generated during operation. High temperature tends to cause deterioration of the organic EL layer.

[0007] Furthermore, in order to obtain a high-speed and high-definition display system, it must be driven by an active matrix (TFT). In that case, a TFT transistor must be formed between the substrate and the ITO electrode. The aperture ratio decreases by the presence of the TFT transistor, and the external conversion efficiency of the light emission decreases.

In other words, in order to secure the required amount of light emission, the power consumption increases, and therefore the amount of heat generation proportional to the power consumption increases, resulting in a higher temperature, and the organic EL layer is more likely to deteriorate.

[0008] Therefore, the second electrode is made transparent, and [substrate-TFT-first electrode-organic EL layer-second electrode (ITO)] is used to emit light from the opposite side of the substrate (top emission). Being! In that case, it is necessary to pay particular attention not to alter the organic EL layer when forming ITO.

For example, Non-Patent Document 1 discloses a contrivance on the manufacturing method such as bonding a substrate on which an organic EL layer is formed and a substrate on which a second electrode (ITO) is formed in order to prevent this alteration.

Non-Patent Document 1: Kathleen M. Vaeth, Information Display 6/03 (2003), pp 12-17, SID.

[0009] The emission intensity of the organic light emitting diode (OLED) is maximum in the direction perpendicular to the organic EL layer, but is also dispersed in other directions, and the relative value is theoretically a right angle. It is a function of Θ represented by cos Θ, where Θ is the angle from the direction.

Therefore, when the emitted light is condensed in the right angle direction, the luminance can be increased, that is, in order to obtain a constant luminance in the right angle direction, it is possible to prevent the deterioration of the organic EL layer even if the power consumption is suppressed.

[0010] Therefore, in order to achieve this OLED focusing, the introduction of various microlens arrays has been studied.

For example, Patent Document 1 discloses a technique including a lens layer formed by sealing the transparent electrode 6 with a glass substrate (glass cap) 7 and ion implantation from the outer surface side.

[0011] Patent Document 2 discloses that an organic film 10 includes a gas nolia layer 11 and an oxygen base film 13 formed thereon. A technology is disclosed in which an ultraviolet curable resin mixed with fine transparent beads is coated thereon, a mic mouth lens 12 is formed with a roll mold, and then laminated to an organic EL substrate formed separately.

[0012] Further, Patent Document 3 discloses a technique in which a microlens array 17 preferably made of a photocurable transparent resin is further provided on a protective film 16 on an anode 15 of an organic EL pixel. .

[0013] As described above, the force at which the microlens array is formed has a variety of positions. The formation method uses ion implantation into the glass, ultraviolet curing resin, or photocurable resin, and it is stable such as ensuring transparency. It is not easy to obtain inexpensive manufacturing conditions. Patent Document 1: Japanese Patent Laid-Open No. 2003-264059

Patent Document 2: Japanese Patent Laid-Open No. 2003-257627

Patent Document 3: JP 2004-039500 A

Furthermore, it should be noted that the organic EL layer itself emits light from both sides with an intensity according to the function cos Θ, that is, the opposite surface not only by the surface force on the transparent electrode film side of interest. The same amount of light is also emitted from the side.

In the conventional technology, regardless of the bottom emission or the top emission, the light emission from the opposite side is wasted by being blocked by the opaque electrode film, and the ratio of light emission amount Z power consumption cannot be increased. It was.

[0015] Non-Patent Document 2 specifically discloses a technique for forming an organic EL element having a transparent electrode film on both surfaces of an organic EL layer on a glass substrate, which enables the use of double-sided light emission. However, light reception (viewing) on one side is dominant as an application of organic EL elements, and the ratio of light emission amount Z power consumption still cannot be increased.

Non-Patent Literature 2: Transparent organic lignt emitting devices, G. u et al., Appl. Phys. Letter. 68 (19), 6 May 1996

[0016] The organic EL element formed in this way is not modified as it is because the OLED, in particular, the organic EL layer and the ITO film deteriorate and deteriorate with time due to moisture and oxygen. If the top-emission type is used, this protective film must be as transparent as possible to visible light. Furthermore, a low-temperature process is necessary so that the OLED is not physically and chemically altered again even when this protective film is formed.

Conventionally, as a protective film (passivation) against moisture and oxygen for silicon semiconductors and the like, a silicon nitride film is the most suitable. A silicon nitride film generally requires a high temperature for film formation. Since it is hard, it has been unsuitable by itself, such as giving stress to organic EL elements, and various ingenuities have been made.

[0018] For example, a technology for obtaining a high-purity silica (SiO 2) film by simply dissolving polysilazane, especially PHPS (PerHydroPolySilazane) in an organic solvent, applying it, and baking it has been realized in the semiconductor industry.

2

However, due to recent advances in catalyst technology, it has become possible to calcinate at a relatively low temperature of 100 ° C or lower, making it applicable to organic EL devices.

[0019] However, the silica film obtained by firing the polysilazane forms a dense protective film macroscopically, but microscopically, it has a protective ability alone when it is not as dense as the silicon nitride film. Is inferior.

Therefore, attempts have been made to obtain the required protection ability by forming a multilayer film by combining polysilazane and other types of films.

[0020] For example, Patent Document 4 discloses a technique in which an intermediate film (polysilazane film) is sandwiched between silicon nitride films with vertical force, covers the OLED, and only the outer peripheral portion is laser-heated to transform the intermediate film into silica. It is disclosed.

[0021] Further, an attempt has been made to apply a fluorine-based polymer film to a part of the multilayer film.

Fluorine is the most strongly bonded to carbon of the polymer skeleton with the highest electronegativity

This is because fluorine-based polymer membranes are generally robust and have both hydrophobic and oleophobic properties, that is, they exhibit water repellency and antifouling properties.

For example, in Patent Document 5, as an example of a four-layer transparent protective film, four layers of a fluorine polymer film, a silicon nitride film, an epoxy polymer film, PET, or a fluorine polymer film are used. The structure listed is disclosed.

[0023] However, these composite films are complicated and expensive to manufacture, but especially when using a silicon nitride film as part of a multilayer film, the required protection capability is maintained without altering the OLED. Is not always easy to get. In addition, the adhesion between the inorganic film and the organic polymer film, particularly the fluorine polymer film, is not always ensured, and the protective ability may deteriorate due to peeling.

Moreover, in the case of these multilayer films, the transparency was not always ensured.

Patent Document 4: Japanese Patent Application Laid-Open No. 2004-119138

Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-139991

Disclosure of the invention

Problems to be solved by the invention

[0024] In order to solve the above problems, an object of the present invention is to provide an organic EL device including a microlens array that can be stably and inexpensively manufactured.

Another object of the present invention is to provide an organic EL element that can be manufactured more stably and inexpensively by integrating a cap and a microlens array.

[0026] Another object of the present invention is to provide an organic EL device that can be manufactured more stably and inexpensively by providing a method for securely bonding a cap and a substrate.

[0027] The present invention also provides an organic EL device that can be manufactured more stably and inexpensively by simultaneously realizing and sealing the protection of the organic EL device and the reliable adhesion of the cap and the substrate. Objective.

[0028] In order to solve the above problems, the present invention provides an organic EL device that increases the ratio of the amount of light emission Z and the power consumption by concentrating the light emission from both sides of the organic EL layer on one side. With the goal.

[0029] The present invention also provides an organic EL device that uses a metal substrate as a substrate to provide a stable and inexpensive manufacturing mechanism that concentrates the light emitted from the double-sided force of the organic EL layer on one side. Objective.

[0030] In order to solve the above-mentioned problems, the present invention has a simple structure 'manufacturing method, the organic EL layer does not deteriorate / deteriorate, and the transparency is ensured. The purpose is to provide a protective film suitable for a type of organic EL device and a method for producing the same.

Means for solving the problem

[0031] In order to achieve the above object, an organic EL device according to the present invention includes an organic EL light emitting diode (OLED) including a transparent electrode film, an organic EL layer, and a counter electrode layer, as described in claim 1. In an organic EL element including a substrate on which the OLED is mounted and a cap provided so as to cover the OLED and having a transparent portion facing the transparent electrode film, the outer surface or the inner surface of the cap, or the A microlens array is provided on the surface side of the transparent electrode film.

[0032] Further, as described in claim 2, the cap is made of silicone resin, and the microphone lens is provided integrally with the cap.

[0033] In addition, as described in claim 3, when the cap and the substrate are bonded, a primer treatment is performed on the bonding portion of the substrate with the cap.

[0034] Also, as described in claim 4, an organic EL light emitting diode (OLED) including a transparent electrode film, an organic EL layer, and a counter electrode layer, a substrate on which the OLED is mounted, and a cover provided to cover the OLED. And a cap whose portion facing the transparent electrode film is transparent, and a microlens array is provided integrally with the cap on the outer surface or inner surface of the cap, and the inner surface of the cap A gap between the upper surface of the substrate including the upper surface of the OLED and a gap between the bonding surface of the cap and the substrate is filled with a silicone resin.

[0035] Further, as described in claim 5, when the cap and the substrate are bonded, both the bonding portion of the substrate and the bonding portion of the cap are subjected to primer treatment.

[0036] Further, as described in claim 6, the silicone resin is polydimethylsiloxane (Poly-Di-Methyl- Siloxane, PDMS).

In order to achieve the above object, the organic EL device according to the present invention includes an organic EL light-emitting diode including a first transparent electrode film, an organic EL layer, and a second transparent electrode film as described in claim 7. (OLED) In an organic EL device including an OLED having a force and a substrate on which the OLED is mounted so that the first transparent electrode film is in contact with the OLED, a light reflection surface is provided on a side of the substrate on which the OLED is mounted. It is characterized by that.

[0038] According to the present invention, the light emitted from the organic EL layer, which has passed through the first transparent electrode film as in the prior art, is directly emitted to the outside, and in addition to this, the second transparent electrode film is applied to the second transparent electrode film. The material that has passed is reflected by the light reflecting surface provided on the substrate and superimposed on the material that has passed through the first transparent electrode film to be emitted to the outside. The ratio of the amount of light emitted to the outside and the Z power consumption can be almost doubled.

[0039] Further, as described in claim 8, the substrate is a metal substrate made of, for example, magnesium, aluminum, or an alloy containing the same, and having an insulating film formed on the surface thereof. To do.

[0040] The metal substrate can be made into a light reflecting surface simply by finishing the surface smoothly so as to be a mirror surface.

In particular, a magnesium substrate can be easily mirror-finished, and a high-quality light reflecting surface can be obtained at low cost.

These metal substrates, especially magnesium substrates, are rich in workability, and can be manufactured at low cost because they can easily form a strong and thin insulating film by surface oxidation, and have high thermal conductivity and high power consumption. Although it is easy to dissipate heat, the organic EL device according to the present invention can be provided with these features.

[0041] Further, as described in claim 9, the light reflecting surface includes a plurality of concave mirror arrays having a concave mirror force.

[0042] The concave mirror array to be provided on the substrate according to the present invention, particularly in the case of a metal substrate, is surface-oxidized after the surface of the original substrate is previously finished in the shape of the concave array by molding, polishing ij, or press. It can be easily provided by filling the concave portion with a transparent resin such as silicone to flatten the final surface.

[0043] The size and pitch of each concave mirror capture and reflect as much lateral light as possible, so out of the O LED size (hereinafter referred to as d) and pitch (hereinafter referred to as D, D> d), D In other words, it is desirable to have a one-to-one correspondence with OLEDs and arrange them as closely as possible.

[0044] The planar shape of each concave mirror is usually circular. In order to increase the amount of light collected, it may be square or rectangular according to the vertical and horizontal pitches of the OLED.

The focal length of each concave mirror (hereinafter referred to as fl) should be approximately 0.5 times or more and 2 times or less of OLED pitch D.

The distance between the concave mirror array and the OLED (hereinafter referred to as si) is approximately 0.5 times the focal length fl of the concave mirror, preferably 2 times or less.

In general, the cross-sectional shape of each concave mirror is preferably a parabola. [0045] The details of the above parameters are such that the reflected light is attenuated by the passing medium, the distortion due to various aberrations of the concave mirror, and the light emission of the adjacent OLE D so that the reflected light can be focused in the direction perpendicular to the surface of the organic EL element. It is determined in consideration of interference with

[0046] Further, as described in claim 10, a cap is further provided so as to cover the OLED, and a portion facing the second transparent electrode film is transparent, and the outer surface or the inner surface of the cap is provided. Or a microlens array comprising a plurality of microlenses on the surface side of the second transparent electrode film.

[0047] According to the present invention, the microlens array to be provided on the cap side, that is, close to the first electrode film, can be provided by various methods.

In particular, stable performance including sealing of the cap and the substrate can be obtained at a low cost by forming the cap and the substrate integrally with, for example, silicone resin.

[0048] The size and pitch of each microlens captures and reflects as much lateral light as possible, so out of the OLED size (hereinafter referred to as d) and pitch (hereinafter referred to as D, D> d), D It is desirable to arrange them as much as possible, that is, with a one-to-one correspondence with OLEDs.

[0049] The planar shape of each microlens is usually a circle. In order to increase the amount of condensed light, it may be square or rectangular according to the vertical and horizontal pitches of the OLED.

The focal length of each microlens (hereinafter referred to as f2) is approximately 0.5 times the OLED pitch D, preferably 2 times or less.

The distance between the microlens and the OLED (hereinafter referred to as s2) is approximately 0.5 to 2 times the focal length f2 of the microlens.

The cross-sectional shape of each microlens is preferably a parabola.

[0050] The details of the above parameters are such that the refracted light can be focused in the direction perpendicular to the surface of the organic EL element so that the light is attenuated by the passing medium, the distortion caused by various aberrations of the microlens, and the adjacent OLED. It is determined in consideration of interference with light emission.

[0051] In order to achieve the above object, the protective film of the organic EL device according to the present invention is laminated with a silica film obtained by firing polysilazane (PHPS) as described in claim 11. Including a fluorine-containing organic fluorine polymer film, and the fluorine-containing organic fluorine polymer film of the silicon-containing organic fluorine polymer film includes a perfluoro hydrocarbon part, a hydrocarbon part, and a It is characterized by comprising a group.

[0052] Further, as described in claim 12, the perfluorohydrocarbon portion is characterized by being a perfluoroalkane or a perfluoroalkene having only a straight chain or a side chain.

[0053] Further, as described in claim 13, the perfluorohydrocarbon part is a perfluoropolyether moiety having only a straight chain or a side chain and containing only a saturated bond or an unsaturated bond. (Perfluoropolyokitacene) is also a feature.

[0054] Further, as described in claim 14, the hydrocarbon portion includes only a saturated bond, is only a straight chain, or has a side chain, and at least one of hydrogen atoms is substituted with the kalein-containing group. It is characterized by.

[0055] Further, as described in claim 15, one or more of the hydrogen atoms are further substituted with a halogen.

[0056] Further, as described in claim 16, the silicon-containing group is a silane composed of one or more linear silicon atoms, wherein one or more hydrogen atoms are an alkoxyl group or a halogen. It is characterized by being replaced.

[0057] Further, in order to achieve the above object, a method for producing a protective film of an organic EL element according to the present invention is as described in claim 17,

Diluting polysilazane (PHPS) with a cyclohexane solvent to obtain a polysilazane solution to which a predetermined metal catalyst is added;

Applying the polysilazane solution onto the ITO film of the organic EL element, and forming a silica film by humidifying and drying at a predetermined temperature and a predetermined humidity of 20 ° C to 100 ° C for a predetermined time. When,

A step of diluting a silicon-containing organic fluorine-based polymer comprising a perfluorinated hydrocarbon portion, a hydrocarbon portion, and a silicon-containing group with perfluorinated hexane to obtain a solution of the above-mentioned silicon-containing organic fluorine-based polymer. When,

Applying the silicon-containing organofluorine polymer solution onto the silica film; and humidifying and drying at a predetermined temperature of 20 ° C. to 100 ° C. for a predetermined time, Fluorine-containing organic fluorine-based polymers are bound to silica atoms at the molecular level. And the step of making it include.

The invention's effect

[0058] The organic EL device according to the present invention includes a microlens array made of silicone resin that can be manufactured stably and inexpensively, so that the luminance in the direction perpendicular to the light emitting surface is increased, and the organic EL layer It is possible to suppress an increase in power consumption that causes deterioration of the battery.

[0059] Further, the organic EL element according to the present invention can be manufactured more stably and inexpensively because the cap and the microlens array are integrally formed.

[0060] Further, the organic EL device according to the present invention can be manufactured more stably and inexpensively because the sealing treatment can be performed firmly by applying a primer treatment to the substrate when the cap made of silicone resin is bonded to the substrate. .

[0061] Further, since the organic EL device according to the present invention is sealed and protected by a silicone resin that can be cured at a low temperature simultaneously with the adhesion between the cap and the substrate, the organic EL device can be manufactured stably and inexpensively without deterioration.

[0062] The organic EL device according to the present invention can emit light from both sides of the OLED to the outside by the light reflecting surface provided on the substrate. It is possible to suppress an increase in power consumption that causes deterioration of the organic EL layer.

[0063] In addition, the organic EL device according to the present invention can be manufactured stably and inexpensively by integrally forming the light reflecting surface using a metal substrate such as magnesium as the substrate.

[0064] The organic EL device according to the present invention is combined with a light reflecting surface provided on the first transparent electrode film side and a microlens provided on the Z or second electrode film side, that is, the cap side. Since it is possible to condense maximum in the direction perpendicular to the element surface, the ratio of effective light emission amount Z power consumption as a display device can be further increased.

[0065] According to the protective film of the organic EL device according to the present invention, the water-repellent property comprising two layers of a dense silica film and a silicon-containing organic fluoropolymer film firmly bonded to the silica film at a molecular level. It is possible to provide a protective film that is rich in oil repellency, and is vulnerable to fragile organic EL elements (OLEDs and their driving) during the manufacturing process and after storage or use with respect to moisture, oxygen, high temperature, and physical impact. Circuit), and top emission type organic EL elements can be provided with high reliability and economically. [0066] Further, according to the method for manufacturing a protective film of an organic EL element according to the present invention, an organic EL element (OLED and its driving circuit) that is vulnerable to moisture, oxygen, high temperature, and physical impact is physically present. Highly water- and oil-repellent protection consisting of two layers: a dense silica film that is not damaged mechanically or chemically, and a silicon-containing organic fluoropolymer film that is firmly bonded to the silica film at the molecular level. A highly reliable and economical manufacturing method for forming a film can be provided.

Brief Description of Drawings

[0067] [FIG. 1] (A), (B), and (C) are cross-sectional schematic views showing organic EL devices in Examples 2 and 3, respectively.

FIG. 2 (A), (B), and (C) are cross-sectional schematic views showing organic EL elements in Examples 4, 5, and 6, respectively.

FIG. 3 is a schematic cross-sectional view showing an organic EL device in Example 7.

FIG. 4 is a schematic cross-sectional view showing the structure of an organic EL device in Example 8.

FIG. 5 is a schematic cross-sectional view showing the structure of an organic EL device in Example 9.

FIG. 6 is a schematic cross-sectional view showing the structure of an organic EL device in Example 10.

FIG. 7 is a schematic cross-sectional view showing the structure of an organic EL device in Example 11.

FIG. 8 is an optical equivalent cross-sectional view of an organic EL element in Example 8.

FIG. 9 is a distribution diagram of the light emission amount of the organic EL device in Example 8.

FIG. 10 is an optical equivalent cross-sectional view of an organic EL element in Example 9.

FIG. 11 is a distribution diagram of the light emission amount of the organic EL device in Example 9.

FIG. 12 is an optical equivalent cross-sectional view of an organic EL device in Example 10.

FIG. 13 is a distribution diagram of the light emission amount of the organic EL device in Example 10.

FIG. 14 is a schematic cross-sectional view of an organic EL device according to Examples 12 to 15 of the present invention.

FIG. 15 is a schematic diagram showing a molecular structure of a protective film of an organic EL layer element in Example 12.

FIG. 16 is a schematic diagram showing a molecular structure of a protective film of an organic EL layer element in Example 13.

FIG. 17 is a schematic diagram of a molecular structure showing various aspects of the silicon-containing organic fluorine-containing polymer according to Examples 12 to 15 of the present invention. FIG. 18 is a flowchart showing a procedure for forming a protective film for an organic EL layer in Example 15.

Explanation of symbols

11, 12, 13, 14, 15, 16 rays

21, 22, 23, 24, 25, 26 rays

51, 52, 53, 54, 55, 56 rays

61, 62, 63, 64, 65, 66 rays

71, 76 rays

100 cap

102 Bottom of cap

110 micro lens array

115 micro lens

105 Cap legs

120 Bonding part

130 Filling section

200 substrates

201 Metal substrate (magnesium substrate)

205 boundary (light reflecting surface)

215 Transparent layer

210, 225 Insulating film

220 Polysilicon layer or amorphous silicon layer (TFT layer)

230 Pixel drive unit (TFT transistor circuit)

231 source

233 source wiring

235 drain

237 Gate insulation film

239 Gate wiring

240 Cathode electrode (first electrode) 250R, 250G, 250B OLED layer

260 Transparent electrode film (second electrode)

270 Protective film

300, 301, 302 OLED layer

305 Mirror image

310 1st transparent electrode film (drain wiring)

320 Second transparent electrode film

322 Mg— Ag layer

401 boundary

410 Silica film obtained by firing polysilazane

420 C-containing organofluorine polymer film

430, 440, 450 Main part of organofluorine polymers containing silicon

432 Penolev Noreolo Anolecan

434, 454 Hydrocarbon part

439, 459

442 Perfluoropolyoxetane

490, 490a, 490b Dirt

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be specifically described with reference to the drawings in the case of a top emission type and an active matrix drive type.

The present invention can be applied to the bottom emission type or passive matrix drive type as long as it is appropriately modified.

[0070] FIGS. 1 (A), (B), and (C) are cross-sectional schematic views showing organic EL elements in Examples 2 and 3, respectively, and FIGS. 2 (A), (B), and (C) are respectively FIG. 3 is a cross-sectional schematic view showing the organic EL element in Examples 4, 5, and 6. FIG. 3 is a cross-sectional view showing the organic EL element in Example 7.

Example 1

Referring to FIG. 1 (A), a cross-sectional schematic view showing an organic EL device according to the present invention, wherein the organic EL device body is formed on a substrate 200 and is made of, for example, a transparent cap 100 made of glass. The leg portion 105 covered with and extending downward on the edge portion of the cap is sealed by being bonded to the substrate 200 via the bonding portion 120 and is blocked from the outside.

[0072] The organic EL element body includes an organic EL light emitting diode (OLED) for one panel and a corresponding pixel driving unit 230. For example, a polysilicon layer or amorphous silicon layer 220 is formed on the upper surface of the substrate 200. As a result, the pixel driving unit 230 is formed.

[0073] In principle, each pixel driving unit 230 is composed of a single TFT transistor, and its gate and source are connected to driving wiring (not shown) in rows and columns, respectively, and its drain is

Connected to the cathode electrode 240 of the OLED (via a conductive metal layer if necessary).

[0074] Each OLED is composed of a transparent electrode film 260 common to the cathode electrode 240 and an organic EL layer 250R, 250G, or 250B corresponding to the three primary colors sandwiched between the two electrodes. film

A protective film 270 is formed on 260.

In this way, the organic EL element body is formed.

When a predetermined signal voltage that changes with time is applied to the pixel drive unit of the organic EL element body after the sealing is completed, the OLED emits light of three primary colors having a light amount that changes in accordance with the signal voltage.

Each of the three primary color lights is emitted from above through the transparent electrode film 260, the protective film 270, and the transparent cap 100, and each pixel has a desired color tone and functions as a display device. .

According to the present invention, the microlens array 110 made of silicone resin is adhered to the inner surface of the cap 100, and each microlens 115 has a convex lens shape and faces the upper surface of the OLED. ing.

[0077] The light emission intensity of each OLED depends on the light emission angle as described above. In FIG. 1 (A), the vertical upper direction is maximized, and the angle from the upper vertical is proportional to cos Θ with respect to Θ. Yes.

Therefore, the microlens 115 collects the light emitted from the OLED in the vertically upward direction.

In FIG. 1 (A), the size and pitch of the microlens 115 are the organic EL layers 250R, 250G, and 250B, and therefore the force that matches the size and pitch of one OLED is not limited to this. In any case, the size and pitch of the microlens 115 must be matched to the size and pitch of the pixel in the case of recent high-definition display, and is m (micron) class.

[0079] The present invention is based on the fact that such micron-class precision machining has been put to practical use for the first time due to recent technological advances. When silicone resin, especially PDMS (Poly-Di-Methyl-Siloxane) is applied, it is chemically inert, and the conformity of the substrate to the warp is good, isotropic, homogeneous, transparent, and elastomeric. It describes that a controllable surface state can be formed by plasma treatment with high durability and subsequent chemical treatment.

Non-Patent Document 3: Y Xia et al: Soft Lithography, Angew. Chem. Int. Ed. 1998, 37, pp550—575.

Therefore, when this PDMS material is used, a desired microlens array can be obtained with good releasability at low cost from, for example, an embossed cage from a micron-class master made of silicon. Silicon's state-of-the-art cache technology is 0.1 micron class, and the above micron class matrix can be obtained at low cost.

[0081] The distance between the tip of the microlens 115 and the OLED upper surface protective film 270 is as small as possible in order to increase the light collection efficiency. However, it is desirable that the distance between the substrate 200 and the cap 100 is warped. Even if there is, the value is set so that a part of the microlens is not pressed and deformed against the protective film.

Example 2

Referring to FIG. 1 (B), which is a schematic cross-sectional view showing an organic EL element according to the present invention, the difference from Example 1 is that the outer surface where the microlens array 110 is not the inner surface of the cap 100. Be prepared for.

In this way, since the organic EL layer is sealed by the cap and separated from the microlens array, even if water, oxygen, or the like is slightly attached to the microlens array.

There is no fear of damaging the organic EL layer.

Example 3

Referring to FIG. 1 (C), it is a schematic cross-sectional view showing the organic EL device according to the present invention. The difference from the first and second embodiments is that the microlens array 110 is attached to the inner surface or the outer surface of the cap 100. The OLED transparent electrode film 260 is attached to the upper surface side of the OLED through the protective film 270.

In this manner, the light can be collected most efficiently by the microlens 115, and the microlens array 110 can most effectively protect the OLED.

Example 4

[0086] Referring to Fig. 2 (A), it is a schematic cross-sectional view showing the organic EL device according to the present invention. The difference from the above-mentioned Examples 1 to 3 is that the inner surface of the cap 100 made of silicone resin is microscopic. The lens 115 is integrally formed with the cap 100, that is, the lens 115 is obtained by integrally molding the microlens 115 and the cap 100 from silicone resin.

[0087] Accordingly, when the PDMS material, which is silicone resin as in Example 1, is used, a desired microlens array and cap are integrated from, for example, embossing from a micron-class matrix made of silicon, for example. Can be obtained inexpensively with good releasability.

[0088] Silicone resin PDMS is transparent as described above, and allows OLED light emission to pass outside, while chemically inert, it protects the internal OLED and adapts to substrate warpage. And has ideal performance as a cap.

[0089] Further, generally, the dangling bonds of Si atoms on the surface of the silicone resin can be stably bonded to OH groups by, for example, oxygen plasma treatment.

When the substrate 200 and the leg portion 105 of the cap 100 are bonded and sealed, the bonding surface (bonding portion 120) of the substrate 200 is preliminarily treated with a primer so that the OH group of the cap 100 is dehydrated. Thus, Si atoms on the surface of the silicone resin are chemically bonded to the molecules of the bonding portion 120, and a strong adhesive seal is obtained.

Example 5

[0090] Referring to FIG. 2 (B), although the microlens size 'pitch corresponds to the organic EL layers 250R, 250G, 250B, and thus the OLED size' pitch, in Example 4 above, On the other hand, in this embodiment, there is a one-to-two correspondence.

Example 6

[0091] Referring also to FIG. 2C, the microlens size and pitch correspond to the OLED size and pitch on a two-to-one basis. [0092] In general, the smaller the microlens, the greater the force-contrast distortion that can be obtained with a shorter focal length. Considering the OLED size 'pitch, the distance between the OLED top surface and the microlens and their variations, etc. Therefore, the size and pitch of the microlenses must be determined so that a stable light collection rate can be obtained over the entire panel surface.

This naturally holds true for the above-described Examples 1, 2, and 3, and Example 7 below, which are other examples.

Example 7

[0093] Referring to FIG. 3, a schematic cross-sectional view showing an organic EL device according to the present invention, in which a transparent cap 100 made of glass, for example, having a microlens 115 on its inner surface is mounted on an OLED-mounted substrate 200. The entire upper surface is covered, and the gap between the two is filled with the silicone resin PDMS including the leg portion 105 of the cap 100 and the adhesive portion 120 of the substrate 200 to form the filling portion 130.

[0094] In this way, PDMS effectively protects the OLED in a single process, and at the same time, the substrate 200 and the cap 100 can be effectively bonded by the bonding portion 120. It can be cured at a low temperature of 48 hours at 65 ° C for 4 hours, so it does not damage the organic EL layer.

[0095] When the substrate 200 and the leg portion 105 of the cap 100 are bonded and sealed, the bonding surface of the substrate and the bonding surface of the leg portion are preliminarily treated in advance to fill the bonding portion 120. The OH groups on the surface of the prepared silicone resin are removed by a dehydration reaction, and the S source on the surface of the silicone resin is chemically bonded to the molecules on the bonding surface of the substrate and the cap, resulting in a strong Adhesion and sealing can be obtained.

[0096] FIGS. 4, 5, 6, and 7 are schematic cross-sectional views showing the structures of the organic EL elements in Examples 8, 9, 10, and 11, respectively. FIG. 8, FIG. 10, and FIG. Optical equivalent cross-sectional views of the organic EL elements in Examples 8, 9, and 10, respectively, FIGS. 9, 11, and 13 are distribution diagrams of the light emission amounts of the organic EL elements in Examples 8, 9, and 10, respectively. is there.

Example 8

FIG. 4 is a schematic cross-sectional view showing the structure of the organic EL element in Example 8.

The organic EL element body is formed on a metal substrate, for example, a magnesium substrate 201. For example, a leg (not shown) covered with a transparent glass cap 100 and extending downward at the edge of the cap is sealed by being bonded to the corresponding edge of the substrate, and is blocked from the outside. Is done.

[0098] The organic EL element body is composed of, for example, a plurality of organic EL light emitting diodes corresponding to one panel.

(OLED) and a corresponding pixel driving unit, for example, a polysilicon layer or an amorphous silicon layer 220 is deposited on the insulating film 210 formed on the upper surface of the substrate 201, and the pixel driving unit is formed therein. Is done.

Each pixel driving unit is in principle a single TFT transistor, and includes a source 231, a gate insulating film 237, a drain 235, a source wiring 233, a gate wiring 239, and a drain wiring 3 10.

The source wiring 233 and the gate wiring 239 each form a row and a column, and are driven by a row / column driving circuit provided at the edge of the pixel driving unit array and connected to the gate wiring to which a selection potential is applied. The drain potential is equal to the pixel signal potential applied to each source line. In this way, an arbitrary signal potential is sequentially applied to the drain line of each pixel driving unit.

[0100] The drain wiring 310 is connected to the drain 235 through an appropriate noria metal layer if necessary.

Of the upper surface of the polysilicon (amorphous silicon) layer, a region between adjacent pixel driving units is covered with a silicon nitride-based silicon insulating film 225, and the drain wiring 310 is stretched thereon. It becomes the first transparent electrode film of OLED.

[0101] Each OLED also has a first transparent electrode film 310, a common second transparent electrode film 320, and an organic EL layer 300 sandwiched between both electrode films, and usually three adjacent organic EL layers 301, 300, 302 force S3 primary colors R, G, B are supported.

In order to increase the electron injection efficiency between the second transparent electrode film and the organic EL layer 300, a low-keke function alloy, for example, an Mg—Ag layer 322 is interposed.

The thickness of the Mg-Ag layer is as thin as 10 nm so as not to impair the transparency. Further, a protective film (not shown) is formed on the second transparent electrode film 320.

[0102] In this way, the organic EL element body is formed. Here, the typical film pressure of each film and layer related to the light emitting part of this organic EL element is listed. Substrate insulating film 210: 10 nm, polysilicon (amorphous silicon) layer 220 (including insulating film 225): 500 1st transparent electrode film 310: 100nm, OLED layer 300: 60nm,

Mg—Ag layer: 10 nm, second transparent electrode film 320: 40 nm.

[0103] After completion of sealing with the cap, when a predetermined signal voltage that changes with time is applied to the row and column wirings of the pixel drive unit of the organic EL element body, each organic EL layer 300 corresponds to the signal voltage. Emits one of the three primary colors with a variable amount of light.

Each of the three primary colors is emitted to the outside through the Mg-Ag film 322, the second transparent electrode film 320, the protective film, and the transparent cap 100, and each pixel has a desired color tone and serves as a display device. It will fulfill the function.

The luminance of the organic EL element is determined by the amount of light emission of the OLED when the signal voltage is maximum. In the following, the “light emission amount” is limited to this case.

[0104] The light emission amount of the organic EL layer is maximum in the vertical direction in Fig. 1 as described above, becomes zero in the horizontal direction, and forms a cos Θ distribution with respect to the angle Θ measured with the upward direction as the baseline. . Therefore, in this embodiment, light emission in the downward direction in FIG. 4, that is, in the range of 90 ° ≤ Θ ≤ 180 °, is transmitted through the first transparent electrode film 310, the polysilicon (amorphous silicon) layer 220, and the insulating layer 210. Then, it reaches the base metal boundary 205 between the insulating layer 210 and the substrate 201, and light cannot be transmitted through the metal substrate 201, and is reflected.

That is, the boundary 205 functions as a light reflecting surface, and the reflected light travels upward like the light emitted from the mirror image 305 (indicated by a two-dot chain line) of the organic EL layer 300. (Hereafter, the light reflecting surface is also indicated by “205”.)

In Figure 4, examples of direct and reflected light rays are shown as 11 and 16 and 61 and 66, respectively.

Next, the distribution of the total intensity of the direct light and the reflected light is approximately estimated.

FIG. 8 is an optical equivalent cross-sectional view of the organic EL element in this example.

Plane dimension d and pitch D of organic EL layer 300, and distance between lower surface 102 of cap s 1 force 0.1 mm ~: Lmm, whereas the distance between organic EL layer and light reflecting surface 205 is the above Even for typical film thicknesses of at most 700 nm, ie: less than L m (microns), organic EL The layer, light reflecting surface, and mirror image 305 are in close contact and are all considered to be at a sl distance from the bottom of the cap.

In this figure, sl = D = 2 X d.

Accordingly, light emitted from the organic EL layer 300 is obtained by superimposing direct light upward and reflected light from below, and the left and right sides of the organic EL layer from the left end, the center, and the right end in this figure are π Ζ2 Emission rays to (= 45 °), 11 and 12, 13 and 14, 15 and 16 are representatively shown.

FIG. 9 is a distribution diagram of the light emission amount of the organic EL element in this example.

The emission intensity Υ (relative value) of the organic EL layer 300 is cos Θ, as shown by the broken line, where the angle of the vertical upward force is 0 in the figure, but the negative Y portion corresponding to the downward emission is reflected. As shown by the solid line, the total emission intensity is 2 X cos θ (-π / 2≤θ≤π Ζ2), which can be doubled compared to the conventional case without reflection.

Example 9

FIG. 5 is a schematic cross-sectional view showing the structure of the organic EL device in Example 9.

Compared to Example 8 above, when an array of recesses is formed on the upper surface of the metal substrate 201 in advance in the drawing and the insulating film 210 is formed by oxidizing the surface in the same manner, it functions as a concave mirror. A light reflecting surface 205 is obtained.

[0110] After the transparent layer 215 is formed on the metal substrate 201 and the upper surface is flattened, the layers after the polysilicon layer or the amorphous silicon layer 220 are formed in the same manner as in the eighth embodiment.

In the case of the active matrix driving type as in this embodiment, the process for forming the polysilicon layer or amorphous silicon layer 220 and the TFT transistor therein may require a high temperature. Apply low melting glass.

If the high temperature is not required for the subsequent process in the case of a noisy matrix drive type, for example, silicone resin, especially PDMS (Poly-Di-Methyl-Siloxane) can be used as the material of the transparent layer 215. .

PDMS is a plasma process that is chemically inert, isotropic, homogenous, and transparent, and has high durability as an elastomer, followed by chemical process. A controllable surface state can be formed, so that it is in close contact with the first transparent electrode film, etc. Force can also absorb the stress due to temperature coefficient difference.

Next, the distribution of the total light emission intensity in this example is estimated.

FIG. 10 is an optical equivalent cross-sectional view of the organic EL element in Example 9.

Direct upward light emission is indicated by rays 11-16 as in Example 1 above. On the other hand, light emitted downward is reflected by the concave mirror, but in this embodiment, the distance s2 between the light reflecting surface 205 and the organic EL layer 300 forming the concave mirror array is equal to the focal length fl of the concave mirror. The reflected light is parallel for each point light source on the organic EL layer.

In general, since the refractive index of the transparent layer 215 is greater than 1, the transparent layer 215 functions as a convex lens for each of the downward emission and reflected light, so to be precise, fl is transparent with a concave mirror that is not the focal length of the concave mirror alone. The focal length of the composite system with two convex lenses by layer 215.

In addition, strictly speaking, the light reflecting surface changes along the concave surface of the concave mirror (the arc-shaped broken line in the figure in the lower side of the light reflecting surface 205), but here it is represented by a plane for simplicity.

In this embodiment, the diameter of the concave mirror is set equal to the pitch D of the organic EL layer.

[0112] That is, in the figure, among the light rays that are emitted downward in the left, center, and right edge of the organic EL layer, between 51 and 52, φ4, between 53 and 54, φ5, between 55 and 56, φ6 Rays in this range are reflected to become parallel rays, rays between 61 and 62, 63 and 64, and 65 and 66, respectively.

FIG. 11 is a distribution diagram of the light emission amount of the organic EL element in this example.

The intensity distribution of the upper emission follows the cos θ (-π 2 ≤ θ ≤ π / 2) indicated by the broken line, but the lower emission is in the above range of φ 4 to φ 6, that is, about 0.1 π ≤ 0. ≤ About π Ζ4 Part or all of the force reflected light will concentrate on 0≤ θ≤0.1 π.

As a result, as shown by the solid line, the total emission intensity is concentrated at about 0.1 π to +0.1 π, and the peak value is about 2.8 at Θ = 0. Compared to about 2.0 in the case of Example 8 above, this is further improved.

In this way, it is possible to improve the light emission intensity / power consumption ratio when the organic EL display device is viewed from the front (Θ˜0).

Example 10

FIG. 6 is a schematic cross-sectional view showing the structure of the organic EL element in Example 10. In contrast to Example 8, for example, as shown in FIG. 6, a convex microlens 115 facing the organic EL layer is further provided on the lower surface 102 of the cap 100.

The upper emission rays 11 and 16 from the organic EL layer are refracted by the microlens to become external rays 21 and 26.

On the other hand, the lower emission light beam is reflected by the light reflecting surface 205 to become reflected light beams 61 and 66, and is refracted by the microphone opening lens to become external light beams 71 and 76.

[0115] As a material for the microlens array, for example, when silicone resin, especially PDM S (Poly-Di-Methyl-Siloxane), is applied, the adaptability to the warp of the cap is very chemically inactive. It is isotropic, homogeneous and transparent, and has high durability as an elastomer, so it can absorb stress due to temperature coefficient differences.

FIG. 12 is an optical equivalent cross-sectional view of the organic EL element in Example 10.

(Strictly speaking, both surfaces or one surface of the microlens 115 changes with a predetermined curvature (the arcuate broken line in the drawing of the microlens 115). Here, for simplicity, it is represented by a plane.

Further, the distance si between the organic EL layer 300 and the microlens 115 is set equal to the focal length f2 of the microlens in this embodiment. )

[0117] Accordingly, in the figure, the light rays emitted from the upper side from the left end, the center, and the right end of the organic EL layer are superimposed on the light rays emitted downward and reflected by the light reflecting surface 205, of which between 11 and 12 Between φ 1, 13 and 14, between φ 2, 15 and 16, the light in the range of φ 3 is reflected and parallel to the parallel rays, 21 and 22, 23 and 24, 25 and 26, respectively. Light.

FIG. 13 is a distribution diagram of the light emission amount of the organic EL element in this example.

In the case of the present embodiment, the upper and lower light emission are superimposed, and the range of φ1 to φ3 in the cos θ (~ π / 2≤ θ≤πΖ2) distribution, that is, about 0.1π≤0. ≤ About π Ζ4 A part or all of the part will be concentrated to 0≤ θ≤0.1 π in the outgoing light.

As a result, as shown by the solid line, the total emission intensity is concentrated in the range of about 0.1 π to +0.1 π. Its peak value is Θ = 0, which is about 3.6. Compared with the increase of about 2.0 in the case of Example 8 above, it is further improved. Example 11

FIG. 7 is a schematic cross-sectional view showing the structure of the organic EL element in Example 11.

In addition, for example, a convex microlens 115 facing the organic EL layer is further provided on the lower surface 102 of the cap 100.

[0120] The upper emitted light beams 11 and 16 from the organic EL layer are refracted by the microlens 115 to become external light beams 21 and 26.

On the other hand, the lower emitted light beams 51 and 56 are reflected by the concave mirror-like light reflecting surface 205 to become reflected light beams 61 and 66, and refracted by the microlens 115 to become outer light beams 71 and 76.

[0121] That is, the upper emitted light beam is collected once by the microlens and the lower emitted light beam is collected twice by the microlens and the concave mirror, so that the position, size, and focal length of the microlens and concave mirror are appropriately adjusted. By selecting, the light collection efficiency can be further increased.

FIG. 14 is a schematic cross-sectional view of the organic EL device according to Examples 12 to 15, FIG. 15 is a schematic diagram showing the molecular structure of the protective film of the organic EL layer device in Example 12, and FIG. FIG. 17 is a schematic diagram showing the molecular structure of the protective film of the organic EL layer device in Example 13, FIG. 17 is a schematic diagram of the molecular structure showing various aspects of the fluorine-containing organic fluorine-based polymer according to Examples 12-15, FIG. 18 is a flowchart showing the procedure for forming the protective film for the organic EL layer in Example 15.

Example 12

Referring to FIG. 14, there is a schematic cross-sectional view of a top emission type organic EL device according to the present invention, in which a TFT layer 220 is formed on a substrate 200, and there are a plurality of inner layers of the TFT layer 220. The TFT transistor circuits 230 and row / column wirings (not shown) for selectively driving these TFT transistor circuits 230 are formed.

[0124] The output of the TFT transistor circuit 230 is connected to the first electrode 240, and an organic EL layer 250R, 250G, or 250B is formed on the first electrode 240, and an ITO transparent film is further formed thereon. The second electrode 260 consisting of the first electrode 'organic EL layer' and the second electrode An organic electroluminescent diode (hereinafter referred to as OLED) is constructed.

[0125] Normally, when a reference potential (ground potential) is applied to the second electrode and a selected voltage is applied to the selected row wiring, all TFT transistor circuits connected to the selected row wiring are activated. Then, a voltage applied to the column wiring or a voltage corresponding thereto is applied to the first electrode, and the organic EL element emits light with a light intensity corresponding to the applied voltage. For color display, an OLED that includes a set of red, green, and blue organic EL layers 250R, 250G, and 250B is selected.

[0126] Regarding the structure and operation of each of the row and column wiring and its drive circuit, TFT transistor circuit, first electrode, organic EL layer, and second electrode of the organic EL element described so far, will be further described. The detailed description of is omitted.

A protective film according to the present invention is formed on the second electrode, and includes a silica film 410 obtained by baking polysilazane and a silicon-containing organic fluorine-based polymer film 420.

Referring to FIG. 15, it is a schematic diagram showing the molecular structure of the protective film of the organic EL layer device in Example 12 of the present invention.

In the figure, the protective film is composed of a silica film 410 obtained by baking polysilazane and a silicon-containing organic fluorine-based polymer film 420, both of which are molecularly bonded with a one-dot chain line 401 as a boundary.

First, a silica film obtained by firing polysilazane will be described.

Polysilazane PHPS (PerHydroPolvSilazane) is based on “One SiH—NH—”.

2

It is an inorganic polymer (polymer) that is soluble in organic solvents, but when it is diluted with an organic solvent and coated, it is dried by humidification and baked. A silica (SiO 2) film 410 is formed.

2

Silica's nore is a force consisting of polycrystals with “one Si—o—” as the basic unit. The Si atoms on the surface of the polycrystal are usually terminated with a hydroxyl group “—OH”.

[0129] Next, the silicon-containing organic fluorine-based polymer will be described.

Referring to FIG. 17, it is a schematic diagram of the molecular structure showing various embodiments of the silicon-containing organofluorine polymer.

[0130] Fig. 17 (A) is the most basic organofluorine polymer, called perfluoroalkane, which contains all the hydrogen atoms of acyclic 'saturated hydrocarbons (alkanes). Place with fluorine atom It has been changed.

Perfluoroalkane has a simple structure and is rich in water and oil repellency, but it cannot secure adhesion to the organic EL elements to be protected.

Even if an unsaturated bond is introduced into perfluoroalkane (perfluoroalkene) or Z and side chains are introduced, it is not easy to achieve both water repellency, oil repellency and adhesion.

FIG. 17B shows an example of a fluorine-containing organic fluorine-based polymer, in which a fluorine-containing group 439 is introduced and bonded to the end of the perfluoroalkanol part 432.

In this case, the silicon-containing group 439 comprises a trimethyloxysilane group “one Si (OCH 3)”,

3 3

The perfluoroalkane part 432 is bonded via a hydrocarbon part 434.

[0132] The hydrocarbon part 434 was introduced as a carrier of the silicon-containing group in order to bond the silicon-containing group 439 to the perfluoroalkane part 432, and when the molecular weight of the hydrocarbon part increases. A small molecular weight may be desirable because the number of associated hydrogen atoms increases and water and oil repellency may be impaired. In this case, the number of carbon atoms is 2 per ka atom, and therefore, a vinylsilane derivative is used as the carrier molecule for the kalein-containing group.

Perfluoroalkane 432 and hydrocarbon part 434 are combined and named the main part 430 of the C-containing organofluorine polymer.

Referring again to FIG. 15, a film 420 made of a silicon-containing organofluorine polymer shown in FIG. 17B is formed on the upper surface of the silica film 410 obtained by firing the polysilazane. is there.

The silicon-containing organofluorine polymer reacts with the hydroxyl group on the silica surface on the side of the silicon-containing group 439, the methyloxy group is removed from the silicon atom of the silicon-containing group 439, and the silicon atom on the surface of the silica 410 In addition, the matrix 430 of the fluorine-containing organic fluorine-based polymer is bonded to the silica surface at the molecular level, and bonded to the adjacent silicon-containing group via the oxygen atom.

[0134] Thus, in the case of high-purity silica obtained by firing polysilazane in particular, since most of its surface is diacidic silicon terminated with a hydroxyl group, the subsequent force is also applied and fired. The fluorine-containing organic fluorine-based polymer consists of silica and diacid It is integrated by key bonding, and strong adhesion at the molecular level can be secured.

[0135] Moreover, the main part 430 of the fluorine-containing organofluorine polymer is composed of perfluoroalkanes, which occupy most of the main part, so that it is rigid and easily oriented. Thus, the two-layer film composed of the silica film 410 and the silicon-containing organic fluorine-based polymer film 420 according to this embodiment is an excellent protective film for the organic EL element.

[0136] Referring back to FIG. 15, the upper surface of the above-contained fluorine-containing organic fluorine-containing polymer is generally easy to attach even if it is difficult to attach dirt 490 due to water repellency and oil repellency. Can be eliminated.

However, even in high-purity silica, crystal irregularities exist due to crystal grain boundaries, crystal defects, etc., for example, as shown in the central part of FIG. If a gap occurs in the alignment and dirt 490 (aqueous or oily molecule) enters the gap, the intruding part 490a may not be removed physically and chemically, which may cause deterioration of the OLED over time. is there.

Example 13

Referring to FIG. 16, in Example 13, a main part 440 of a silicon-containing organofluorine polymer having a flexible molecular structure is introduced.

Specifically, as shown in FIG. 17 (C), perfluorinated polyoxetane is applied as an organic fluorine-based polymer to form a perfluorooxetane portion 442.

Perfluorooxetane is more commonly referred to as perfluoro (poly) ether and is a straight-chain consisting of several “one CF—” or three (in the case of perfluoropolyoxetane) or

2

A perfluoroalkane having a side chain is bonded through an oxygen atom o (ether bond).

[0138] Since there are a plurality of ether bond sites due to oxygen atoms, the main part 440 of the C-containing organofluorine polymer is rich in flexibility, as shown in the center of FIG. Even if there is a gap due to, the main part of the fluorine-containing organic fluorine-containing high molecule around the gap fills the gap while bending, and repels the dirt molecule 490. The water repellency and oil repellency of dirt can be improved.

Example 14 [0139] In the above Examples 12 and 13, an organic fluoropolymer part, a hydrocarbon part, and a key made of perfluoroalkane, perfluoropolyoxetane (perfluoropolyether). Only typical and basic cases of element-containing groups are shown.

In the fluorine-containing organofluorine polymer according to the present invention, introduction of side chain or Z and unsaturated bond in the organofluorine polymer part, change of main chain carbon number in hydrocarbon part, introduction of side chain, modified hydrogen The formation of various derivatives is possible by the substitution of halogens or hydrocarbons of the above and the substitution of methyloxy groups in the group containing silicon with hydrogen, hydrocarbons, hydroxyl groups, or alkoxy groups. By setting the total molecular weight of the polymer, a protective film with high antifouling characteristics that match the crystal irregularity characteristics of the corresponding silica surface and the characteristics of the soiling substance, and that is easy to apply and sinter is obtained. Can do.

[0140] As an example, as shown in Fig. 17 (D), a hydrocarbon part 454, which is a 4-carbon nuclear power instead of a 2-carbon atom, was introduced into Example 13 and its first and third carbon atoms were introduced. Bind trimethyloxysilane to the atom.

In this example, the main portion 450 of the fluorine-containing organofluorine polymer is bonded to the silica surface by two “—Si-0—” bonds, so that the adhesion strength at the molecular level is further improved. In addition, since the orientation direction at the base of the main portion 450 is substantially parallel to the silica surface, crystal irregularities on the silica surface are more efficiently covered, and the antifouling property is further improved.

Example 15

[0141] Referring to Fig. 18, as Example 15, this is a flowchart showing a procedure for forming a protective film for an organic EL layer, which is common to Examples 12 to 14 described above.

[0142] In step S1, polysilazane (PHPS) is diluted with a cyclohexane solvent to obtain polysilazane.

Obtain a (PHPS) solution.

In order to enable humid drying at a relatively low temperature in later step S3, a predetermined metal catalyst is added.

[0143] In step S2, a PHPS solution is applied on the ITO film of the organic EL element.

[0144] In step S3, humidification drying is performed at a temperature of 60 ° C and a humidity of 90% for 1 hour.

Thereby, a dense and high-purity silica film is formed. [0145] In step S4, a fluorine-containing organic fluorine-based polymer composed of a perfluorohydrocarbon portion, a hydrocarbon portion, and a silicon-containing group is diluted with perfluorinated hexane to form the above-mentioned silicon-containing organic fluorine-based polymer. Obtain a solution.

[0146] In step S5, the solution of the silicon-containing organic fluorine-based polymer is applied onto the silica film.

[0147] In step S6, the film is dried at room temperature for 1 hour. Alternatively, humidify and dry at 60 ° C and 90% humidity for 1 hour.

As a result, the silicon-containing organic fluorine-based polymer is bonded to the silica silicon at the molecular level via the silicon-containing group.

[0148] Through the above steps S2, S3, S5, and S6, the process can be performed statically at low temperature and normal pressure, and does not cause physical or chemical damage to the organic EL device.

It is suitable for organic EL devices that are fragile with respect to physical impact.

Industrial applicability

[0149] Organic EL devices are attracting attention as devices for next-generation display systems that have low power consumption, high quality, low profile, and can also display curved surfaces. Therefore, it is necessary to further improve the effective luminous efficiency in the same display area. According to the present invention, an inexpensive and highly reliable peripheral structure that can increase the effective luminous efficiency even when the same organic EL layer is used is provided, which greatly contributes to the development of next-generation display systems. Can contribute.

Claims

The scope of the claims

[1] An organic EL light emitting diode (OLED) including a transparent electrode film, an organic EL layer, and a counter electrode layer, a substrate on which the OLED is mounted, and a portion provided to cover the OLED and facing the transparent electrode film An organic EL element comprising: a transparent cap, wherein the microlens array is provided on an outer surface or an inner surface of the cap or on a surface side of the transparent electrode film.

2. The organic EL device according to claim 1, wherein the cap is made of a silicone resin, and the microlens is formed integrally with the cap.

[3] The organic EL device according to [2], wherein, when the cap and the substrate are bonded, a primer treatment is performed on a bonding portion of the substrate with the cap.

[4] An organic EL light emitting diode (OLED) including a transparent electrode film, an organic EL layer, and a counter electrode layer, a substrate on which the OLED is mounted, a portion provided to cover the OLED and facing the transparent electrode film A transparent lens cap, a microlens array is provided integrally with the cap on the outer surface or inner surface of the cap, and the upper surface of the substrate including the inner surface of the cap and the upper surface of the OLED. The organic EL element is filled with a silicone resin including a gap between the cap and the substrate, in addition to a gap between the cap and the substrate.

5. The organic EL device according to claim 4, wherein when the cap and the substrate are bonded, a primer treatment is applied to both the bonded portion of the substrate and the bonded portion of the cap.

[6] The above-mentioned silicone repellency polydimethylsiloxane (Poly- Di- Methyl- Siloxane,

6. The organic EL device according to claim 1, wherein the organic EL device is a PDMS).

[7] An organic EL light emitting diode comprising a first transparent electrode film, an organic EL layer, and a second transparent electrode film

(OLED) and a substrate on which the OLED is mounted so that the first transparent electrode film is in contact with the OLED, wherein the substrate is provided with a light reflecting surface on the side on which the OLED is mounted. Organic EL device.

[8] The substrate is a metal substrate having an insulating film formed on a surface thereof. The organic EL device according to claim 7.

9. The organic EL device according to claim 7, wherein the light reflecting surface includes a concave mirror array having a plurality of concave mirror forces.

[10] A cap is provided so as to cover the OLED, and a portion facing the second transparent electrode film is transparent, and is provided on an outer surface or an inner surface of the cap or of the second transparent electrode film. 10. The organic EL device according to claim 7, wherein a microlens array comprising a plurality of microlenses is provided on the surface side.

[11] A silica film obtained by firing polysilazane (PHPS), and a silicon-containing organic fluorine polymer film laminated thereon, and the silicon-containing organic film of the silicon-containing organic fluorine polymer film. A protective film for an organic EL device, characterized in that the fluoropolymer comprises a perfluorohydrocarbon portion, a hydrocarbon portion, and a silicon-containing group.

[12] The protective film for an organic EL device according to [11], wherein the perfluorohydrocarbon part is a perfluoroalkane or a perfluoroalkene having only a straight chain or having a side chain, and also a force. .

[13] The perfluorohydrocarbon portion has only a straight chain or a side chain, and also has a perfluoropolyether (perfluoropolyoctacene) force including only a saturated bond or an unsaturated bond. 12. The protective film for an organic EL element according to claim 11, wherein the protective film is an organic EL element.

[14] The hydrocarbon portion includes only a saturated bond, is only a straight chain, or has a side chain, and at least one of hydrogen atoms is substituted with the above-mentioned group containing a hydrogen atom.

The protective film for the organic EL device according to 11.

15. The protective film for an organic EL element according to claim 14, wherein one or more of the hydrogen atoms are further substituted with halogen.

[16] The silicon-containing group may be substituted with one or a plurality of hydrogen atomic energy, an alkoxyl group, or a halogen in one or a plurality of linear silicon silanes. The protective film for the organic EL device according to 11.

[17] A step of diluting polysilazane (PHPS) with a cyclohexane solvent to obtain a polysilazane solution to which a predetermined metal catalyst is added;

Applying the polysilazane solution on the ITO film of the organic EL device; Forming a silica film by humidifying and drying at a predetermined temperature of 20 ° C. to 100 ° C. and a predetermined humidity for a predetermined time;

Applying the silicon-containing organofluorine polymer solution onto the silica film;

Humidified and dried for a predetermined time at a predetermined temperature and a predetermined humidity of 20 ° C or higher and 100 ° C or lower to bond the silicon-containing organofluorine polymer to the silica atoms at the molecular level. Steps,

A process for producing a protective film for an organic EL device, characterized by comprising: