JP2009054450A - Organic light emitting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic light-emitting device in which mechanical strength of the complementary color layer formed by vapor deposition is high, which has high interlayer adhesion, and in which light emission of high efficiency can be achieved without receiving process damages of color conversion dye of the complementary color layer. <P>SOLUTION: This is a light-emitting element including a transparent substrate, the complementary color layer to absorb at least one part of light of a light source and to emit light of wavelength distribution different from an absorption wavelength, a protection layer, a gas barrier layer, and an organic EL element. The complementary color layer and the protection layer are discontinuously patterning-formed on the transparent substrate by the vapor deposition. A site is provided in which upper and lower layers of the complementary color layer and the protection layer are directly joined in the pixel. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is an organic electroluminescence (hereinafter referred to as “organic EL”) display capable of high-definition and excellent visibility and capable of multicolor display, a white light-emitting organic light emission used in backlights of color liquid crystal displays and other lighting devices. Regarding devices.

As an example of a light-emitting element applied to a display device, an organic EL element having a thin film laminated structure of an organic compound is known. Organic EL elements are thin-film self-luminous elements and have excellent characteristics such as low drive voltage, high resolution, and high viewing angle. Therefore, various studies have been made for their practical application.
The organic EL element has a structure including at least an organic light emitting layer between an anode and a cathode. The organic light emitting layer is a layer having a function of emitting light by recombination of holes and electrons generated by applying a voltage to the anode and the cathode. The organic EL element has a structure in which a hole injection layer, a hole transport layer, an electron transport layer and / or an electron injection layer are interposed as required. More specifically, for example, the following structures are exemplified.
(1) Organic light emitting layer (2) Hole injection layer / organic light emitting layer (3) Organic light emitting layer / electron transport layer (4) Hole injection layer / organic light emitting layer / electron transport layer (5) Hole injection layer / Hole transport layer / organic light emitting layer / electron transport layer (6) Hole injection layer / hole transport layer / organic light emitting layer / electron transport layer / electron injection layer The structures of (1) to (6) described above are used. In the organic EL device having an anode, an anode is connected to the organic light emitting layer or the hole injection layer, and a cathode is connected to the organic light emitting layer, the electron transport layer, or the electron injection layer.

It is known that an organic EL element emits blue, green, and red light depending on the type of dye added to the organic light emitting layer. In order to realize a full-color display, light emitting elements of three primary colors may be arranged in subpixels as pixels (pixels). However, since the characteristics of the light emitting elements of the respective colors are different from each other, the formation of the subpixel and the driving method thereof are complicated, which causes an increase in cost. Therefore, it has been attempted to obtain three primary colors from white light with a color filter. Therefore, realization of a multicolor or white light emitting element that can be used in a color filter system is desired.
The white light emitting element includes, for example, a method in which two or more light emitting layers including a mixed layer type light emitting layer are provided and two or more kinds of dopants are contained, thereby obtaining two or more kinds of light emission, and a host material of the light emitting layer ( Various methods such as a method of uniformly doping a red light emitting material into a blue green light emitting material), a method of laminating a blue light emitting layer and a green light emitting layer, and adding a red fluorescent compound thereto are studied.
In the above method, in order to obtain white light emission, there are a method of laminating two or more light emitting layers and doping a plurality of different fluorescent dyes, or a method of adding two or more different fluorescent dyes even if the light emitting layer is a single layer. It was necessary. However, in the former case, it is necessary to increase the number of layers, and in the latter case, in order to obtain optimal white light emission, it is necessary to control the red fluorescent dye having low energy at a very low concentration. For this reason, both of them have problems such as a complicated layer structure or difficulty in controllability.

In addition, the white light-emitting element manufactured by these methods has a problem that the color changes due to the magnitude of the current flowing through the element and the deterioration of the organic EL element.
In recent years, as an example of a multi-color or full-color display method for a display configured using an organic EL element, it absorbs near-ultraviolet light, blue light, blue-green light, or white light emitted from the organic EL element, and has a wavelength. A color conversion (CCM) method using a color conversion layer including one or more types of color conversion dyes that emit light in the visible light range by performing distribution conversion has been studied. When the color conversion method is used, since the light emission color of the light source is not limited to white, it is possible to increase the degree of freedom in selecting the light source. For example, green and red light can be obtained by wavelength distribution conversion using an organic EL element that emits blue to blue green light.
The structure of a color conversion type organic light emitting device is shown in FIG. In the configuration of FIG. 8, three types of color filter layers 32 (R, G, B), three types of color conversion layers 33 (R, G, B), and a planarizing layer 34 are formed on the transparent substrate 31. A color conversion filter is formed. Furthermore, an organic EL device including a gas barrier layer 35 and a transparent electrode 41, an organic EL layer 42, and a reflective electrode 43 is formed on the color conversion filter to constitute an organic light emitting device.
The color conversion layer 33 used in the color conversion method generally includes one or more fluorescent dyes (including dyes, pigments, and pigments or particles obtained by separately dispersing dyes in the resin) dispersed in the resin. It has been formed by a wet process in which a dispersion of the fluorescent dye and resin is applied and dried.

However, the color conversion layer 33 formed by such a wet process is generally much thicker than other layers constituting the organic light-emitting device, and generally has a film thickness of 5 μm to several tens of μm. Further, when a plurality of types of color conversion layers 33 are used, there is a possibility that the thicknesses of the respective color conversion layers 33 are different to form steps, and a flattening layer 34 is provided to compensate for these steps. Is required.
Furthermore, it is difficult to completely dry the color conversion layer 33 formed by the wet process, and moisture remaining in the color conversion layer 33 during the manufacturing process and / or driving of the organic light emitting device is caused by the organic EL layer 42. In order to prevent this, it is necessary to provide the gas barrier layer 35 in order to prevent non-luminous defects called dark areas.
Regarding the above problems, it has been studied to form a color filter layer and a color conversion layer by a dry process (see, for example, Patent Documents 1 to 3). According to this method, instead of the thick layer formed by the wet process, a thin layer formed by the dry process can be used as the color conversion layer. Hereinafter, a thin layer formed by a dry process is called a complementary color layer, and a thick layer formed by a wet process is called a color conversion layer to be distinguished. By using a thin complementary color layer, it is possible to prevent the moisture that may remain in the complementary color layer or the like from the effect of the gas barrier layer from being transmitted to the organic EL layer and generating a dark area. . Furthermore, by matching the refractive indexes of the complementary color layer, the gas barrier layer, and the transparent electrode, it is possible to use light emitted from the organic EL element with higher efficiency.
JP 2001-196175 A JP 2002-175879 A JP 2002-184575 A

In the above solution, the complementary color layer has a film thickness in the range of 100 nm to 1 μm by vapor deposition of a color conversion dye made of an organic substance, specifically, a color filter layer (a flattening layer if present). ) Formed over the entire surface. Therefore, an organic vapor-deposited film is present in the laminated structure sandwiched between the gas barrier layer and the color filter layer (a planarizing layer, if present).
In general, an organic vapor deposition film has low mechanical strength and a linear expansion coefficient different from that of a gas barrier layer, a color filter layer, a flattening layer, etc. sandwiching the organic vapor deposition film. Damage occurs. In addition, the deposited film has low adhesion to the underlying color filter layer or planarization layer, and causes mechanical peeling between the complementary color layer and the gas barrier layer, color filter layer, planarization layer, or the like. This causes a decrease in yield and a generation of pixel defects due to driving and a decrease in lifetime due to the manufacture of an organic light-emitting device formed by forming a sequentially laminated structure.
Further, the complementary color layer is formed by high energy particles such as plasma, neutral atoms or ionized atoms, high-speed electrons, or ultraviolet rays generated in a film forming process such as sputtering or CVD when forming a gas barrier layer on the complementary color layer. There is a problem that decomposition of the color conversion dye in the medium and a decrease or disappearance of the color conversion ability associated therewith occur.

In order to solve the above problem, in the present invention, when the complementary color layer and the protective layer are formed by a dry process, the complementary color layer and the protective layer are formed by forming a through portion in one pixel constituting the image to be displayed. A region is provided in which the upper and lower layers sandwiching the layer are directly joined in at least a part of the pixel.
In addition, following the formation of the complementary color layer by a dry process, a protective layer made of a film-resistant material having sputtering resistance and / or plasma resistance is formed by a dry process.
That is, the present invention is an organic light-emitting device including a transparent substrate, a complementary color layer, a protective layer, and an organic EL element, and the complementary color layer has a through portion in a pixel using a dry process. Formed and absorbs at least part of the light emitted from the organic EL element to emit light having a wavelength distribution different from the absorption wavelength, and the protective layer has a pattern having the same shape as the complementary color layer at least in the pixel. It is formed only immediately above the portion where the complementary color layer exists, and the upper and lower layers sandwiching the complementary color layer and the protective layer have a portion that is directly joined at the penetrating portion.
It is preferable to further include one or more color filter layers arranged separately from each other between the transparent substrate and the complementary color layer. It is preferable that a gas barrier layer is further provided between the complementary color layer and the protective layer and the organic EL element.

It is preferable that a first planarization layer is further provided between the color filter layer and the complementary color layer. Moreover, it is preferable that a second planarization layer is further provided between the protective layer and the gas barrier layer.
In these preferred configurations, the upper and lower layers sandwiching the complementary color layer and the protective layer are a color filter layer and a gas barrier layer, a first planarization layer and a gas barrier layer, a color filter layer and a second planarization layer, or a first planarization layer. A combination of the planarization layer and the second planarization layer can be used.
The complementary color layer and the protective layer are preferably formed by a vapor deposition method using patterning with a mask.
The masks used when the complementary color layer and the protective layer are formed by vapor deposition preferably have the same pattern. Further, it is preferable to use a mask used when forming the complementary color layer also when forming the protective layer. The complementary color layer is preferably made of one or more kinds of color conversion dyes. The protective layer preferably contains a film-resistant material having sputter resistance and / or plasma resistance.

By forming the complementary color layer and the protective layer discontinuously in this manner, the stress due to the difference in linear expansion coefficient between the complementary color layer and the protective layer and the gas barrier layer, color filter layer, each planarizing layer, etc. sandwiching them can be reduced. Mitigates and prevents damage to the complementary color layer and the protective layer. Further, by adopting a structure having a portion directly bonded in the pixel between the gas barrier layer, the color filter layer, each flattening layer, or the like, the adhesion between the layers is ensured and the problem of peeling is avoided. As a result, it is possible to manufacture the organic light emitting device with a high yield, and further, it is possible to prevent the occurrence of pixel defects due to driving and the decrease in the lifetime due to this.
Further, by forming a protective layer on the complementary color layer, it is possible to prevent damage to the complementary color layer that occurs in a film forming process such as a sputtering process or a CVD process in a subsequent process.
By configuring the organic light emitting device in this way, light emission including blue is realized by one type of fluorescent dye added in a single light emitting layer, and light including blue emitted from the light emitting layer is converted into a color conversion dye. It is possible to emit red light by absorption and color conversion with a complementary color layer containing. In addition to the red light, there is transmitted light including blue that passes through the complementary color layer but is not absorbed and color-converted by the color conversion dye of the complementary color layer, and transmitted light including blue that passes through the portion without the complementary color layer. The transmitted light containing blue and the red light absorbed and color-converted by the complementary color layer can be combined so as to emit white light to the outside of the organic light emitting device, and white light emission can be realized.

  Further, since the complementary color layer is formed thin, unlike the conventional color conversion layer, a step that causes a failure such as disconnection or short circuit of the transparent electrode and the reflective electrode is alleviated. Therefore, a configuration in which a flattening layer is not provided on the complementary color layer is also possible.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic cross-sectional view for illustrating a configuration example of the present invention. The transparent substrate 11, the color filter layer 12, the first planarizing layer 15, the complementary color layer 13, the protective layer 17, the gas barrier layer 14, the transparent electrode 21, and the organic The EL layer 22 and the reflective electrode 23 are formed in this order. The complementary color layer and the protective layer are formed on the first planarization layer as a discontinuous film having a through portion by a dry process with patterning, and the gas barrier layer and the first planarization layer are directly bonded at the through portion in the pixel. Has a structure. The transparent electrode 21, the organic EL layer 22, and the reflective electrode 23 constitute an organic EL element that serves as a light emission source. The color filter layers 12R, 12G, and 12B represent a red color filter layer, a green color filter layer, and a blue color filter layer, respectively.
The complementary color layer is preferably formed on the first planarization layer, but may be directly provided on the color filter layer if desired. FIG. 2 is a schematic cross-sectional view showing this configuration example. On the transparent substrate 11, three kinds of color filter layers 12 (R, G, B), a complementary color layer 13, a protective layer 17, a gas barrier layer 14, and an organic material are shown. An EL element is formed. Similar to the example of FIG. 1, the organic EL element includes a transparent electrode 21, an organic EL layer 22, and a reflective electrode 23. In addition, the complementary color layer 13 and the protective layer 17 are formed as discontinuous films on each color filter layer by a dry process involving patterning, and the color filter layer and the gas barrier layer are directly joined at the penetrating portion in the pixel. Have.

Furthermore, it is possible to adopt a configuration in which the color filter layer is not provided. In this case, the complementary color layer is disposed directly on the transparent substrate. The two layers that are directly bonded at the penetrating portion in the pixel are a combination of a layer disposed immediately above the complementary color layer and the protective layer and a transparent substrate, and the layer disposed immediately above the complementary color layer and the protective layer is a gas barrier. In the case of a layer, it is a combination of a transparent substrate and a gas barrier layer.
By forming such a layer structure, light of blue color is emitted by one kind of fluorescent dye added in a single light emitting layer, and this light is absorbed by a complementary color layer containing a color conversion dye and color converted. To emit red light. In addition to the red light, there is transmitted light including blue that passes through the complementary color layer but is not absorbed or converted by the color conversion pigment of the complementary color layer, and transmitted light including blue that passes through the portion without the complementary color layer. It is possible to design such that the transmitted light containing blue and red light absorbed and color-converted by the complementary color layer are combined to emit white light to the outside of the element, and an organic light emitting device that emits white light can be realized. .
The complementary color layer is formed with a film thickness of 50 nm to 2 μm, more preferably with a film thickness in the range of 150 nm to 600 nm.
The complementary color layer 13 will be described in more detail. The complementary color layer 13 has a color conversion pigment, absorbs a part of incident light (light emission from the organic EL element), performs wavelength distribution conversion, and has different wavelength distributions including non-absorption of incident light and converted light. It is a layer for emitting the light which has. Preferably, the complementary color layer 13 converts blue or blue-green light from the organic EL element into white light. The white light in the present invention is not only light containing a wavelength component in the visible region (400 to 700 nm) at a ratio corresponding to relative luminous sensitivity, but also light that does not contain the wavelength component uniformly but appears white to the naked eye. Is also included.

  The color conversion dye is a dye that absorbs incident light and emits light in a different wavelength range, and preferably absorbs blue to blue-green light emitted from a light source to emit light in a desired wavelength range (for example, green (Or red). As color conversion dyes, DCM-1 (I), DCM-2 (II), DCJTB (III), 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a, 4a- Greens such as dyes for red light emitting materials such as diaza-s-indacene (IV), Nile red (V), propanedinitrile, rhodamine dyes that emit red light, cyanine dyes, pyridine dyes, oxazine dyes Any of those known in the art, such as a coumarin dye or a naphthalimide dye that emits light, can be used.

補色層１３は、パターニングを伴うドライプロセスで形成される。具体的には、カラーフィルター層１２等の上に、マスクによるパターニングを伴う蒸着法等により、波長分布変換を行う色変換色素を形成することによって、補色層１３を不連続な膜として形成する。蒸着は通常の真空蒸着装置を利用して行うことができる。蒸着原料である色変換色素を蒸着させる際、蒸着原料を坩堝に入れて真空中で加熱、蒸発させるが、坩堝材質として、モリブデン、タングステン、チタン、クロム、鉄、ニッケル、銅などの金属類およびそれらを含む合金類、あるいは石英ガラス、窒化硼素、アルミナ、チタニアなどのセラミックや金属酸化物、金属窒化物などを利用できる。
蒸発させるための加熱方法として、電熱線による抵抗加熱方式や電子ビーム加熱方式などを利用できる。蒸着原料の加熱温度は、１２０℃以上、４５０℃以下が好ましい。蒸着に適する温度は、蒸着原料の種類により異なるため、実用的な時間内で蒸着が可能な蒸発レートが得られ、かつ、熱分解が生じることのない範囲の温度になるように、蒸着原料ごとに温度、蒸発レートを設定することが好ましい。多くの有機材料系原料では、１２０℃未満の場合は蒸発に時間が掛かり過ぎ、実用的でない。一方、４５０℃を越えると多くの有機材料系原料で熱分解が生じるおそれが大きい。なお、これよりも低い温度で熱分解が生じる材料も多く存在するため、熱分解が生じることのない温度の範囲を別途調べておくことが好ましい。

The complementary color layer 13 is formed by a dry process involving patterning. Specifically, the complementary color layer 13 is formed as a discontinuous film by forming a color conversion dye for performing wavelength distribution conversion on the color filter layer 12 or the like by an evaporation method accompanied by patterning with a mask. The vapor deposition can be performed using a normal vacuum vapor deposition apparatus. When vapor-depositing the color conversion dye, which is a vapor deposition raw material, the vapor deposition raw material is put in a crucible and heated and evaporated in a vacuum, but the crucible material includes metals such as molybdenum, tungsten, titanium, chromium, iron, nickel, copper, and the like. Alloys containing them, ceramics such as quartz glass, boron nitride, alumina, and titania, metal oxides, metal nitrides, and the like can be used.
As a heating method for evaporating, a resistance heating method using a heating wire, an electron beam heating method, or the like can be used. The heating temperature of the vapor deposition material is preferably 120 ° C. or higher and 450 ° C. or lower. The temperature suitable for vapor deposition varies depending on the type of vapor deposition material, so that an evaporation rate that can be vapor-deposited within a practical time is obtained, and the vapor deposition material has a temperature that does not cause thermal decomposition. It is preferable to set the temperature and evaporation rate. For many organic material-based raw materials, if it is less than 120 ° C., it takes too much time to evaporate and is not practical. On the other hand, when it exceeds 450 ° C., there is a high possibility that thermal decomposition occurs in many organic material raw materials. In addition, since there are many materials that undergo thermal decomposition at a temperature lower than this, it is preferable to separately examine a temperature range in which thermal decomposition does not occur.

The substrate temperature is appropriately determined depending on the material used for the organic EL light-emitting display of the present invention, but is preferably 50 ° C. to 100 ° C. in view of the properties of the material and the manufacturing process. The pressure in the vacuum vapor deposition apparatus at the time of color conversion dye vapor deposition is preferably controlled to a pressure of 1 × 10 ⁻⁵ Pa to ⁵ × 10 ⁻⁴ Pa.
The color conversion dye to be deposited may be one kind or plural kinds. In the case of a plurality of types, it is possible to take a method of co-evaporating by separating the evaporation source of each material in consideration of easiness of evaporation of each material. By putting each material in a crucible and controlling the temperature of each evaporation source, the composition ratio of the complementary color layer 13 can be prepared with high accuracy. It is preferable that at least one of the color conversion dyes used in the present invention absorbs light emitted from the EL element and emits red light having a wavelength of 580 nm or more. Alternatively, other materials may be co-deposited together with the color conversion dye in order to improve the properties of the complementary color layer 13 such as the binding property of the deposited color conversion dye. Examples of materials that can be co-evaporated with the color conversion dye include aluminum complexes such as tris (8-quinolinolato) aluminum (Alq ₃ ) or tris (4-methyl-8-quinolinolato) aluminum (Almq ₃ ), 4,4 ′. Examples thereof include materials such as -bis (2,2-diphenylvinyl) biphenyl (DPVBi) and 2,5-bis- (5-tert-butyl-2-benzoxazolyl) thiophene.

The film thickness of the complementary color layer 13 is determined so that the complementary color layer 13 can contain a sufficient amount of dye capable of absorbing EL light at a concentration that can suppress the influence of concentration quenching of the color conversion dye. The film thickness to be set varies depending on the ease of concentration quenching of the dye used and the molar extinction coefficient. However, when compared with the typical film thickness of a conventional color conversion layer formed by a wet process in which a color conversion dye / matrix resin composition is applied and dried, it is markedly greater than a few μm to a few dozen μm. Since it is thin, it has a structure in which a step that causes a failure such as disconnection or short circuit of the transparent electrode and the reflective electrode is relaxed. Therefore, it is possible not to provide a flattening layer on the complementary color layer.
When the thickness of the complementary color layer 13 is 300 nm or more, a second planarizing layer having a thickness of 1 to 2 μm can be provided on the protective layer 17. Configuration examples are shown in FIGS. FIG. 4 shows a transparent substrate 11, a color filter 12, a first planarizing layer 15, a complementary color layer 13, a protective layer 17, a second planarizing layer 16, a gas barrier layer 14, and further an organic EL element. . In FIG. 5, the transparent substrate 11, the color filter 12, the complementary color layer 13, the protective layer 17, the second planarization layer 16, and the gas barrier layer 14 are formed in this order without forming the first planarization layer, and the organic EL element Is formed. By doing so, the flatness of the upper plane of the gas barrier layer can be further enhanced.

Subsequent to the formation of the complementary color layer 13, the protective layer 17 is formed on the complementary color layer 13 before the second gas barrier layer 15 is formed by sputtering or CVD. The protective layer 17 is a color in the complementary color layer 13 from high-energy particles such as plasma, neutral atoms or ionized atoms, high-speed electrons, or ultraviolet rays generated in the film forming process such as sputtering or CVD of the second gas barrier layer 15. It is effective to protect the conversion dye. By providing the protective layer 17, it is possible to prevent the color conversion pigment from being decomposed due to various factors as described above and the accompanying deterioration and loss of the color conversion ability.
The protective layer 17 is formed using a film-resistant material having sputtering resistance and / or plasma resistance. An example of such a material is a metal complex, particularly a metal chelate complex. Metal chelate complexes that can be used include metal phthalocyanines such as copper phthalocyanine (CuPc), or tris (8-hydroxyquinolinato) aluminum (Alq ₃ ) or tris (4-methyl-8-hydroxyquinolinato) aluminum (Almq). ₃ ) including an aluminum chelate complex. Alternatively, inorganic fluorides, particularly alkaline earth metal fluorides (MgF ₂ , CaF ₂ , SrF ₂ , BaF _2, etc.) can be used as a material for forming the protective layer 17.

As a film forming method for forming the protective layer 17, a film-resistant material as described above is deposited by using a method using low energy film forming particles such as a resistance heating evaporation method or an electron beam heating evaporation method. Is preferred. In the embodiment of the present invention, when the protective layer 17 is formed, a vapor deposition method that is difficult to cause damage is used in order to avoid decomposition of the color conversion dye of the complementary color layer serving as a base and a decrease in color conversion ability. It is also possible to use other methods such as a sputtering method and a CVD method by devising a film forming method or the like.
The thickness of the protective layer 17 is such that the protective layer 17 protects the complementary color layer 13 from the above-mentioned various damage factors in the film forming step of the second gas barrier layer 15 formed thereon, thereby eliminating or reducing the damage. Need to be sufficient. Moreover, it is preferable to have a film thickness that covers the upper surface of the complementary color layer 13 and can exist as a uniform film. The protective layer 17 preferably has a thickness of 5 to 100 nm, more preferably 10 to 50 nm. By having such a film thickness, the protective layer 17 that is a uniform film can effectively protect the complementary color layer 13.
The complementary color layer 13 and the protective layer 17 are formed as discontinuous films having through portions inside each pixel by a dry process involving patterning with a mask.

Since the two layers disposed above and below the complementary color layer and the protective layer can be directly joined through the penetration portion, the mechanical strength of the complementary color layer and the protective layer formed by the vapor deposition method is reinforced. Further, the adhesion strength of the complementary color layer, the protective layer, and the upper and lower layers thereof is improved. The formation of the through portion is preferably performed for all the pixels, but it is possible to appropriately select a pixel for forming the through portion within a range in which the strength of the vapor deposition film is not reduced. What is necessary is just to form the part.
As a mask used for patterning when the complementary color layer 13 and the protective layer 17 are formed by a vapor deposition method, a discontinuous complementary color layer formed by the mask when the screen of the organic EL light emitting display is viewed with the naked eye. It is necessary that the deposited film has a pattern for preventing it from being identified as uneven color. For this purpose, as illustrated in FIG. 9, the color filter layer 12 (first flattening layer 15 if present) is provided with striped vapor deposition films having a width of 5 to 50 μm and spaced by a width of 5 to 10 μm. A mask having a pattern as formed above is preferred. The mask pattern is not limited to stripes. As long as the pattern has the above function, for example, a lattice pattern (FIG. 10) or a staggered pattern (FIG. 11) can also be used.

The masks used when the complementary color layer 13 and the protective layer 17 are formed by the vapor deposition method have the same pattern. Here, the same mask may be used when the complementary color layer 13 and the protective layer 17 are formed by vapor deposition. Preferably, after the complementary color layer 13 is formed by a vapor deposition method using patterning with a mask, the protective layer 17 is preferably formed by a vapor deposition method while maintaining the positional relationship between the mask and the substrate in the step. By doing so, it is possible to prevent a pattern shift due to a mask alignment shift in the patterning of the complementary color layer 13 and the protective layer 17.
Here, in the case where the complementary color layer 13 and the protective layer 17 are formed by vapor deposition, when the patterning by the mask is not accompanied, the complementary color layer 13 and the protective layer 17 are the color filter layer 12 (the first flat if present). In the laminated structure sandwiched between the gas barrier layer 14 and the color filter layer 12 (the first planarization layer 15 if present), an organic vapor deposition film (complementary color layer) is formed. 13) exists. In general, a vapor-deposited film of an organic material has low mechanical strength, and further has a linear expansion coefficient different from that of the gas barrier layer 14 and the color filter layer 12 (the first planarization layer 15 when present) sandwiching the organic film, In the laminated structure, damage to the deposited film occurs due to stress stress.

The deposited film has low adhesion to the underlying color filter layer 12 (first planarization layer 15 if present), and the complementary color layer 13, protective layer 17, gas barrier layer 14, and color filter layer 12. This causes mechanical delamination with the first planarization layer 15 (if present). This causes a decrease in yield and a generation of pixel defects due to driving and a decrease in lifetime due to the manufacture of an organic light-emitting device formed by forming a sequentially laminated structure.
In the present invention, by forming the complementary color layer 13 and the protective layer 17 discontinuously, the complementary color layer 13 and the protective layer 17 and upper and lower layers sandwiching them, for example, the gas barrier layer 14 and the color filter layer 12 (if present) The stress due to the difference in linear expansion coefficient from the first planarization layer 15) is relieved, and the complementary color layer 13 and the protective layer 17 are prevented from being damaged. Further, by adopting a structure in which the gas barrier layer 14 has a portion disposed directly on the color filter layer 12 (the first planarization layer 15 if present), adhesion between the layers is ensured, and there is a problem of peeling. Avoided. Thereby, it becomes possible to manufacture the panel of an organic EL display with a high yield, and further, it is possible to prevent the occurrence of pixel defects due to driving and the reduction of the lifetime due to this.
It is preferable that the material of the second planarization layer has an excellent light transmittance from the point that light from the organic EL element is emitted to the outside through the second planarization layer. Preferably, it has a high transmittance of 50% or more, more preferably 85% or more with respect to light having a wavelength of 400 to 800 nm.

The second planarizing layer 16 is generally formed by a coating method such as a spin coating method, a roll coating method, or a knife coating method. In this case, applicable materials include thermoplastic resins (polyester resins (polyethylene terephthalate, etc.), polyamide resins, polyimide resins, polyetherimide resins, polyacetal resins, polyether sulfone, polyvinyl alcohol and derivatives thereof (polyvinyl butyral, etc.) ), Polyphenylene ether, norbornene resin, isobutylene maleic anhydride copolymer resin, cyclic olefin resin), non-photosensitive thermosetting resin (alkyd resin, aromatic sulfonamide resin, urea resin, melamine resin, benzoguanamine resin) Alternatively, a photocurable resin can be used.
Moreover, in the conventional color conversion layer formed by application | coating and drying of the composition of a color conversion pigment | dye / matrix resin, there exists a possibility of including the water | moisture content which causes deterioration of an organic EL element in the layer. However, since the complementary color layer of the present invention is formed using a vapor deposition method which is a dry process, there is no possibility of including such moisture, and therefore, it does not cause deterioration of the organic EL element.
The gas barrier layer 14 is a layer for preventing the permeation of moisture from the color filter layer 12 to the organic EL layer side and protecting the complementary color layer 13 from the formation process of the transparent electrode 21 of the organic EL element formed thereon. It is. Therefore, the gas barrier layer 14 is formed of a material having a barrier property against moisture, oxygen, and low molecular components.

Furthermore, the gas barrier layer 14 is preferably transparent in the emission wavelength region in order to efficiently transmit the light emission of the organic EL layer 22 to the complementary color layer 13 side. Regarding transparency, the gas barrier layer 14 preferably has a high transmittance of 50% or more in the range of 400 to 800 nm. Suitable materials for the gas barrier layer 14 include SiN, SiNH, AlN, and the like.
The gas barrier layer 14 has a film thickness in the range of 100 nm to 2 μm, more preferably 100 nm to 300 nm, and is formed over the entire surface of the complementary color layer 13 and the protective layer 17.
The gas barrier layer 14 can be formed by using a dry process such as sputtering or CVD. The sputtering method may be a high frequency sputtering method or a magnetron sputtering method. The CVD method is preferably a plasma CVD method. As means for generating plasma in this step, any means known in the art such as capacitively coupled or inductively coupled high frequency power, ECR, and helicon wave may be used. In addition to power having an industrial frequency of 13.56 MHz, power having a frequency in the UHF or VHF region can be used as the high frequency power. As the Si source in the present invention, SiH ₄ , SiH ₂ Cl ₂ , SiCl ₄ , Si (OC ₂ H ₅ ) _{4 and the} like can be used, and as the Al source, AlCl ₃ , Al (O-i-C). ₃ H ₇ ) ₃ or the like can be used. In addition, it is convenient to use NH ₃ as the N source in the present invention.

The organic EL device that can be used in the present invention includes an organic EL layer sandwiched between a pair of electrodes, includes at least an organic light emitting layer, and, if necessary, a hole injection layer, a hole transport layer, an electron transport layer And / or a structure in which an electron injection layer is interposed. Alternatively, a hole injection / transport layer having both hole injection and transport functions and an electron injection / transport layer having both electron injection and transport functions may be used.
Specifically, an organic EL element having the following layer structure is employed.
(1) Anode / organic light emitting layer / cathode (2) Anode / hole injection layer / organic light emitting layer / cathode (3) Anode / organic light emitting layer / electron injection layer / cathode (4) Anode / hole injection layer / positive Hole transport layer / organic light emitting layer / cathode (5) Anode / hole injection layer / organic light emitting layer / electron transport layer / cathode (6) Anode / hole injection layer / hole transport layer / organic light emitting layer / electron transport layer / Cathode (7) Anode / hole injection layer / hole transport layer / organic light emitting layer / electron transport layer / electron injection layer / cathode In the above layer configuration, the anode and the cathode are either transparent electrodes or reflective electrodes, respectively. It is. In this technique, it is known that it is easy to make the anode transparent. In the present invention, it is preferable to use the anode as a transparent electrode and the cathode as a reflective electrode. The transparent electrode is preferably transparent in the region of light emitted from the organic EL layer.

As the material of each layer of the organic EL layer, known materials are used. For example, in order to obtain blue to blue-green light emission as the organic light emitting layer, for example, fluorescent brighteners such as benzothiazole, benzimidazole, and benzoxazole, metal chelated oxonium compounds, styrylbenzene compounds, aromatic Group dimethylidin compounds are preferably used.
The transparent electrode 21 preferably has a high transmittance of 50% or more, more preferably 85% or more with respect to light having a wavelength of 400 to 800 nm. The transparent electrode 21 is made of ITO (In—Sn oxide), NESA film, Sn oxide, IZO (In—Zn oxide), Zn oxide, Zn—Al oxide, Zn—Ga oxide, or these It can be formed using a conductive transparent metal oxide in which a dopant such as F or Sb is added to the oxide.
The transparent electrode 21 is formed using a vapor deposition method, a sputtering method, or a chemical vapor deposition (CVD) method, and is preferably formed using a sputtering method. Further, when a transparent electrode 21 composed of a plurality of partial electrodes is required as will be described later, a conductive transparent metal oxide is uniformly formed over the entire surface, and then etched to give a desired pattern. The transparent electrode 21 composed of a plurality of partial electrodes may be formed. Or you may form the transparent electrode 21 which consists of a some partial electrode using the mask which gives a desired shape.

When the transparent electrode 21 is used as a cathode, it is preferable to improve the electron injection efficiency by providing a buffer layer at the interface with the organic EL layer 22. As the material of the buffer layer, alkali metals such as Li, Na, K or Cs, alkaline earth metals such as Ba and Sr, alloys containing them, rare earth metals, or metal fluorides thereof can be used. However, it is not limited to them. The film thickness of the buffer layer can be appropriately selected in consideration of the driving voltage, transparency, and the like, but in a normal case, it is preferably 10 nm or less.
The reflective electrode 23 is preferably formed using a highly reflective metal, amorphous alloy, or microcrystalline alloy. High reflectivity metals include Al, Ag, Mo, W, Ni, Cr and the like. High reflectivity amorphous alloys include NiP, NiB, CrP, CrB, and the like. The highly reflective microcrystalline alloy includes NiAl and the like. The reflective electrode 23 may be used as a cathode or an anode.
When the reflective electrode 23 is used as a cathode, the above-described buffer layer may be provided at the interface between the reflective electrode 23 and the organic EL layer 22 to improve the electron injection efficiency with respect to the organic EL layer 22. Alternatively, in the case where the reflective electrode 23 is used as a cathode, an alkali metal such as Li, Na, or K, which is a material having a low work function, Ca, Mg, which is a material having a low work function, compared to the aforementioned high reflectivity metal, amorphous alloy, or microcrystalline alloy , Sr and other alkaline earth metals can be added and alloyed to improve electron injection efficiency. When the reflective electrode 23 is used as the anode, a conductive transparent metal oxide layer may be provided at the interface between the reflective electrode 23 and the organic EL layer 22 to improve the hole injection efficiency for the organic EL layer 22. .

The reflective electrode 23 is formed using any means known in the art such as a vapor deposition method (resistance heating or electron beam heating), a sputtering method, an ion plating method, or a laser ablation method, depending on the material to be used. can do. As will be described later, when the reflective electrode 23 composed of a plurality of partial electrodes is required, the reflective electrode 23 composed of a plurality of partial electrodes may be formed using a mask giving a desired shape. Alternatively, before the organic EL layer 22 is laminated, a separation partition wall (not shown) having a reverse taper-shaped cross-sectional shape may be formed, and the reflective electrode 23 formed of a plurality of partial electrodes separated thereby may be formed. .
In order to form a plurality of independent light emitting portions in the organic EL element, each of the transparent electrode 21 and the reflective electrode 23 is formed from a plurality of parallel stripe-shaped portions, and the stripe and the reflective electrode forming the transparent electrode 21 It is preferable that the stripes forming the stripes 23 cross each other (preferably orthogonally). In this way, the organic EL element can perform matrix driving. That is, when a voltage is applied to the specific stripe of the transparent electrode 21 and the specific stripe of the reflective electrode 23, the organic EL layer 22 emits light at a portion where the stripes intersect.
Alternatively, a plurality of portions in which one electrode (for example, transparent electrode 21) is a uniform planar electrode having no stripe pattern and the other electrode (for example, reflective electrode 23) corresponds to each light emitting portion. The electrode may be patterned. In that case, a plurality of switching elements corresponding to the respective light emitting portions are provided, and so-called active matrix driving can be performed by connecting the partial electrodes corresponding to the respective light emitting portions on a one-to-one basis.

The transparent substrate 11 may be any material that has excellent visible light transmittance and that does not cause a decrease in the performance of the organic EL light emitting display in the process of forming the organic EL light emitting display. A preferable transparent substrate is a glass substrate and a rigid resin substrate formed of a resin such as polyolefin, acrylic resin (including polymethyl methacrylate), polyester resin (including polyethylene terephthalate), polycarbonate resin, or polyimide resin. including. Alternatively, a flexible film formed from a polyolefin, an acrylic resin (including polymethyl methacrylate), a polyester resin (including polyethylene terephthalate), a polycarbonate resin, or a polyimide resin may be used as the substrate. Glass and resins such as polyethylene terephthalate and polymethyl methacrylate are included. Borosilicate glass or blue plate glass is particularly preferable.
The color filter layer 12 in the present invention is a layer that splits incident light and transmits only light in a desired wavelength region. In the configuration of FIGS. 1 and 2, three color filter layers of a red color filter layer 12R, a green color filter layer 12G, and a blue color filter layer 12B are used, but one, two, or four types are used as necessary. The above color filter layer may be used.

The color filter layer 12 is obtained by dispersing a dye or pigment having a desired absorption in a polymer matrix resin, and any material known in the art such as a commercially available flat panel display material, for example, It can be formed by using a color filter material for liquid crystal (color mosaic manufactured by Fuji Film Electronics Materials Co., Ltd.). The color filter layer 12 in the present invention has a film thickness of 0.5 to 5 μm, more preferably 1 to 3 μm, in order to obtain light in a desired wavelength region with high color purity.
The color filter layer 12 of the present invention is required to be formed using a wet process including application of a liquid material (solution or dispersion), photopatterning, and removal of unnecessary portions with a developer. Is preferable for realizing the above. After completion of the formation by the wet process, the transparent substrate 11 and the color filter layer 12 are heated at a high temperature to sufficiently remove water remaining in the color filter layer 12, thereby improving the stability of the finished organic EL light emitting display. Therefore, it is preferable.
Although not illustrated in FIGS. 1 and 2, a black matrix that does not transmit light may be formed in the gaps between the color filter layers 12 (R, G, and B). Similarly to the color filter layer 12, the black matrix can be produced by a wet process using any material known in the art such as a commercially available flat panel display material. The black matrix is effective in reducing the step formed by the color filter layer 12 in addition to improving the contrast ratio of the organic EL light emitting display.

When the black matrix is provided, the black matrix may be formed first, or the color filter layer 12 may be formed first. Here, a part of the black matrix and a part of the color filter layer 12 may be superposed (overlapped) so that the light from the organic EL element always passes through the color filter layer 12 and is emitted. When forming the black matrix, it is preferable to perform the high-temperature heating step after the formation of all the color filter layers 12 and the black matrix in order to remove the moisture described above.
The first planarization layer 15 is a layer for compensating for a step caused by the color filter layer 12. In addition, since the light from the organic EL element is emitted to the outside through the first planarization layer 15, the material of the first planarization layer 15 has excellent light transmittance, that is, a wavelength of 400 to 800 nm. Preferably, it has a high transmittance of 50% or more, more preferably 85% or more with respect to the light.
The first planarization layer 15 is generally formed by a coating method such as a spin coating method, a roll coating method, or a knife coating method. In this case, applicable materials include thermoplastic resins (polyester resins (polyethylene terephthalate, etc.), polyamide resins, polyimide resins, polyetherimide resins, polyacetal resins, polyether sulfone, polyvinyl alcohol and derivatives thereof (polyvinyl butyral, etc.) ), Polyphenylene ether, norbornene resin, isobutylene maleic anhydride copolymer resin, cyclic olefin resin), non-photosensitive thermosetting resin (alkyd resin, aromatic sulfonamide resin, urea resin, melamine resin, benzoguanamine resin) Alternatively, a photocurable resin can be used.

After the first planarization layer 15 is formed, the laminate (including the black matrix if present) of the transparent substrate 11, the color filter layer 12, and the first planarization layer 15 is heated at a high temperature to form the color filter layer. In order to improve the stability of the organic light emitting device, it is preferable to sufficiently remove moisture remaining in the first planarization layer 15 and the first planarization layer 15. Alternatively, the color filter layer 12 (including a black matrix, if present) is heated at a high temperature before the first planarization layer 15 is formed, and moisture in the color filter layer 12 is removed. After the first planarization layer 15 is formed, the moisture remaining in the first planarization layer 15 may be removed by heating again at a high temperature.
The first planarization layer 15 has a thickness of 0.5 to 3 μm, more preferably 1 to 2 μm, in a region that does not overlap with the color filter layer 12, and is provided by a plurality of types of color filter layers. The step can be compensated and a flat upper surface can be provided.
Hereinafter, it demonstrates still in detail using the Example of an organic light-emitting device.

Hereinafter, referring to FIG. 1 in the first embodiment. Note that the black matrix is not shown.
The glass substrate 11 having a thickness of 0.7 mm was subjected to ultrasonic cleaning in pure water, dried, and further UV ozone cleaned. Color mosaic CK-7800 (manufactured by Fuji Film Electronics Materials Co., Ltd.) is applied to a cleaned glass substrate using a spin coating method, and patterning is performed using a photolithographic method. A black matrix in which a plurality of stripe-shaped portions having a thickness of 1 μm are arranged at a pitch of 0.11 mm was formed.
Subsequently, red, green, and blue color filter layers were formed using color mosaics CR-7001, CG-7001, and CB-7001, respectively. After applying each color filter layer material, patterning is performed by photolithography, and a plurality of striped portions having a width of 0.10 mm and a thickness of 1 μm on the glass substrate 11 are arranged at a pitch of 0.33 mm. A color filter layer 12R, a green color filter layer 12G, and a blue color filter layer 12B were formed. In this structure, each of the plurality of striped portions of the black matrix was overlapped with one of the color filter layers 12 in an area of 0.01 mm from both sides.

Next, a transparent protective coating agent NN810L (manufactured by JSR) was applied by a spin coating method, and patterning was performed using a photolithographic method, thereby forming a first planarizing layer 15 covering the color filter layer 12 and the black matrix. The film thickness of the planarizing layer 15 in the region in contact with the black matrix was 1.5 μm.
The substrate having the first flattening layer 15 or less obtained as described above can be left by heating to 200 ° C. for 30 minutes in a dry nitrogen atmosphere (both oxygen and moisture concentrations are 10 ppm or less). Sexual water was removed.
Next, the substrate on which the first planarizing layer 15 was formed was mounted on a resistance heating type hot plate above the vacuum deposition apparatus, and a patterning mask was placed in close contact with the lower surface of the substrate. On the other hand, the color conversion dye DCM-1, which is a material for the complementary color layer, was placed in a molybdenum crucible and placed at a position facing the substrate below in the vacuum deposition apparatus, and a heating sheath heater was mounted around the crucible. The distance between the substrate and the crucible was four times the substrate length. Then, the inside of the apparatus was depressurized, and the substrate was maintained at 70 ° C. using a proportional control temperature controller.
Next, the substrate on which the first planarization layer 15 was formed was transferred into a vacuum deposition apparatus maintained in a reduced pressure state via a load lock chamber connected to the vacuum deposition apparatus. Here, when a substrate is carried in and out by a method via a load lock chamber connected to the vacuum deposition apparatus, the substrate is removed from the vacuum chamber in the vacuum deposition apparatus while the vacuum tank of the vacuum deposition apparatus is kept in a reduced pressure state. It is possible to move between the load lock chamber and the outside of the apparatus. First, the substrate was mounted on a resistance heating type hot plate above the vacuum deposition apparatus. Next, a mask for patterning was brought into close contact with the lower surface of the substrate using a mask support mechanism in a vacuum deposition apparatus. In addition, in this vacuum vapor deposition, a molybdenum crucible containing a color conversion dye DCM-1 as a material for the complementary color layer 13 and a quartz made with an aluminum quinolylate complex (Alq3) as a material for the protective layer 17 are used. These crucibles are mounted on a resistance heating type vapor deposition source which is partitioned by a shielding plate at a position facing the substrate below the vacuum vapor deposition apparatus. Here, the distance between the substrate and the crucible was four times the substrate length. The substrate was maintained at 50 ° C. using a proportional control temperature controller while maintaining the reduced pressure state of the vacuum vapor deposition apparatus.

After the pressure in the apparatus reaches 1 × 10 ⁻⁴ Pa, the crucible containing the color conversion dye DCM-1 is heated to 340 ° C., and DCM-1 is deposited at a deposition rate of 0.3 Å / s, A complementary color layer 13 having a thickness of 200 nm was formed. Here, as a mask for patterning, the mask having the shape shown in FIG. 6 has a pattern in which striped vapor deposition films having a width of 50 μm are formed on the first planarizing layer 15 with an interval of 10 μm in width. Was used.
Subsequently, Alq ₃ was heated to 300 ° C. at a pressure of 1 × 10 ⁻⁴ Pa while maintaining the state in which the substrate and the mask for patterning were brought into close contact with each other in a vacuum vapor deposition apparatus, and 0.3 Å / s. The protective layer 17 having a film thickness of 50 nm was formed by vapor deposition at a vapor deposition rate.
Then, a SiNH film having a film thickness of 300 nm was stacked using the plasma CVD method, and the gas barrier layer 14 was obtained. The source gas was 100 SCCM SiH ₄ , 500 SCCM NH ₃ , and 200 SCCM N ₂ , and the gas pressure was 80 Pa. Further, as the power for generating plasma, 0.5 kW of RF power of 13.56 MHz was applied.
An organic EL device was formed on the gas barrier layer formed as described above. First, an IZO film having a thickness of 200 nm was formed using a DC sputtering method. Patterning was performed by a photolithographic method using In—Zn oxide as a target, O ₂ and Ar as sputtering gases, and then using an oxalic acid aqueous solution as an etching solution, to obtain a transparent electrode 21. The transparent electrode 21 was formed from a plurality of stripe-shaped portions located above the color filter layer 12 and extending in the same direction as the stripes of the color filter layer 12 and having a width of 0.1 mm and a pitch of 0.11 mm.

Next, a polyimide film is formed using an insulating coating agent Photo Nice (manufactured by Toray Industries, Inc.), and a width of 0.1 mm and a length of 0.3 mm are formed on each stripe-shaped portion of the transparent electrode using a photolithographic method. An insulating film was formed in which openings (portions serving as light emitting portions of the organic EL element) were arranged with a pitch of 0.33 mm in the length direction.
Subsequently, a reflective electrode separation partition wall (not shown) was formed. A negative photoresist ZPN1168 (manufactured by ZEON Corporation) is applied by spin coating, pre-baked, and a stripe-shaped pattern extending in a direction perpendicular to the stripe of the transparent electrode 21 is baked using a photomask, and hot at 110 ° C. Post-exposure baking was performed on the plate for 60 seconds, development was performed, and finally heating was performed on a hot plate at 160 ° C. for 15 minutes to form a reflective electrode separation partition. The obtained reflective electrode separation partition wall had a reverse-tapered cross-sectional shape and was composed of a plurality of stripe-shaped portions extending in a direction perpendicular to the stripe of the transparent electrode 21.
As described above, the substrate on which the reflective electrode separation barrier rib was formed was mounted in a resistance heating vapor deposition apparatus, and the hole injection layer, the hole transport layer, the organic light emitting layer, and the electron injection layer were formed without breaking the vacuum. . The vacuum chamber pressure during deposition was reduced to 1 × 10 ^-4 Pa. Copper phthalocyanine (CuPc) with a film thickness of 100 nm as the hole injection layer, and 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) with a film thickness of 20 nm as the hole transport layer Then, DPVBi with a thickness of 30 nm was stacked as the light emitting layer, and Alq ₃ with a thickness of 20 nm was stacked as the electron injection layer to obtain an organic EL layer 22.

Thereafter, without breaking the vacuum, a 200 nm thick Mg / Ag (10: 1 weight ratio) film is deposited, and the reflection is made of a plurality of stripe-shaped partial electrodes having a width of 0.30 mm and a pitch of 0.33 mm. An electrode 23 was obtained.
The device thus obtained was sealed using a sealing glass and a UV curable adhesive in a dry nitrogen atmosphere (both oxygen and moisture concentrations of 10 ppm or less) in the glove box, to obtain an organic light emitting device.
The obtained device initially emitted white light having a luminance of 1000 cd / m ² when a current having a current density of 53 mA / m ² was passed. The obtained device was continuously driven for 5,000 hours under the condition of emitting white light (initial chromaticity (CIE), x = 0.31, y = 0.33) at a luminance of 1000 cd / m ² , but the dark area The occurrence of was not observed.

Hereinafter, referring to FIG. 3 in the second embodiment. Note that the black matrix is not shown.
An organic light emitting device was obtained by repeating the same procedure as in Example 1 except that the thickness of the complementary color layer 13 was 1 μm and the second planarizing layer 16 was provided after the protective layer 17 was formed. Here, after the complementary color layer 13 was formed, the second planarizing layer was coated with a transparent protective coating agent NN810L (manufactured by JSR) to a thickness of 1.5 μm by a spin coating method.
The obtained device was continuously driven for 5,000 hours under the condition of emitting white light (initial chromaticity (CIE), x = 0.31, y = 0.33) at a luminance of 1000 cd / m ² , but the dark area The occurrence of was not observed.

Hereinafter, referring to FIG. 2 in the third embodiment. Note that the black matrix is not shown.
An organic light emitting device was obtained by repeating the same procedure as in Example 1 except that the first planarizing layer 15 was not formed. The obtained device was continuously driven for 5,000 hours under the condition of emitting white light (initial chromaticity (CIE), x = 0.31, y = 0.33) at a luminance of 1000 cd / m ² , but the dark area The occurrence of was not observed.

Hereinafter, referring to FIG. 4 in the fourth embodiment. Note that the black matrix is not shown.
An organic light emitting device was obtained by repeating the same procedure as in Example 2, except that the first planarizing layer 15 was not formed. The obtained device was continuously driven for 5,000 hours under the condition of emitting white light (initial chromaticity (CIE), x = 0.31, y = 0.33) at a luminance of 1000 cd / m ² , but the dark area The occurrence of was not observed.
(Comparative Example 1)
Hereinafter, in Comparative Example 1, reference is made to FIG. Note that the black matrix is not shown.
An organic light emitting device was obtained by repeating the same procedure as in Example 1 except that a mask for patterning vapor deposition was not used when forming the complementary color layer 13 and the protective layer 17. However, the adhesion between the complementary color layer 13 and the first planarization layer 15 is poor, and there is a portion where the complementary color layer 13 and the protective layer 17 are partially peeled off. In addition, it was observed that non-lighted pixels were partially generated due to the peeling of the complementary color layer 13 and the protective layer 17 with driving.
(Comparative Example 2)
Hereinafter, in Comparative Example 2, reference is made to FIG. Note that the black matrix is not shown.

An organic light emitting device was obtained by repeating the same procedure as in Example 1 except that a mask for patterning vapor deposition was not used when forming the protective layer 17. However, the adhesiveness between the protective layer 17 and the first planarization layer 15 is poor, and there are places where the protective layer 17 is partially peeled off. In addition, it was observed that non-lighted pixels were partially generated as the protective layer 17 was peeled off with driving.
(Comparative Example 3)
Hereinafter, in Comparative Example 3, reference is made to FIG. Note that the black matrix is not shown.
An organic light emitting device was obtained by repeating the same procedure as in Example 1 except that the protective layer 17 was not formed. The obtained device initially emitted white light having a luminance of 1000 cd / m ² when a current having a current density of 72 mA / m ² was passed. Compared with Example 1, the current efficiency is lowered, and it can be said that a large current is required to obtain light emission of the same luminance. This is due to damage caused by high-energy particles such as plasma, neutral atoms or ionized atoms, fast electrons, or ultraviolet rays when the second gas barrier layer 15 is formed by plasma CVD following the formation of the complementary color layer 13. This is considered to be caused by the decomposition of the color conversion pigment in the complementary color layer 13 and the decrease in the color conversion ability. The obtained device was continuously driven for 5,000 hours under the condition of emitting white light (initial chromaticity (CIE), x = 0.31, y = 0.33) at a luminance of 1000 cd / m ² , but the dark area The occurrence of was not observed.

It is typical sectional drawing which shows the structure of the organic light emitting device of Example 1 of this invention. It is typical sectional drawing which shows the structure of the organic light emitting device of Example 3 of this invention. It is typical sectional drawing which shows the structure of the organic light emitting device of Example 2 of this invention. It is typical sectional drawing which shows the structure of the organic light emitting device of Example 4 of this invention. It is typical sectional drawing which shows the structure of the organic light emitting device of the comparative example 1 of this invention. It is typical sectional drawing which shows the structure of the organic light emitting device of the comparative example 2 of this invention. It is typical sectional drawing which shows the structure of the organic light emitting device of the comparative example 3 of this invention. It is typical sectional drawing which shows the structure of the organic light-emitting device of the conventional color conversion system which has the color conversion layer formed of the wet process It is a schematic diagram of the stripe-shaped mask for patterning at the time of forming a complementary color layer. It is a schematic diagram of the lattice-shaped mask for patterning at the time of forming a complementary color layer. It is a schematic diagram of the staggered mask for patterning at the time of forming a complementary color layer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Transparent substrate 12R, 12G, 12B Color filter layer 13 Complementary color layer 14 Gas barrier layer 15 1st planarization layer 16 2nd planarization layer 17 Protective layer 21 Transparent electrode 22 Organic EL layer 23 Reflective electrode 31 Transparent substrate 32R, 32G, 32B Color filter layer 33R, 33G, 33B Color conversion layer 34 Flattening layer 35 Gas barrier layer 41 Transparent electrode 42 Organic EL layer 43 Reflecting electrode

Claims (12)

  A light-emitting device comprising a transparent substrate, a complementary color layer, a protective layer, and an organic EL element, wherein the complementary color layer is formed with a through-hole in a pixel using a dry process, and the organic EL element Absorbs at least a part of the light emitted by the light, emits light having a wavelength distribution different from the absorption wavelength, and the protective layer has a pattern having the same shape as the complementary color layer in at least the pixel and the complementary color layer exists An organic light-emitting device, which is formed only directly above and has a portion where the upper and lower layers sandwiching the complementary color layer and the protective layer are directly joined at the penetrating portion.   One or more color filter layers arranged separately from each other between the transparent substrate and the complementary color layer, and a gas barrier layer between the protective layer and the organic EL element, and the upper and lower sides sandwiching the complementary color layer and the protective layer The organic light emitting device according to claim 1, wherein the layers are the color filter layer and the gas barrier layer.   The first planarization layer is further provided between the color filter and the complementary color layer, and upper and lower layers sandwiching the complementary color layer and the protective layer are the first planarization layer and the gas barrier layer. The organic light-emitting device described.   The second flattening layer is further provided between the protective layer and the gas barrier layer, and upper and lower layers sandwiching the complementary color layer and the protective layer are the color filter layer and the second flattening layer. The organic light emitting device according to 1.   A second planarizing layer is further provided between the protective layer and the gas barrier layer, and upper and lower layers sandwiching the complementary color layer and the protective layer are the first planarizing layer and the second planarizing layer. Item 4. The organic light-emitting device according to Item 3.   6. The organic light-emitting device according to claim 1, wherein the complementary color layer is formed by a vapor deposition method using patterning with a mask.   The organic light-emitting device according to claim 1, wherein the protective layer is formed by a vapor deposition method using patterning with a mask.   The organic light emitting device according to claim 7, wherein masks used when the complementary color layer and the protective layer are formed by vapor deposition have the same pattern.   The organic light-emitting device according to claim 8, wherein a mask used when the complementary color layer is formed by an evaporation method is also used when the protective layer is formed by an evaporation method.   The protective layer is formed by vapor deposition while maintaining the positional relationship between the mask and the substrate in the step after the complementary color layer is formed by vapor deposition using patterning using a mask. The organic light-emitting device described.   The organic light-emitting device according to claim 1, wherein the complementary color layer is composed of one or more kinds of color conversion dyes. The organic light-emitting device according to claim 1, wherein the protective layer includes a film-resistant material.

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