JP4990587B2 - Light emitting device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a light emitting device and a method for manufacturing the same, and more particularly to a light emitting device used for a flat display panel, a backlight for a liquid crystal display, a light source for illumination, and the like, and a method for manufacturing the same.

  As an organic electroluminescent element (organic EL element), a transparent electrode serving as an anode, a hole transport layer, an organic light emitting layer, an electron injection layer, and an electrode serving as a cathode were laminated on the surface of one side of the transparent substrate. A configuration is known as an example. In such an organic electroluminescence device, by applying a voltage between the anode and the cathode, electrons injected into the light emitting layer through the electron injection layer and injected into the light emitting layer through the hole transport layer. Holes recombine in the light-emitting layer, and the energy obtained by the recombination excites organic molecules in the light-emitting layer to emit light, and this light emitted from the light-emitting layer is emitted from the light-transmitting electrode and the light-transmitting light. Is taken out through the conductive substrate.

  The organic light-emitting element has characteristics such as being self-luminous, exhibiting relatively high-efficiency light emission characteristics, and being capable of emitting light in various colors by adjusting the composition of the organic material used in the light-emitting layer. It is expected to be used as a light emitter such as a display device such as a flat panel display, or as a light source such as a backlight or illumination for a liquid crystal display, and has already been put into practical use in part. However, the organic light emitting element has a trade-off relationship between the luminance and the lifetime, and has a property that the lifetime is shortened when the luminance is increased in order to obtain a clearer image or bright illumination light.

  In order to solve this problem, in recent years, an organic light-emitting device has been proposed in which a plurality of light-emitting layers are provided between an anode and a cathode, and a layer for forming an equipotential surface between each light-emitting layer or a charge generation layer is provided. (For example, refer to Patent Document 1).

  FIG. 10 shows an example of the structure of such an organic light-emitting element. A plurality of light-emitting layers 22 are provided between an electrode 20 serving as an anode and an electrode 21 serving as a cathode, and an equipotential is provided between adjacent light-emitting layers 22. A layer that forms a surface or a charge generation layer 23 is laminated, and this is laminated on the surface of a translucent substrate 24. The electrode 20 serves as a translucent electrode, and the electrode 21 reflects light. Formed as a conductive electrode. In FIG. 10, a hole transport layer and an electron injection layer are provided on both sides of the light emitting layer 22, but the hole transport layer and the electron injection layer are not shown. By dividing the plurality of light emitting layers 22 with the equipotential surface forming layer or the charge generation layer 23 in this way, when a voltage is applied between the electrodes 20 and 21, the plurality of light emitting layers 22 are connected in series. In such a state, the light is emitted simultaneously and the light from each light emitting layer 22 is added. Therefore, when a constant current is applied, the light can be emitted with higher brightness than the conventional organic light emitting element, and the brightness-lifetime as described above can be achieved. It is possible to avoid trade-offs.

  However, problems such as emission luminance, viewing angle dependency of the emission spectrum, film thickness dependency, and decrease in light utilization efficiency, which are known in organic light emitting elements, have a film thickness on the order of optical wavelength. Optical interference effect, organic due to total reflection, derived from being a thin film device, having a reflective surface consisting of a refractive index step or a metal surface in the element, and generating light in a high refractive index medium These problems are more conspicuous in organic light-emitting devices having a plurality of light-emitting layers as described above, due to phenomena such as light confinement in a high-refractive index medium such as a light-emitting layer, a substrate, and an electrode. Will occur.

  If the light interference effect is appropriately used, it is possible to improve color purity, control directivity, etc., and is particularly useful for applications such as flat panel displays. For example, in cited document 2, the optical distance between the light emitting layer and the light reflective electrode is adjusted to an odd multiple of 1/4 wavelength, or the optical distance between the light emitting position and the maximum refractive index step position is set to 1/4 wavelength. It is described that it is possible to emphasize this wavelength by adjusting to an even number of times, and it is known that the optical distance between the light emitting layer and the light reflective electrode has a great influence on the light emission spectrum. It has been. Further, Patent Document 3 discloses that the most efficient light emission can be obtained by making all the optical film thicknesses from the respective light emitting positions of the plurality of light emitting layers to the light reflective electrodes an odd multiple of 1/4 wavelength. It is described that the emission spectrum shape becomes narrower.

  However, as described above, the optical distance between the light-emitting layer and the light-reflective electrode, the optical distance between the light-emitting layer and the maximum refractive index step position, that is, the color purity is optimized by optimizing the film thickness of the element. In the organic light-emitting element, fluctuations in emission luminance and emission color when the film thickness changes are large. This means that the film thickness tolerance at the time of manufacturing the organic light emitting device is narrowed, which directly leads to the problem of productivity. In particular, in the above organic light emitting device having a structure in which a plurality of light emitting layers, equipotential surface forming layers, or charge generation layers are laminated, the optical characteristic deviation (abnormal film thickness / refractive index) of any of the layers is other. Even the optical position of this layer is affected, so that the accuracy and necessity of film thickness control is further increased.

  Further, in Patent Document 3, it is preferable from the viewpoint of efficiency that the optical distance between the light emitting layer and the light reflective electrode is set to an odd number (2n + 1) [n = 0, 1, 2,. However, in reality, as the value of n increases, there arises a new problem that the angle dependency of luminance and spectrum increases. That is, in an organic light emitting device having only one light emitting layer, the film thickness is often designed with an optical length corresponding to n = 0 in many cases, and therefore, variations in light emission luminance and light emission color with respect to film thickness change are not necessarily large. However, in an organic light emitting device having a plurality of light emitting layers as described above, each light emitting layer is necessarily located at a position (2n + 1) [n = 0, 1, 2,. Therefore, as the number of layers increases, a specific wavelength is more remarkably emphasized, and there is a problem that an emission spectrum greatly different from the spectrum originally possessed by the light emitting layer is given and at the same time the angle dependency becomes large. Therefore, an organic light emitting device including a plurality of light emitting layers as described above can surely realize high current efficiency and quantum efficiency that cannot be realized by a conventional organic light emitting device. The emission spectrum and viewing angle dependency do not necessarily have preferable characteristics.

  On the other hand, the organic light emitting device disclosed in Patent Document 1 has a plurality of light emitting layers connected in series as shown in FIG. 10, for example, so that the current value supplied to each light emitting layer is always the same. In addition, it is practically impossible to individually control the emission color of each light emitting layer during driving. When manufacturing an organic light emitting device, it is possible to obtain an organic light emitting device in which each light emitting layer emits light in various light emission colors by selecting and designing each light emitting layer so as to exhibit a predetermined light emitting color. However, once the emission color is determined, it cannot be changed. In addition, for example, when a plurality of light emitting layers exhibiting RGB emission colors are stacked, white light emission can be obtained by adding the light emission colors, but the light emission characteristic behavior with respect to the luminance of the light emitting layer exhibiting each light emission color If they are different, there arises a problem that the emission color at each luminance changes. Further, when the life of each of the plurality of light emitting layers is different, the emission color from the previously deteriorated light emitting layer decreases with driving, which causes a problem of color shift. For example, when an organic light emitting element is used as a light emission source of a display, the color balance of the displayed emission color is out of order, and when used as a light source of illumination, deterioration is visually recognized as a color shift, which is not preferable. .

  Patent Documents 4 and 5 propose a stacked organic light emitting device in which a plurality of light emitting layers having electrodes are stacked. This organic light-emitting element is formed by laminating a plurality of light-emitting layers having independent or partly shared electrodes through an insulating layer as necessary, and is said to be usable for display applications. . However, even in the organic light emitting device having this structure, the distance between the light emitting layers is small even when an insulating layer is inserted, and the above-described problem of optical interference cannot be avoided. In fact, on the premise that there is optical interference, Patent Document 5 proposes an element design policy in which the position of each light emitting layer is set based on the light emission wavelength to emit light with high color purity. This proposal uses interference design, and the main point is that, as in the case of Patent Document 2, the distance between the light emitting layer and the light reflecting layer is set to a film thickness that emphasizes light of a predetermined wavelength. Therefore, the problem of the angle dependence of the emission wavelength still exists. As described above, the organic light emitting devices having the structures of Patent Documents 4 and 5 can change the light emission color during driving, but other problems, in particular, the light emission color when the number of stacked light emitting layers is increased. The problem with respect to the angle dependence is not solved.

  Although the laminated structure of organic light emitting elements such as organic EL elements has been described above, this problem also applies to light emitting elements having a light emitting portion laminated structure, such as semiconductor laser elements and inorganic light emitting elements such as inorganic EL elements. It was.

Japanese Patent Laid-Open No. 11-329748 JP 2000-323277 A JP 2003-272860 A Japanese Patent No. 3496681 JP 2001-511296 A

  The present invention has been made in view of the above circumstances, and improves the luminous efficiency, reduces the angle dependence of the emission spectrum, and realizes high-quality light emission that emits light of a desired color tone regardless of the angle. An object of the present invention is to provide a light-emitting element capable of adjusting the color tone.

Therefore, the present invention provides a first light emitting portion formed by providing a first electrode, a light emitting layer, and a second electrode in this order on the surface of the substrate, and a third electrode, a light emitting layer, and a fourth on the surface of the substrate. A light emitting element formed by laminating a second light emitting part formed by providing the electrodes in this order, and the substrate or the substrate between the electrodes or substrates in contact with the first and second light emitting parts It is characterized by being filled with a filler having a refractive index substantially equal to that of the electrode.
With this configuration, the attenuation of the light amount caused by the difference in refractive index at these interfaces is reduced, the light generated inside the element is efficiently extracted outside, the light emission efficiency is improved, and the interference of light occurring inside is suppressed. Thus, the angle dependency of the emission spectrum is reduced.

That is, of the first to fourth electrodes, at least one of the outer electrodes and the inner electrode are both translucent, and the substrate is made of a translucent material. The first light emitting unit and the second light emitting unit are laminated so that the respective substrates face each other with a predetermined distance, and a spacer for defining the predetermined distance is disposed between these substrates, and is substantially the same as the substrate. A filler having an equal refractive index is filled, and a difference in refractive index between the spacer and the filler is ± 0.1 or less. Further, the spacer functions as a pixel restricting portion having an opening that defines a light emitting region, and controls the thickness of the filler by the height of the pixel restricting portion. Formed using.

Of the first to fourth electrodes, at least one of the electrodes located on the outside, the substrate on the side in contact with the electrode, and the electrode located on the inside are both translucent, and The second electrode of the first light emitting unit and the fourth electrode of the second light emitting unit are stacked so as to face each other with a predetermined distance, and a spacer for defining the predetermined distance is disposed between these electrodes. In addition, a filler having a refractive index substantially equal to those of the electrodes is filled, and a difference in refractive index between the spacer and the filler is ± 0.1 or less. Further, the spacer functions as a pixel restricting portion having an opening that defines a light emitting region, and controls the thickness of the filler by the height of the pixel restricting portion. Formed using.

Of the first to fourth electrodes, at least one of the electrodes located on the outside, the substrate on the side in contact with the electrode, and the electrode located on the inside are both translucent, and The substrate of the first light emitting unit and the fourth electrode of the second light emitting unit are stacked so as to face each other with a predetermined distance, and the predetermined distance is defined between the facing substrate and the fourth electrode. A spacer is disposed and a filler having a refractive index substantially equal to or between those of these substrates or electrodes is filled, and the difference in refractive index between the spacer and the filler is ± 0.1 or less. It is characterized by being. Further, the spacer functions as a pixel restricting portion having an opening that defines a light emitting region, and controls the thickness of the filler by the height of the pixel restricting portion. Formed using.

When the refractive index of the filler is a and the refractive index of an electrode or substrate having a refractive index substantially equal to that of the filler is b, b−0.5 ≦ a ≦ b + 0.5. It is a feature.
Here, for the allowable range of the difference between the refractive index of the filler and the substrate, from the experimental results, ± 0.5, preferably within ± 0.3, more preferably within ± 0.1 so as to satisfy the above formula, Is desirable.

  According to the above configuration, since the light emitting portions are joined by the filler having a refractive index substantially equal to that of the adjacent substrate or electrode, the light from the light emitting layer of each light emitting portion is attenuated by refraction inside the element. In addition, the angle dependence of the emission spectrum is small, and high-quality light emission that exhibits light emission of a desired color tone regardless of the angle can be realized. In addition, by providing a moisture-proof film layer having a refractive index substantially equal to that of the adjacent second or fourth electrode on at least one surface of the second or fourth electrode, the light can be transmitted to the outside while having moisture resistance. Can be taken out efficiently. Moreover, the organic light emitting element which can adjust color tone can be obtained by joining the light emission part of a different color tone.

Hereinafter, the best mode for carrying out the present invention will be described.
(Embodiment 1)
As shown in FIG. 1, the light-emitting element according to the first embodiment of the present invention includes a first electrode 1, a light-emitting layer 3, and a second electrode 2 formed in this order on a translucent substrate 100. The first light emitting unit 4 and the second light emitting unit 8 in which the third electrode 5, the second light emitting layer 7, and the fourth electrode 6 are formed in this order on the translucent substrate 200. A structure in which the light-transmitting substrate 100 of the light-emitting portion 4 and the light-transmitting substrate 200 of the second light-emitting portion 8 are stacked with a filler 9 having a refractive index substantially equal to that of both the light-transmitting substrates 100 and 200. It is the organic light emitting element (organic EL light emitting element) formed in this. Of the four electrodes described above, at least one of the electrodes located outside and both the electrodes located inside are translucent.

  The first and second light-emitting layers 3 and 7 constituting the first and second light-emitting portions 4 and 8 can be of any known structure and composition. It can be formed as a light emitting layer that emits light from a material, a doped light emitting layer in which a dopant is introduced into a so-called host material, a light emitting layer having a structure in which two or more light emitting layers having different compositions are stacked or juxtaposed. Here, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a carrier block layer, and the like are laminated between the light emitting layers 3 and 7 and the electrodes 1, 2, 5, and 6 as necessary. However, these layers are not shown in FIG. 1 (the same applies to each of the drawings described later).

Of the first to fourth electrodes 1, 2, 5, 6, the material of the translucent electrode is not particularly limited as long as it does not impair the function of the organic light emitting device, but ITO (indium tin oxide) ), IZO (indium zinc oxide), AZO (aluminum zinc oxide), GZO (gallium zinc oxide), ATO (aluminum tin oxide), SnO _{2, and the} like, Ag, Au, Al A thin metal film, a conductive organic material, or a combination thereof can be suitably used. The translucent electrode preferably has a high transmittance. In addition, when the interface between adjacent layers and / or the reflectivity of the electrode itself is low, the effects of the present invention can be obtained more effectively. The reflectance at the interface with the adjacent layer is, for example, by forming a so-called antireflection film between the translucent electrode and the layer (including the air layer) adjacent to the translucent electrode. This can be reduced. Or you may provide the layer of the refractive index located between both refractive indexes simply.

  The material of the light-reflective electrode is not particularly limited as long as it has sufficient light reflectance without impairing the function of the organic light-emitting element, and Al, Ag, Au, Ni, Cr or other metal electrodes, or a combination of any of the above-described translucent conductive film and any reflective layer such as these metal electrodes or dielectric multilayer film, or a conductive organic material can be preferably used.

  As a translucent substrate, a glass plate or film and the like, such as a resin plate, a plastic sheet, a composite of glass and plastic, a translucent ceramic plate, a cured resin body, and a sheet / film made of an organic-inorganic hybrid material For example, a light-transmitting base material can be used.

  The filler 9 provided between the translucent substrate 100 of the first light emitting unit 4 and the translucent substrate 200 of the second light emitting unit 8 is substantially the same as the translucent substrate 100 and the translucent substrate 200. It is made of a material having a refractive index, and various materials can be used, from solid materials such as sheets, films, gels, seals and plates to liquids such as water and refractive index matching oil. If it is substantially the same as the refractive index of a board | substrate, it will not be limited to this. Here, “substantially the same” includes the same case.

  According to the above configuration, since the light emitting portions are joined by the filler 9 having a refractive index substantially equal to that of the adjacent translucent substrates 100 and 200, the light emitting layers 3 and 7 of the light emitting portions 4 and 8 are connected. Can be prevented from being refracted at the interface with the filler, so that attenuation due to refraction can be prevented, and the angle dependence of the emission spectrum is small, and light emission of a desired color tone is exhibited regardless of the angle. High-quality light emission can be realized. Further, by providing a moisture-proof film layer having a refractive index substantially equal to that of the fourth electrode on the outer side of the fourth electrode, which is the outermost layer, light can be efficiently extracted outside while having moisture-proof properties. .

In the case of the present embodiment, since the light emitting layer is separated by the thickness of the translucent substrates 100 and 200 and the first and third electrodes 1 and 5, there is a sufficient interference prevention effect. The distance between the translucent substrate 100 and the translucent substrate 200 is preferably narrow, but there is also a problem of the surface roughness of the substrate, and strictly speaking, a gap without the filler 9 is formed at present. . In this case, both come into contact with each other through the air layer, so refraction at the interface with the air layer becomes a problem. Therefore, it is desirable that the refractive index matching oil is applied and brought into pressure contact so as not to form a gap so as to be in close contact. Alternatively, a gel or the like may be applied to at least one of the light-transmitting substrates 100 and 200 so as to be pressed and adhered.
When it is necessary to fill in such a small gap, it is desirable to use a refractive index matching liquid such as a refractive index matching oil. In the case of a liquid, the composition is easy to adjust and the handling is easy.
Furthermore, an adhesive resin or the like is also effective as a filler. By using a material having both adhesiveness and characteristics for adjusting the refractive index, a light emitting element having desired optical characteristics can be obtained. It becomes.

(Embodiment 2)
Next, a second embodiment of the present invention will be described. As shown in FIG. 2 as an example, the light-emitting element according to the second embodiment of the present invention has a layered structure that is substantially the same as the light-emitting element according to the first embodiment shown in FIG. The electrode 2 and the fourth electrode 6 of the second light emitting portion 8 are stacked so as to face each other. Of the four electrodes described above, at least one of the electrodes located outside and both the electrodes located inside are translucent.

  According to the above configuration, since the light emitting portions are joined by the filler 9 having a refractive index substantially equal to that of the adjacent second electrode 2 and fourth electrode 6, the light emitting layers of the light emitting portions 4 and 8 are provided. Since light from 3 and 7 can be prevented from being refracted at the interface with the filler, attenuation due to refraction can be prevented, and the angle dependence of the emission spectrum is small, and a desired color tone can be obtained regardless of the angle. It is possible to realize high-quality light emission that exhibits the above light emission. Further, in this configuration, since the translucent substrates 100 and 200 are the outermost layers, contamination such as entry of moisture from the outside can be avoided without providing special sealing or a moisture-proof film. In addition, the mechanical strength is large, and the handling workability is good.

  In this configuration, the second electrode 2 of the first light emitting unit 4 and the fourth electrode 6 of the second light emitting unit 8 are arranged so as to face each other, and both are fixed via the filler 9. In order to adjust the distance between the light emitting layers, it is desirable to adjust the thickness of the filler 9, and to adjust the thickness of the filler layer, a spacer having a desired height is disposed. It is desirable to do. It is preferable from the viewpoint of reliability that the spacer basically exists in a portion that does not overlap with the light emitting surface, and the refractive index of the spacer is the same as that of the filler or at least ± 0 in both cases of overlapping and not overlapping. It is desirable to select materials so that the refractive index difference is within .3, more preferably within ± 0.1.

(Embodiment 3)
Next, a third embodiment of the present invention will be described. The light emitting element of Embodiment 3 of the present invention has almost the same laminated structure as that of FIG. 1 described in Embodiment 1 as shown in FIG. 3, but of the above four electrodes, At least one of the outer electrodes and the inner electrode are both translucent, and the translucent substrate 100 of the first light emitting unit 4 and the fourth electrode of the second light emitting unit 8. 6 are laminated so as to oppose each other, and the refractive index between the translucent substrate and the electrode is approximately equal to the refractive index of the translucent substrate or the electrode, or the refractive index between the translucent substrate and the electrode. The filler 9 is filled and formed.
According to the present embodiment, since the light emitting portions are joined by such a filler 9, it is possible to reduce the refractive index step, and light from the light emitting layers 3 and 7 of the light emitting portions 4 and 8 is transmitted. Refraction can be relatively prevented from being refracted at the interface with the filler, attenuation due to refraction can be prevented, and the angle dependence of the emission spectrum is small, and light emission of a desired color tone can be performed regardless of the angle. The high-quality light emission shown can be realized.

(Embodiment 4)
Next, a fourth embodiment of the present invention will be described. The light emitting element of the fourth embodiment of the present invention, as shown in FIG. 4 as an example, has almost the same laminated structure as that of FIG. 3 described in the third embodiment, but the surface of the fourth electrode 6. In addition, a moisture-proof film layer 10 having a refractive index substantially equal to that of the fourth electrode is formed. When such a moisture-proof film layer 10 is formed, light can be efficiently extracted outside while having moisture-proof properties.

The moisture-proof film layer 10 which passes through such a light, but are not particularly limited as long as it is not contrary to the spirit of the present invention, for example _SiO 2, SiO, SiN, LiF, the deposition of MgF ₂ or the like, sputtering, CVD Translucent materials that can be formed by any means such as spin coating, dip coating, coating, ink jet, gravure, screen, etc., such as inorganic resin and organic resin It can be formed of a material that can be used by sticking or arranging a light-sensitive film or an organic material or an inorganic material.

  Here, the refractive index of the translucent substrate 100 or the second electrode 2 between the moisture-proof film layer 10 and the translucent substrate 100 of the first light emitting unit 4 or between the second electrode 2 and It is formed by being filled with a filler 9 having a refractive index substantially equal or between the light-transmitting substrate 100 and the second electrode 2. Further, in the present embodiment, it is preferable to optically optimize in consideration of the refractive index and thickness of the moisture-proof film.

(Embodiment 5)
Next, a fifth embodiment of the present invention will be described. The light emitting element according to the fifth embodiment of the present invention has the same structure as that of FIG. 4 described in the fourth embodiment, but in this embodiment, the surface of the fourth electrode 6 has this structure. The moistureproof film layer 10 has a refractive index different from that of the fourth electrode 6 and a thickness of 40 to 140 nm. The thickness of the moisture-proof film layer mentioned here is such that the light emitted from the light-emitting layer does not cause interference. Therefore, when such a moisture-proof film layer 10 is formed, the moisture-proof film layer 10 has moisture-proof properties and transmits light to the outside. It can be taken out efficiently.

(Embodiment 6)
Next, a sixth embodiment of the present invention will be described. The light-emitting element according to the sixth embodiment of the present invention has the same structure as that of FIG. 3 described in the third embodiment. However, in this embodiment, the light-transmitting element facing the fourth electrode 6 is used. The surface of the substrate 100 is roughened. Examples of the roughening method include a method of physically roughing the surface, such as sand blasting and etching, and a method of providing a light-transmitting layer having light scattering, light diffusing, and diffractive properties. As long as it is possible, the method is not limited to these methods.

(Embodiment 7)
Next, a seventh embodiment of the present invention will be described. The light-emitting element of Embodiment 7 of the present invention has the same structure as the structure shown in FIG. 2 described in Embodiment 2 above, but the distance between the second electrode and the fourth electrode facing each other. However, the light emitted from the light emitting layer is formed at a large interval so as not to cause interference. Here, the thickness at which light does not cause interference is not particularly limited as long as it is generally on the order of several times the emission wavelength, for example, a thickness of about 1 μm or more, preferably about 5 to 10 μm. If it is. In consideration of the attenuation of light, it is desirable that the thickness of the filling layer is small. In order not to cause interference, it is desirable to make the filling layer as thin as several times the emission wavelength.

  In each of the above-described embodiments, the light emitting unit is an example of a light emitting element composed of the first light emitting unit 4 and the second light emitting unit 8. Also in the case of a light emitting element having a portion, at least two of the light emitting portions adjacent to each other satisfy the configurations of the first light emitting portion 4 and the second light emitting portion 8 as described above. I just need it.

Further, modified examples of the first to fourth embodiments will be described with reference to FIGS. 5, 6, 7, and 8. In each of the embodiments, the light emitting portions 4 and 8 are formed by a plurality of light emitting layers 3 and 7 stacked via the layer 11 forming the equipotential surface or the charge generation layer 11, so-called stacked type, tandem type, multiphoton. It is formed as a light emitting part of a mold. Both the first and second light-emitting portions 4 and 8 may be formed of the plurality of light-emitting layers 3 and 7, and either one of the first and second light-emitting portions 4 and 8 may be formed in this manner. A plurality of such light emitting layers 3 and 7 may be formed. Examples of the material of the equipotential surface forming layer 11 or the charge generation layer 11 include metal thin films such as Ag, Au, and Al, metal oxides such as vanadium oxide, molybdenum oxide, rhenium oxide, and tungsten oxide, ITO, IZO, AZO, Translucent conductive film such as GZO, ATO, SnO ₂ , so-called n-type semiconductor and p-type semiconductor laminate, metal thin film or translucent conductive film and n-type semiconductor and / or p-type semiconductor laminate, n Examples thereof include a mixture of a p-type semiconductor and a p-type semiconductor, a n-type semiconductor and / or a mixture of a p-type semiconductor and a metal. The n-type semiconductor or p-type semiconductor may be an inorganic material or an organic material, or a mixture of an organic material and a metal, an organic material and a metal oxide, an organic material and an organic acceptor / It may be obtained by a combination of a donor material, an inorganic acceptor / donor material, etc., and can be selected and used as needed without any particular limitation. Further, the light emitting layers 3 and 7 stacked in the light emitting units 4 and 8 can be arranged in different colors, and may further include light emitting layers of different colors in one light emitting unit.

  In the organic light emitting device of each embodiment formed as described above, the light emitted from the light emitting layer 3 of the first light emitting unit 4 or the light emitting layer 7 of the second light emitting unit 8 Of the two electrodes, the light passes through the translucent electrode located on the inner side and is taken out through at least one translucent electrode located on the outer side. Part of the light emitted from the light emitting layer 3 of the first light emitting unit 4 and the light emitting layer 7 of the second light emitting unit 8 is reflected by the remaining one outer electrode and taken out through the translucent electrode. Further, in the organic light emitting device of FIG. 1, at least one translucent electrode located outside is protected by a translucent protective member, so that mechanical damage from the outside, deterioration from moisture, etc. Can be prevented.

  Since these organic light emitting devices of the present invention are provided with the filler 9 having a refractive index substantially equal to the electrode or substrate provided on the adjacent side of the two light emitting portions, the interface between the two light emitting portions. Thus, the light generated in the light emitting portion can be efficiently extracted outside without loss due to refraction. In addition, when the distance between the second electrode and the fourth electrode facing each other is set such that the light emitted from the light emitting layer does not cause interference, the angle dependency of the emission spectrum can be reduced. is there. The angle dependence of the emission spectrum is caused by the interference between the light generated from the light emission position and the light reflected by the reflection surface. By setting the distance from the surface to a distance that does not cause optical interference, the angle dependency can be reduced. In the case of the first, third, and fourth embodiments shown in FIGS. 1, 3, and 4, the optical interference suppressing effect is substantially caused by the optically transparent substrate 100 of the first light emitting unit 4. In the case of the second embodiment shown in FIG. 2, the thickness of the filler 9 corresponds to an optical length that does not substantially cause optical interference. It is expressed by the layer of the thickness to do.

  The organic light emitting device according to the present invention has a structure in which the first and second light emitting portions 4 and 8 are formed between the different electrodes 1, 2, 5 and 6. . Then, like the organic light emitting devices of the first to fourth embodiments shown in FIGS. 1, 2, 3, and 4, a light-transmitting filling is provided between the first light emitting unit 4 and the second light emitting unit 8. Since the material 9 and the moisture-proof film layer 10 are interposed, the light emitting portions 4 and 8 are electrically independent, and the light emitting portions 4 and 8 can be individually driven to emit light. By having such an electrical structure, the first light emitting unit 4 and the second light emitting unit 8 can be driven by applying different electric fields as necessary, and the light emission characteristics can be changed as necessary. Is possible.

  For example, in the case of a display in which a white organic light-emitting element is formed with the organic light-emitting element of the present invention and used in combination with a color filter, a light emitting unit that emits light of a color tone that is quickly deteriorated with respect to a white color shift that is a basic emission color It is possible to correct even during use by providing an element structure provided with other than the white light emitting portion. Alternatively, when light emitting units having the same emission color are stacked, intensity correction can be performed by causing a new light emitting unit to emit light as the light emission intensity decreases. On the other hand, in lighting applications, as mentioned in the case of the above-mentioned display, it can be used for correcting color misregistration of emission color and decrease in emission intensity. Alternatively, for example, by preparing a white light emitting unit and a red light emitting unit, the light source can be used for obtaining a light source capable of toning light in a range from white light emission to red light emission. In addition, if necessary, it is possible to prepare a color tone to be adjusted and to adjust the color with the output ratio of the two light emitting units, or to provide three or more light emitting units and output each light emitting unit. By adjusting, color matching along the black body locus is also possible. The light emission color and the number of light emission parts of each light emission part can be arbitrarily set according to the above uses, purposes, and necessity.

  The driving method of each of the first and second light emitting units 4 and 8 can be performed by combining existing arbitrary methods, and the relationship between the light emitting outputs of the light emitting units 4 and 8 can be set as appropriate. It can be done. The outputs of the light emitting units 4 and 8 may be controlled by any of voltage, current, and power, or may be adjusted by energizing with an arbitrary current / voltage waveform such as a pulse. The outputs of the light emitting units 4 and 8 can be controlled using various methods, and the light emitting units 4 and 8 may be controlled independently, or, for example, the emission color moves on a black body locus. As described above, the outputs of the light emitting units 4 and 8 may be controlled in accordance with a predetermined relationship.

Next, the manufacturing method of the organic light emitting element of this invention is demonstrated.
The organic light-emitting device of the present invention can be manufactured by any method. FIGS. 9A to 9C briefly show the manufacturing process of the organic light-emitting device. For example, as shown in FIG. 9A, a light-transmitting conductive film formed on a light-transmitting substrate 100 is used as a light-transmitting first electrode 1, on which a first light-emitting layer 3 and then A light-transmitting second electrode 2 is laminated to form the first light-emitting portion 4, while the light-transmitting light formed on the light-transmitting substrate 200 as shown in FIG. 9B. A light-transmitting third electrode 5 is used as a light-transmitting conductive film, and a second light-emitting portion 8 is formed thereon by stacking a second light-emitting layer 7 and then a light-transmitting fourth electrode 6. After that, as shown in FIG. 9C, the translucent substrates 100 and 200 are installed adjacent to each other, and filled with a filler 9 having a refractive index substantially equal to that of the translucent substrate therebetween. An organic light emitting device like the first embodiment shown in FIG. 1 can be manufactured. Further, the light-transmitting substrate 100 of the first light-emitting portion 4 and the fourth electrode 6 of the second light-emitting portion 8 are stacked so as to face each other, and these light-transmitting properties are interposed between the facing light-transmitting substrate and the electrodes. The organic light emitting device as in Embodiment 3 shown in FIG. 3 is filled by filling with a filler 9 having a refractive index substantially equal to the refractive index of the substrate or the electrode or between the transparent substrate and the electrode. Can be manufactured.

  In the case of forming a light emitting element having a structure in which a light emitting region is divided for each pixel as in a display device, a pixel restricting portion having an opening for defining a light emitting region is sandwiched between the light emitting portions as a spacer, and the pixel It is also possible to control the thickness of the filler 9 by the height of the restricting portion. In this case, a light shielding film such as a chrome thin film or a tungsten thin film constituting the pixel restricting portion is formed, and an opening pattern is formed using photolithography, thereby controlling the pixel area and the thickness of the filler with high accuracy. Can be done.

  In addition, when used as a display device in this way, the electrodes must be individual electrodes and formed by matrix wiring, etc., and adjustment is necessary because the refractive index differs between the region where the electrodes are present and the region where the electrodes are not present. However, there is a case where such adjustment of the refractive index becomes unnecessary by using the pixel restricting portion.

  In the above-described embodiment, the organic electroluminescence element has been described. However, the present invention is not limited thereto, and the light emitting element having a light emitting portion having a stacked structure, such as an inorganic light emitting element such as a surface emitting semiconductor laser and an inorganic EL element. It is also applicable to.

Next, the present invention will be specifically described with reference to examples.
(Preparation of blue light-emitting element A)
A glass substrate 100 with ITO as the first electrode 1 having a 110 nm thick ITO (sheet resistance 12Ω / □, refractive index 1.9) formed on one side of a 0.7 mm thick glass substrate (refractive index 1.5). Prepared. The glass substrate 100 with ITO was subjected to ultrasonic cleaning with pure water, acetone, and isopropyl alcohol for 10 minutes each, then steam cleaned with isopropyl alcohol vapor for 2 minutes, dried, and further UV ozone cleaned for 10 minutes.

Subsequently, this ITO-attached glass substrate was set in a vacuum deposition apparatus, and 4,4′-bis [N- (naphthyl) -N-phenyl-amino] biphenyl (manufactured by e-Ray) under a reduced pressure of 5 × 10 −5 Pa. “Α-NPD”) and molybdenum oxide (MoO ₃ ) are vapor deposited to a thickness of 10 nm with a film formation rate ratio of 3: 1 and a total film formation rate of 0.13 nm / s, and hole injection is performed on ITO serving as the anode. A layer was formed. Next, “α-NPD” was deposited on the hole injection layer to a thickness of 70 nm at a deposition rate of 0.1 nm / s to form a hole transport layer. Next, on the hole transporting layer, a layer in which a dinaphthyl anthracene derivative (“BH-2” manufactured by Kodak Co., Ltd.) is doped with 4% by mass of a distyrylarylene derivative (BCzVBi) is laminated to a thickness of 50 nm to emit blue light. A layer was provided. Next, on this light-emitting layer, bathocuproin (“BCP” manufactured by Dojindo Laboratories Co., Ltd.) is 10 nm thick, and “BCP” and Cs are co-deposited to a thickness of 10 nm at a molar ratio of 1: 1 to form an electron injection layer. Provided. On top of this, “α-NPD” and molybdenum oxide (MoO ₃ ) are evaporated to a thickness of 10 nm with a film formation rate ratio of 3: 1 and a total film formation rate of 0.13 nm / s to form a charge generation layer. did. Thereafter, a hole transport layer having a thickness of 70 nm, a light-emitting layer having a thickness of 50 nm, an electron transport layer having a thickness of 10 nm, and an electron injection layer having a thickness of 10 nm were stacked thereon. Further thereon, Al is laminated to a thickness of 10 nm at a film formation rate of 0.4 nm / s to form a light-transmitting cathode, thereby sandwiching two layers of blue light emitting layers with a charge generation layer interposed therebetween. A blue light-emitting element A provided in step 1 was obtained.

(Preparation of yellow light-emitting element B)
Using a glass substrate with ITO in which a 110 nm thick ITO (sheet resistance 12Ω / □, refractive index 1.9) is formed on a 0.7 mm thick glass substrate (refractive index 1.5), this ITO-attached glass plate is vacuumed. In the same manner as described above, a layer in which “α-NPD” and molybdenum oxide were co-deposited at a ratio of 3: 1 was 10 nm thick, and “α-NPD” was 50 nm as the hole transport layer. Thickness, light emitting layer doped with 4% by mass of rubrene in “BH-2” 50 nm thick, “BCP” 5 nm thick as electron transport layer, “BCP” and Cs molar ratio 1: 1 as electron injection layer Co-deposited layers were each formed in this order in a thickness of 15 nm, and on this, “α-NPD” and molybdenum oxide (MoO ₃ ) were formed at a deposition rate ratio of 3: 1, and the total deposition rate was 0.13 nm / 1 as s The charge generation layer was formed by evaporation to a thickness of 0 nm. Thereafter, a hole transport layer having a thickness of 50 nm, a light emitting layer having a thickness of 50 nm, an electron transport layer having a thickness of 5 nm, and an electron injection layer having a thickness of 15 nm were laminated thereon in the same manner as described above. Finally, aluminum was stacked at a thickness of 80 nm at a deposition rate of 0.4 nm / s to form a light-reflective anode, thereby providing two light-emitting layers that emit yellow light with the charge generation layer interposed therebetween. A yellow light emitting device B was obtained.

(Preparation of yellow light-emitting element C)
A glass substrate having a thickness of 80 nm formed on a 0.7 mm-thick glass substrate (refractive index 1.5) with aluminum being deposited at a deposition rate of 0.4 nm / s, and then a 110 nm-thick ITO (sheet resistance 12Ω / □) is formed. In the same manner as described above, a layer in which “α-NPD” and molybdenum oxide are co-evaporated at a ratio of 3: 1 as a hole injection layer is 10 nm thick, and “α-NPD” is 50 nm thick as a hole transport layer. As the electron transporting layer, “BH-2” doped with 4% by mass of rubrene is 50 nm thick, “BCP” is 5 nm thick, and the electron injection layer is a co-evaporated layer having a molar ratio of “BCP” to Cs of 1: 1. 15 nm thick, each formed in this order, and on top of this, “α-NPD” and molybdenum oxide (MoO 3) at a film formation rate ratio of 3: 1 and a total film formation rate of 0.13 nm / s to a thickness of 10 nm Steam And, to form a charge generation layer. Thereafter, a hole transport layer having a thickness of 50 nm, a light emitting layer having a thickness of 50 nm, an electron transport layer having a thickness of 5 nm, and an electron injection layer having a thickness of 15 nm were laminated thereon in the same manner as described above. Finally, a yellow light-emitting element C in which two layers of a light-emitting layer emitting yellow light are provided with a charge generation layer interposed therebetween by laminating ITO with a thickness of 100 nm using an RF sputtering apparatus to form a translucent cathode. Obtained.

Example 1
The blue light emitting element A and the yellow light emitting element B are provided so that the translucent glass substrate faces each other, and a gap between them is used as a filler by using matching oil (uniopto refractive index matching liquid, refractive index 1.5). Thus, an organic light-emitting element having a structure in which the blue light-emitting element A and the yellow light-emitting element B were laminated was obtained (see the structure of the first embodiment shown in FIG. 1).

(Example 2)
The blue light-emitting element A and the yellow light-emitting element C are provided so that the cathode surfaces face each other, 10 micron silica particles are used as spacers, and a matching oil (a refractive index matching liquid made by UNIOPT, refractive index 1. 65) to obtain an organic light emitting device having a structure in which the blue light emitting device A and the yellow light emitting device C are laminated (see the structure of the second embodiment shown in FIG. 2).

(Example 3)
On the cathode surface of the blue light emitting element A, an alumina film (refractive index 1.6) 100 nm as a moisture-proof film layer is provided by 200 W and RF sputtering, and a yellow light emitting element B is provided thereon, and a matching oil (Uniopt. The organic light-emitting device having a structure in which the blue light-emitting device A and the yellow light-emitting device B are laminated is obtained using the refractive index matching liquid (refractive index: 1.65) (Embodiment 3 shown in FIG. 3). See structure).

Example 4
An alumina film (refractive index of 1.6) 100 nm as a moisture-proof film layer is provided by 200 W on the cathode surface of the blue light-emitting element A by RF sputtering, and a yellow light-emitting element B whose glass substrate surface is roughened by sandblasting is filled thereon. An organic light-emitting device having a structure in which a blue light-emitting device A and a yellow light-emitting device B are stacked by providing a matching oil (Uniopt refractive index matching liquid, refractive index 1.6) as a material was obtained (shown in FIG. 3). (See the structure of the third embodiment).

(Comparative Example 1)
In Example 1, the organic light emitting element was obtained like Example 1 except having used water (refractive index 1.33) as the filler 9. In FIG.

(Comparative Example 2)
In Example 2, an organic light emitting device was obtained in the same manner as in Example 2 except that silicon oil (refractive index: 1.35) was used as the filler 9.

(Comparative Example 3)
In Example 3, an organic light emitting device was obtained in the same manner as in Example 3 except that a fluorine coating agent (INT-340 (refractive index: 1.36) manufactured by NI Material Co., Ltd.) was used as the protective film layer and the filler 9. It was.

As described above, the organic light-emitting devices obtained in Examples 1 to 4 and Comparative Examples 1 to 3 are connected to a power source (KEITHLEY model 2400) and driven at a constant current (10 mA / cm ² ), and the front luminance is changed to color. Measurement was performed using a luminance meter ("SR-3" manufactured by Topcon Corporation: measurement distance 30 cm). At the same time, the chromaticity of light emission obtained from the front of the organic light emitting device and from the direction of 45 degrees with respect to the front was measured.

The results of measuring the front luminance, front chromaticity, and 45 ° chromaticity of the organic light emitting devices of Examples 1 to 4 and Comparative Examples 1 to 3 are shown in the following table. From this result, according to Examples 1 to 4 of the present invention, by selecting the refractive index of the filler 9 so as to be approximately equal to the refractive index of the adjacent substrate or electrode, a filler having a lower refractive index can be obtained. As compared with the light emitting devices of Comparative Examples 1 to 3 used, it was found that excellent characteristics can be obtained in which the front luminance is large and the front chromaticity and the 45 ° chromaticity are substantially equal.

  As described above, according to the present invention, in a light-emitting element in which a plurality of light-emitting portions are stacked, the light emission efficiency can be improved and the angle dependency can be suppressed. It can be applied to various fields such as devices.

FIG. 3 shows a light-emitting element according to Embodiment 1 of the present invention. The figure which shows the light emitting element of Embodiment 2 of this invention. FIG. 6 shows a light-emitting element according to Embodiment 3 of the present invention. FIG. 6 shows a light-emitting element according to Embodiment 4 of the present invention. The figure which shows the modification of the light emitting element of Embodiment 1 of this invention. The figure which shows the modification of the light emitting element of Embodiment 2 of this invention. The figure which shows the modification of the light emitting element of Embodiment 3 of this invention. The figure which shows the modification of the light emitting element of Embodiment 4 of this invention. The figure which shows the manufacturing process of the light emitting element of embodiment of this invention. The figure which shows the light emitting element of a prior art example

Explanation of symbols

100, 200 Translucent substrate 1 First electrode 2 Second electrode 3 Light-emitting layer 4 First light-emitting portion 5 Third electrode 6 Fourth electrode 7 Light-emitting layer 8 Second light-emitting portion 9 Filler 10 Moisture-proof Film layer 11 Layer for forming equipotential surface or charge generation layer 20 Electrode 21 for anode 21 Electrode for cathode 22 Light emitting layer 23 Layer for forming equipotential surface or charge generation layer 24 Translucent substrate

Claims (8)

A first light emitting portion formed by providing a first electrode, a light emitting layer, and a second electrode in this order on the surface of the substrate; and a third electrode, a light emitting layer, and a fourth electrode on the surface of the substrate in this order. A light emitting element formed by laminating a second light emitting part formed and comprising:
Of the first to fourth electrodes, at least one of the outer electrodes and the inner electrode are both translucent, and the substrate is made of a translucent material. The light emitting unit and the second light emitting unit are laminated so that the respective substrates face each other with a predetermined distance, and a spacer for defining the predetermined distance is disposed between the substrates, and the refractive index is approximately equal to the substrate. filler is filled with the rate state, and are the refractive index difference is ± 0.1 following the filler and the spacers,
The spacer functions as a pixel restricting portion having an opening that defines a light emission region, and controls the thickness of the filler by the height of the pixel restricting portion, and the pattern of the opening uses photolithography. A light emitting element formed by A first light emitting portion formed by providing a first electrode, a light emitting layer, and a second electrode in this order on the surface of the substrate; and a third electrode, a light emitting layer, and a fourth electrode on the surface of the substrate in this order. A light emitting element formed by laminating a second light emitting part formed and comprising:
Of the first to fourth electrodes, at least one of the electrodes positioned on the outside, the substrate on the side in contact with the electrode, and the electrode positioned on the inside are both translucent, and the first The second electrode of the light emitting unit and the fourth electrode of the second light emitting unit are stacked so as to face each other with a predetermined distance, and a spacer for defining the predetermined distance is disposed between these electrodes, is filled filler having substantially the same refractive index as the electrodes become in state, and are the refractive index difference is ± 0.1 following the filler and the spacers,
The spacer functions as a pixel restricting portion having an opening that defines a light emission region, and controls the thickness of the filler by the height of the pixel restricting portion, and the pattern of the opening uses photolithography. A light emitting element formed by A first light emitting portion formed by providing a first electrode, a light emitting layer, and a second electrode in this order on the surface of the substrate; and a third electrode, a light emitting layer, and a fourth electrode on the surface of the substrate in this order. A light emitting element formed by laminating a second light emitting part formed and comprising:
Of the first to fourth electrodes, at least one of the electrodes positioned on the outside, the substrate on the side in contact with the electrode, and the electrode positioned on the inside are both translucent, and the first The substrate of the light emitting unit and the fourth electrode of the second light emitting unit are stacked so as to oppose each other with a predetermined distance, and a spacer for defining the predetermined distance is provided between the opposing substrate and the fourth electrode. together are placed, it is filled material filled with a substantially equal or between refractive index and the refractive index of the substrate or the electrodes become in state, and are the refractive index difference is ± 0.1 following the filler and the spacer ,
The spacer functions as a pixel restricting portion having an opening that defines a light emission region, and controls the thickness of the filler by the height of the pixel restricting portion, and the pattern of the opening uses photolithography. A light emitting element formed by The light-emitting device according to claim 1,
A light-emitting element comprising a moisture-proof film layer having a refractive index substantially equal to that of the adjacent second or fourth electrode on at least one surface of the second or fourth electrode. The light emitting device according to claim 4,
The moisture-proof film layer has a thickness of 40 to 140 nm. The light emitting device according to claim 3,
A light-emitting element in which a surface of a substrate facing the fourth electrode is roughened. The light emitting device according to claim 2,
A light-emitting element formed so that light emitted from the light-emitting layer does not interfere with the distance between the second electrode and the fourth electrode facing each other. The light emitting device according to any one of claims 1 to 7,
The light-emitting element in which the filler is b−0.5 ≦ a ≦ b + 0.5, where a is a refractive index of the filler and b is a refractive index of the electrode or substrate in contact with the filler.

Images