JP2002015864A - Method of manufacturing organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing an active-matrix drive type of high accuracy organic electroluminescent element with satisfactory productivity. SOLUTION: This method of manufacturing an organic electroluminescent element has a process for forming a pixel electrode substrate 20, provided with a light-emitting layer 25 made of the organic material on matrix-like pixels 26r, 26g and 26b, a process for forming a color element stamp 10 provided with the prescribed-shaped light reactive resin patterns 2r, 2g and 2b containing the coloring matter with the predetermined space, a process for positioning the pixel electrode substrate 20 and the coloring matter stamp 10 so that the pixels 26r, 26g and 26b and the option reactive resin layer patterns 2r, 2g and 2b are arranged opposite to each other, a process for heating one of the pixel electrode substrate 20 and the coloring matter stamp 10 at the prescribed temperature for the prescribed time so as diffuse at least the coloring matter among the material included in the optical reactive resin layer patterns 2r, 2g and 2b in a light-emitting layer 25, and a process for forming an opposite electrode 29 on the light emitting layer 25.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing an organic electroluminescence device (organic EL device).

[0002]

2. Description of the Related Art Organic electroluminescent elements (hereinafter referred to as organic EL elements) are self-luminous, have high-speed response, do not have a viewing angle dependency, and are expected to have low power consumption. And application development to displays of personal computers and the like.

Hereinafter, a typical organic EL will be described with reference to FIG.
The structure of the element and its light emitting principle will be described. In FIG. 12, reference numeral 120 denotes an organic EL element, and the transparent glass substrate 1
21 on the surface of ITO (indium tin oxi)
de) and the like, an anode 122 made of a transparent conductive film, a hole transport layer 123 made of an organic film, and an electron transporting light emitting layer 12
4. It has a configuration in which a cathode 125 of an aluminum-magnesium alloy is sequentially laminated. For example, an aryldiamine compound is used as the hole transport layer 123, and tris (8-quinolino-
E) Aluminum (Alq ₃ ) organic metal complex or the like is applied.

When a voltage E is applied between the anode 122 and the cathode 125, holes are injected from the anode 122, and the holes are transported to the hole transport layer 123. On the other hand, electrons are injected from the cathode 125, and the electrons are transported to the light-emitting layer 124 having an electron transporting property. Then, the holes and electrons reach the interface between the hole transport layer 123 and the light emitting layer 124, and the holes and electrons recombine near this interface. At this time, the binding energy of holes and electrons moves to the luminescent dye molecules in the luminescent layer 124, and is converted to light and emitted when returning from the excited state that excites the dye molecules to the ground state.

Here, since the light emitting layer 124 is made of tris (8-quinolinol) aluminum, green light is emitted. The light thus generated is transmitted to the transparent glass substrate 121.
Is taken out to the outside. In order to control the color purity of emitted light and increase the luminance, for example, doping (also referred to as diffusion transfer) of a dye having a predetermined emission wavelength using an organometallic complex as a host material is performed. As a host material of the light emitting layer, a material that emits light in the same wavelength region as the absorption spectrum of the doped dye or in a shorter wavelength region than that is required.

[0006]

In order to perform full-color display with an organic EL element, red (R), green (G), and blue (B) are required.
It is necessary to form a set of three types of pixels that emit light in a matrix. In particular, in order to provide a high-definition full-color display element, it is necessary to accurately form the light-emitting layer 124 corresponding to three primary colors on fine pixels.

By the way, a method of forming a light emitting layer of a corresponding color on a pixel includes (a) a method of forming a low molecular light emitting material of each color by vacuum deposition through a metal mask (for example, Japanese Patent Application Laid-Open No. No. 41069), and (b) a method in which a light emitting material of each color is ejected to a pixel corresponding portion using a polymer light emitting layer material by an ink jet method (for example, Japanese Patent Application Laid-Open No. H10-123).
No. 77), (c) After forming a polymer light emitting layer on a substrate by spin coating or dip coating, R, G, and B fluorescent dyes are coated on the light emitting layer surface using an ink jet method or a screen printing method. A method of forming each of the dye layers contained therein and diffusing the dye into the light emitting layer by infrared heating (Japanese Patent Application Laid-Open No. 7-235378 or US Pat.
No. 692), (d) a polymer light emitting layer formed on a substrate by spin coating or dip coating, and a high-concentration dye layer formed by coating on the substrate are opposed to each other via a shadow mask. Sublimation and diffusion from the high concentration layer to the light emitting layer side (Applied Physics)
Letters, Vol. 74, No. 13, 1913-191
(1999), (e) A polymer light emitting layer formed on a substrate and a high-concentration dye layer formed by coating on a substrate are brought into close contact with each other, and a current is applied to an ITO pixel electrode to heat the dye to form a high-concentration dye layer. (Ipn.JA)
ppl. Phys. , 38, Part2 10A, L
1143-L1145, 1999).

[0008] Of these, (a) and (d) use a mask, and therefore a highly accurate positioning and adjusting mechanism of the mask is required for fine pixels, and the productivity is inevitably reduced.
Also, as the opening of the mask becomes smaller, the thickness of the mask also needs to be reduced accordingly. For example, when the size of the opening is 5 μm, the thickness of the mask must be 5 μm or less, and it is extremely difficult to manufacture the mask.

In the ink-jet or printing method of (b) or (c), a bank (also called a shore or a bank) must be formed in advance between pixels in order to accurately position the ink to be applied. The higher the definition, the more difficult it becomes to manufacture. In addition, in the pixel electrode heating method (e), the diffusion of the dye also occurs in the in-plane direction of the light emitting layer because the heating spreads greatly in the lateral direction of the electrode, and color mixing between adjacent pixels is likely to occur. In particular, the higher the definition, the more the problem of color mixing increases. As described above, the conventional techniques relating to the method of forming a light emitting layer corresponding to full color display are difficult to apply to high definition pixels, and have many difficult problems.

The present invention has been made in order to solve the above problems, and provides a method of manufacturing an active matrix driven organic electroluminescence device having high definition and good productivity. The purpose is to:

[0011]

According to a first aspect of the present invention, there is provided a process for forming a pixel electrode substrate having a light emitting layer made of an organic material on pixels provided in a matrix, and comprising at least a dye. A step of forming a dye stamp having a photoreactive resin layer pattern of a predetermined shape at predetermined intervals,
The pixels and the photoreactive resin layer pattern are opposed to each other, and after positioning and positioning the pixel electrode substrate and the dye stamp, a step of bringing them into close contact, and at least one of the pixel electrode substrate or the dye stamp. Heating at a predetermined temperature for a predetermined time, diffusing at least the dye among the substances contained in the photoreactive resin layer pattern into the light emitting layer, and forming a counter electrode on the light emitting layer. It is characterized by the following. According to the first invention, a dye stamp having a photoreactive resin pattern containing at least a dye on a substrate in a dense state is prepared in advance by using a thin film microfabrication technique. At least a dye contained in the photoreactive resin pattern is disposed so as to be opposed to a pixel electrode substrate having pixels formed by processing, and the photoreactive resin pattern and the pixel are positioned and closely contacted with each other. Is to be thermally diffused into the light emitting layer provided on the pixel,
Even if the pixels are fine and high definition, the dye can be accurately doped into the light emitting layer corresponding to the pixels, and a high definition organic EL device can be manufactured. According to a second aspect of the present invention, in addition to the features of the first aspect, the pixels are arranged in a matrix on a substrate as a set of three types of pixels related to three primary colors of light. 3 on other substrate
A matrix comprising a set of first, second, and third photoreactive resin layer patterns each containing a colorant relating to primary color light, wherein the pixel and the photoreactive resin correspond to each other. The method is characterized in that it is performed by positioning the layer pattern. According to the second invention, the dye stamp is provided with the photoreactive resin layer pattern relating to the three primary colors of light corresponding to the pixels relating to the three primary colors of light, and the photoreactive resin layers of the corresponding colors correspond to each other. Since the conductive resin layer pattern and the pixels are positioned, a full-color high-definition organic EL device can be easily manufactured. Further, since the dyes for the three primary colors can be simultaneously doped into the light emitting layers on the pixels of the corresponding colors, the production of the organic EL device is efficient. According to a third aspect of the present invention, in addition to the features of the first aspect, the pixels are arranged on a substrate in a matrix in a form of a set of three types of pixels related to light of three primary colors. A first dye stamp provided at predetermined intervals with a first photoreactive resin layer pattern of a predetermined shape containing at least a first dye of three primary colors on another substrate, and a predetermined shape containing at least a second dye. A second dye stamp provided with a second photoreactive resin layer pattern at a predetermined interval; and a third dye stamp provided at a predetermined interval with a third photoreactive resin layer pattern of a predetermined shape containing at least a third dye. The first dye stamp and the pixel electrode substrate are opposed to each other, and the first photoreactive resin layer pattern and the pixel of the corresponding color are positioned and arranged, and are included in the first photoreactive resin layer pattern. Substance A step of diffusing migrate the first dye in the light-emitting layer even without, second, third dye stamp, in which individual, and having a step which is carried out by repeating the process. According to the third aspect, the dye of the corresponding color is individually doped into the light emitting layer on the pixel. Therefore, it is possible to select and perform the optimal heating diffusion condition for each dye, and to achieve high brightness. It is possible to manufacture a high-definition organic EL device.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. FIG. 1 is a sectional view showing a schematic configuration of a dye stamp applied to the first embodiment of the present invention. In the figure, reference numeral 10 denotes a dye stamp, which is provided with a photoreactive resin layer pattern 2 having a predetermined shape on a Si substrate 1 at a predetermined interval. The photoreactive resin layer pattern 2 is formed in a matrix with a set of photoreactive resin layer patterns 2r, 2g, and 2b individually containing R, G, and B dyes.

The photoreactive resin layer of the dye stamp applied to the present invention has a g-line (436 nm) and an i-line (365n).
m), mid UV (300-350 nm), deep
Any material having reactivity to UV (200 to 300 nm) or electron beam may be used. For example, in the case of a positive resist, OFPR-800 (trade name) manufactured by Tokyo Ohka as a novolak resin or THMR-iP
3100 (product name) is applicable.

In the case of a negative resist, OMR-85 manufactured by Tokyo Ohka, which is an azide rubber resin, is used. In the case of a photopolymer, an acryloyl group or a methacryloyl group having photocurability to ultraviolet rays is used. Functional or polyfunctional acrylate prepolymers, acrylic or methacrylic vinyl monomer compounds and the like are used. For example, KAYARAD MAND manufactured by Nippon Kayaku
A (trade name) and KAYARAD HX220 (trade name)
Etc. can be applied. When a photopolymer is used, Darocur 1173 manufactured by Merck is used as a polymerization initiator.
And the like are added.

As the dye, RG having fluorescence is used.
Any type can be applied as long as it develops the B system, but for the R system, for example, a porphyrin compound, a chlorin compound, a perylene compound, a dicyanopyran compound, a squarylium compound, a distyryl compound, a eurolysine compound, and the like can be applied. In the G system, coumarin compounds, quinacridone compounds, quinolinol metal complex compounds and the like can be used. In the B system, existing fluorescent dyes such as distyrylaryl compounds, diarylamine compounds, triarylamine compounds, tetraphenylbutadiene, and perylene can be used. Can be used.

The concentration of the dye dissolved in the solution of the photoreactive resin layer is not particularly limited. However, when the dye is diffused and transferred into the light emitting layer provided on the pixel electrode substrate described in FIG. In order to easily control the concentration of the dye diffused in the light emitting layer by controlling the heating temperature and time,
It is preferable to be in the range of about 0.01 to 1.0 wt%. However, in order to make the diffusion transfer condition of the dye the same as that of the RGB dye, the optimal concentration of the dissolved RGB in the photoreactive resin layer solution is selected and applied for each dye.

When the light-emitting polymer material forming the light-emitting layer emits light of the B-system with good color purity, the fluorescent dye to be diffused may be only two types of R-system and G-system. FIG. 2 is a cross-sectional view illustrating a schematic configuration of a pixel electrode substrate applied to the present invention. The pixel electrode substrate 20
An active matrix layer 22 for driving a pixel electrode, a pixel electrode layer 23, a hole transport layer 24, and a light emitting layer 25 are sequentially stacked on a Si substrate 21. The pixels 26r, 26g, and 26b corresponding to the three primary colors have the hole transport layer 24 and the light emitting layer 25 on the pixel electrodes 23r, 23g, and 23b of the corresponding colors, respectively.
6r, 26g, 26b are separated from each other by a partition wall 27.

The light-emitting layers 25 provided in the pixels 26r, 26g, and 26b are made of a polymer light-emitting material such as a polyfluorene compound, a polyphenylenevinylene compound, a polythiophene compound,
A polymer such as a polyvinyl carbazole compound or a polycarbonate compound, or a copolymer of the above polymer with a molecular group having a charge injection function and a color purity improving function can be used. As a film forming method, a spin coating method, a casting method, a dip method, a spray method, a Langmuir-Blodgett method, etc. of a wet method can be applied, and a film thickness range of about 10 to 200 nm, preferably 20 to 100 nm. Is formed.

If necessary, a hole transporting material such as a carbazole compound or an electron transporting material such as an oxadiazole compound can be used in the light emitting layer material such as the above polymer light emitting material. . Further, the pixel electrodes 23r, 2r
An electron injection layer of a polythiophene compound, a polyaniline compound, a phthalocyanine compound, or the like, and an electron transport layer comprising a plurality of diarylamine groups may be provided on 3g and 23b, and the light emitting layer 25 may be formed thereon.

A method for manufacturing an organic EL device according to the first embodiment of the present invention will be described with reference to FIG. FIG. 3 is a schematic manufacturing process diagram of the manufacturing method according to the first embodiment of the present invention. First, as shown in FIG. 3A, the dye stamp 10 and the pixel electrode substrate 20 are arranged to face each other. At this time, the photoreactive resin layer patterns 2r, 2g, and 2b correspond to the pixels 2 of the corresponding color.
6r, 26g, 26b, and the light emitting layer 2
5 is arranged closely. Thereafter, at least one of the dye stamp 10 or the pixel electrode substrate 20 is heated at a predetermined temperature for a predetermined time, and the photoreactive resin layer patterns 2r, 2g,
The light emitting layer 25 contains the R, G, and B dyes respectively contained in 2b.
The light-emitting layers 25R, 25 corresponding to each color
G, 25B are formed.

Here, the heating is performed in an inert atmosphere,
Further, if necessary, the dye stamp and the pixel electrode substrate may be pressed. The diffusion amount of the dye into the light emitting layer 25 is:
Affects EL emission intensity. That is, when the amount of diffusion of the dye is small, the EL emission intensity is low, and when the amount is excessive, the emission intensity is reduced due to concentration quenching. Thus, there is an optimum value for the amount of dye diffusion, and the heating temperature and heating time must be strictly controlled. This will be described later in detail.

Next, as shown in FIG.
5, an electron transport layer 28 and a transparent cathode layer 29 are formed. Thus, a full-color compatible organic EL element 50 is manufactured. The organic EL element 50 shown in FIG. 3B has a configuration in which light of each color emitted from the pixel is emitted upward through the transparent cathode layer 29. The photoreactive resin layer patterns 2r, 2g, and 2b contain at least a dye, but may also contain a hole transport material or an electron transport material as needed.

As described above, it is known that the diffusion amount of the dye into the light emitting layer 25 has a strong influence on the EL light emission intensity. When the dye is diffused into the light emitting layer 25, the diffusion concentration and the uniformity are determined by the heating temperature, the melting point of the dye, and the light emitting layer 25.
Glass transition temperature (T
g) and the like, but the present inventors have conducted intensive studies and found that the heating temperature and the heating time can be easily controlled by management.

FIG. 4 is a diagram showing the correlation between the heating time and the emission intensity (PL intensity) using the heating temperature as a parameter.
FIG. 4 shows an example in which polyvinyl carbazole is used as the polymer material of the light emitting layer, urethane acrylate is used as the polymer material of the photoreactive resin layer, and G-coumarin 6 is used as the dye. In the figure, the broken line indicates the case where the heating temperature is 90 ° C., the dotted line indicates the case where the heating temperature is 110 ° C., the solid line indicates the case where the heating temperature is 120 ° C., and the dashed line indicates the case where the heating temperature is 140 ° C. Since it is difficult to measure the diffusion concentration of the dye, here, the diffusion concentration of the dye was evaluated based on the PL intensity by photoluminescence measurement of the light emitting layer.

FIG. 4 shows that the higher the substrate heating temperature, the higher the amount of dye diffusion, the higher the PL intensity, and the higher the diffusion speed. If the heating temperature is 140 ° C. or higher, the amount of dye diffusion increases and the PL intensity increases, but control is difficult because the diffusion speed is too high. On the other hand, when the heating temperature is 110 ° C. or lower, the dye is not sufficiently diffused, and the PL intensity decreases. From this result, it can be seen that the heating temperature for facilitating the control of the diffusion concentration and the diffusion speed of the dye is 120 ° C. The heating time is selected from 60 to 90 minutes when the diffusion concentration of the dye is substantially saturated.

Similarly, optimum conditions are selected for the R and B dyes. In the manufacturing method according to the first embodiment of the present invention, in order to diffuse and transfer each of the R, G, and B dyes collectively, a common condition is selected and applied as long as the difference in the PL intensity of each color is acceptable.

Next, a method for forming the dye stamp 10 used in the first embodiment of the present invention will be described with reference to FIG. FIG. 5 is a schematic process diagram illustrating a method for forming a dye stamp. First, as shown in FIG.
R photoreactive resin layer 2R containing R dye on the surface of substrate 1
Is formed by a wet method such as spin coating.

Next, as shown in FIG. 5B, an R photomask 3 having openings of a predetermined shape at predetermined intervals is placed on the R photoreactive resin layer 2R, Mask 3
Is irradiated from above to expose the R-light reactive resin layer 2R. At this time, when the R photoreactive resin layer 2R is a positive type,
The exposed part is cured and the unexposed part is uncured, and becomes soluble in a developer used in a subsequent step. When the photoreactive resin layer is of a negative type, the photoreactive resin layer has the opposite effect to that of the positive type. Therefore, when a negative-type photoreactive resin layer is applied, the opening of the mask to be used needs to be formed in an inverted relationship with the opening of the positive mask. Since the manufacturing steps are almost the same, a description will be given here based on an application example of a positive-type photoreactive resin layer.

Next, as shown in FIG. 5C, the exposed R photoreactive resin layer 2R is washed with a developing solution. At this time, the R photoreactive resin layer 2R at the unexposed portion is dissolved in the developing solution, and a photoreactive resin layer pattern 2r having a predetermined shape containing the R dye is formed at predetermined intervals on the surface of the Si substrate 1. The developer applied here, when the photoreactive resin layer is a resist, an inorganic alkali or organic alkali aqueous solution, for example,
There are NMD-3 (trade name) and DE-3 (trade name) manufactured by Tokyo Ohka. When the photoreactive resin layer is a photopolymer, alcohols such as ethanol and isopropyl alcohol, and ketones such as acetone and 2-butanone can be removed by dissolving only the uncured photopolymer.

In FIG. 5D, a G photoreactive resin layer 2G containing a G dye is formed on the surface of the Si substrate 1 by spin coating. Next, as shown in FIG. 5E, a G photomask 4 having openings of a predetermined shape at predetermined intervals.
Is placed on the G photoreactive resin layer 2G, and ultraviolet light is irradiated from above the G photomask 4 so that the G photoreactive resin layer 2G
Is exposed.

Further, as shown in FIG. 5 (f), unnecessary portions of the unexposed portions in the G photoreactive resin layer 2G are removed by dissolving with a developing solution, and the unexposed portions are removed adjacent to the R photoreactive resin layer pattern 2r. A G photoreactive resin layer pattern 2g having a predetermined shape containing a G dye is formed at predetermined intervals. Similarly, FIG.
As shown in (g), a B photoreactive resin layer 2B containing a B dye is formed on the surface of the substrate 1 by spin coating. In FIG. 5H, a B photomask 5 having openings of a predetermined shape at predetermined intervals is placed on the B photoreactive resin layer 2.
The B photoreactive resin layer 2B is exposed by irradiating light on the B photomask 5 from above.

Then, as shown in FIG. 5 (i), unnecessary portions of the unexposed portions of the B photoreactive resin layer 2B are dissolved and removed with a developing solution, and the R photoreactive resin layer pattern 2r and the G photoreactive resin are removed. A B light reactive resin layer pattern 2b having a predetermined shape containing a B dye is formed at predetermined intervals adjacent to the conductive resin pattern 2g. Thus, R and R are placed on the substrate 1 as shown in FIG.
The dye stamp 10 having the R, G, and B reactive resin layer patterns 2r, 2g, and 2b individually containing G and B dyes in a matrix is formed.

Here, the pattern shapes of the R, G, and B photomasks 3, 4, and 5 used for forming the photoreactive resin layer pattern 2 by photolithography by exposure are as shown in FIG. For example, three types are conceivable. That is, as shown in FIG. 6A, stripe-shaped openings O1, O2, and O3 are provided at predetermined intervals, and as shown in FIG. 6B, a plurality of strip-shaped openings O1, O2, and O3 are arranged in the column direction. One having openings P1, P2, P3 at predetermined intervals, and one having strip-shaped openings Q1, Q2, Q3 arranged in a plurality of steps at predetermined intervals, as shown in FIG. 6 (c). It is. These photomasks are
The arrangement of the pixels corresponding to the three primary colors is appropriately selected depending on whether it is a stripe arrangement or a staggered arrangement.

The openings O1, O2, O3, P1, P2, P3 or Q of the R, G, B photomask shown in FIG.
1, Q2 and Q3 are provided to be shifted from each other by a predetermined dimension (in FIG. 6, they are shifted in the left-right direction in the plane of the paper). Next, another method for forming the dye pattern 10 will be described with reference to FIG. FIG. 7 is a view for explaining a method of irradiating a laser to the positive-type photoreactive resin layer to remove unnecessary portions of the photoreactive resin layer and forming the same. Here, only the portions different from FIG. 5 will be described.

First, as shown in FIG. 7A, an R photomask 300 is placed on an R photoreactive resin layer 2R containing an R dye formed by coating on a Si substrate 1. In this case, the R photoreactive resin layer 2R may be either a positive type or a negative type. However, the R photomask 300 applied here is a negative type mask whose opening has an inversion relationship with the R photomask 3 of FIG. Therefore, R
The R photoreactive resin layer 2R at the portion irradiated with the laser through the opening of the photomask 300 is decomposed and removed, and as shown in FIG. 7B, the R photoreactive resin layer pattern 2r having a predetermined shape is formed. It is formed at a predetermined interval.

The laser to be used is a pulsed ultraviolet laser. For this reason, thermal damage of the photoreactive resin layer is small, and since the wavelength is short, the absorption depth of laser light into the photoreactive resin layer is small, so that the processing accuracy is high. Furthermore, since the pulse oscillation is used, the processing depth can be easily controlled by the number of pulses, so that only the other photoreactive resin layer applied on the photoreactive resin layer pattern is selectively removed. Is possible. Next, the photomask is replaced with a mask used for forming the G and B photoreactive resin layer patterns, and the above-described steps from FIG. 7A to FIG. The dye pattern 10 shown in FIG. 1 is formed.

In the method of manufacturing an organic EL device according to the first embodiment of the present invention, a photoreactive resin layer pattern 2 containing R, G, and B dyes individually is formed by using a thin film fine processing technique. The dye stamp 10 formed densely and provided with a pixel 26 at a position corresponding to the photoreactive resin layer pattern 2.
pixel electrode substrate 20 provided with and formed r, 26g, 26b
Are prepared in advance, and the photoreactive resin layer pattern 2 of the dye stamp 10 and the pixels 26r, 26g,
6b are opposed to each other, and the dye contained in the photoreactive resin layer pattern 2 is heated and diffused into the light emitting layer 25 on the pixels 26r, 26g, and 26b. Fine organic EL devices can be manufactured with high productivity.

Next, the organic E according to the second embodiment of the present invention will be described.
A method for manufacturing the L element will be described with reference to FIGS. FIG. 8 is a schematic sectional view showing a form of a dye stamp applied to the second embodiment of the present invention. FIG. 8 (a)
The R dye stamp 101 provided with the R photoreactive resin layer pattern 2r on the Si substrate 1 is a G dye stamp 10 provided with the G photoreactive resin layer pattern 2g on the Si substrate 1.
2, (c) shows a B dye stamp 103 provided with a B photoreactive resin layer pattern 2b. Each of the dye stamps in FIG. 7 can be manufactured by the steps in FIGS. 5A to 5C or FIGS. 7A to 7B.

When the photoreactive resin layer pattern 2 is formed by exposure to light, the photo-oxidation and photo-decomposition of the dye molecules may occur due to the irradiation light, or the dye may have strong light absorption in the wavelength range of the irradiation light. In the case where the photochemical reaction or curing polymerization reaction of the photoreactive resin layer is hindered by the application of
As shown in, first, to form a photoreactive resin layer pattern consisting only of a photoreactive resin layer containing no dye,
A method in which a predetermined dye is diffused and contained later is effective.

FIG. 9 is a schematic process diagram for explaining a method for producing a dye stamp in which a dye is contained after forming the photoreactive resin layer pattern. First, as shown in FIG. 9A, a photoreactive resin layer 2 containing no dye is formed on a Si substrate 1.
N is formed by spin coating. Next, as shown in FIG. 9B, the R photomask 3 is placed on the photoreactive resin layer 2N and exposed to ultraviolet light. Then, unnecessary portions are dissolved and removed with a developer to form a photoreactive resin layer pattern 2n shown in FIG. 9C.

Further, as shown in FIG. 9D, an R dye is deposited or spin-coated on the photoreactive resin layer pattern 2n to form a film. Then, as shown in FIG.
As shown in (2), an R dye is contained in the photoreactive resin layer pattern 2n. Then, the unnecessary dye is washed and removed to form the R dye stamp 101 of FIG. 8A. The G dye stamp 102 and the B dye stamp 103 in FIG. 8 replace the photomask used in FIG. 9B with the G photomask 4 and the B photomask 5, respectively, and further, in FIG. , G dye,
It can be prepared by applying a B dye.

FIG. 10 shows the above R, G, B dye stamp 1.
It is a schematic process drawing showing the manufacturing method of 2nd Embodiment of this invention using 01,102,103. As shown in FIG. 10A, first, the R dye stamp 101 is attached to the pixel electrode substrate 2.
0. At this time, R dye stamp 1
01 of the photoreactive resin layer pattern 2r
It is positioned and closely attached to the pixels 26r, 26g, 26b of the corresponding color of 0. And the R dye stamp 10
1 or at least one of the pixel electrode substrates 20 is heated to transfer and diffuse the R dye contained in the photoreactive resin layer pattern 2r to the light emitting layer on the pixel to form the light emitting layer 25R containing the R dye. . At this time, the heating may be performed in an inert atmosphere, and the dye stamps and the pixel electrode substrate 20 may be pressurized as needed. The heating temperature and heating time are E
The optimum condition is selected from the relationship with the L emission intensity.

Next, as shown in FIG.
The G dye stamp 102 is replaced with the pixel electrode substrate 20 in the same manner as described above.
The G dye contained in the photoreactive resin layer pattern 2g of the G dye stamp 102 is heated under the optimal diffusion condition of the G dye to cause the G dye contained in the light-emitting layer 25 on the corresponding pixel to be heated.
To form a light emitting layer 25G containing a G dye.

Further, as shown in FIG. 10 (c), the B dye stamp 103 is disposed so as to face the pixel electrode substrate 20, and is heated under the optimum diffusion condition of the B dye so that the light of the B dye stamp 103 is provided. The B dye contained in the reactive resin layer pattern 2b is transferred and diffused into the light emitting layer 25 on the corresponding pixel to form a light emitting layer 25B containing the B dye. Next, FIG.
As shown in FIG. 1D, a full-color organic EL element 50 is formed by sequentially laminating the electron transporting layer 28 and the transparent cathode layer 29 so as to cover the light emitting layer 25.

As described above, in the manufacturing method according to the second embodiment of the present invention, similarly to the first embodiment of the present invention, a full-color high-definition organic EL element can be manufactured with high productivity. Further, since the dye is not exposed to ultraviolet rays, any dye can be applied regardless of the type. In addition, when controlling the diffusion concentration of a dye or the like into the photoreactive resin pattern, an organic EL device having higher luminance and higher color purity can be obtained because it can be managed under optimum diffusion conditions for each of the RGB colors.

In the above, the organic EL device having the cathode on the top surface has been described as an example. However, the electrode on the top surface does not need to be a cathode, and may be an anode as shown in FIG. The configuration of the organic EL element 500 in this case is such that the active matrix layer 2 for driving the pixel electrodes on the Si substrate 21 is formed.
2, the pixel electrode layer 23, the electron transport layer 28, the light emitting layer 25, the hole transport layer 24, and the transparent anode layer 30 are stacked in order. Also, the pixel 260 corresponding to the three primary color lights
r, 260 g, and 260 b respectively correspond to the electron transport layer 28 and the light emitting layer 2 on the pixel electrodes 23 r, 23 g, and 23 b of the corresponding colors.
5, pixels 260r, 260g, 2
60b are separated from each other by a partition wall 27.

In the organic EL device 500 of this configuration,
Light emitted from the light emitting layer 25 is emitted through the transparent anode layer 30. In the present invention, an organic E layer having a light emitting layer 25 containing a dye on the hole transport layer 24 or the electron transport layer 28 is used.
Although the L element has been described as an example, it is also possible to dope a hole or an electron transporting low molecular material into the polymer material of the light emitting layer 25 together with a dye. In this case, the organic E composed of the hole transport layer 24, the light emitting layer 25, and the electron transport layer 28
Since the electron transport molecule concentration can be increased without increasing the thickness of the L layer, the light emitting efficiency is improved.

[0048]

According to the present invention, there is provided a method of manufacturing a photoreactive resin layer pattern containing at least a dye on a substrate by using a dye stamp formed by fine processing in advance. The reactive resin layer pattern and the corresponding pixel are positioned and arranged in close contact with each other, and the dye contained in the photoreactive resin layer pattern is doped into the light emitting layer on the pixel. In addition, an organic EL device having good productivity can be manufactured. Further, the use of a dye stamp composed of the above-mentioned photoreactive resin layer pattern individually containing the dyes for the three primary colors enables the production of a full-color high-definition organic EL element. If the dye stamps for the three primary colors are separately provided, and the three types of dye stamps are individually used to dope the corresponding dye in the light emitting layer on the pixel of the corresponding color, the optimum for each dye It is possible to apply high heat diffusion conditions and to manufacture a high-luminance, high-definition full-color organic EL device.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a dye stamp applied to a first embodiment of the present invention.

FIG. 2 is a cross-sectional view illustrating a schematic configuration of a pixel electrode substrate applied to the present invention.

FIG. 3 is a schematic process diagram for explaining the manufacturing method according to the first embodiment of the present invention.

FIG. 4 is a diagram showing a correlation between a heating time and a light emission intensity with respect to a diffusion amount of a dye, using a heating temperature as a parameter.

FIG. 5 is a schematic process diagram illustrating a method for forming a dye stamp applied to the manufacturing method according to the first embodiment of the present invention.

FIG. 6 is a plan view illustrating a photomask for forming a dye stamp.

FIG. 7 is a schematic process diagram showing another method for forming a dye stamp.

FIG. 8 is a schematic sectional view showing a form of a dye stamp applied to a second embodiment of the present invention.

FIG. 9 is a schematic process diagram illustrating a method for manufacturing a dye stamp in which a dye is contained after a photoreactive resin layer pattern is formed.

FIG. 10 is a schematic process diagram illustrating a manufacturing method according to a second embodiment of the present invention.

FIG. 11 is a schematic sectional view showing another configuration example of the organic EL element.

FIG. 12 is a schematic cross-sectional view illustrating a general organic electroluminescence element.

[Explanation of symbols]

1. Si substrate (substrate), 2. Photoreactive resin layer pattern,
2r ... R photoreactive resin layer pattern (first photoreactive resin layer pattern), 2g ... G photoreactive resin layer pattern (second photoreactive resin layer pattern), 2b ... B photoreactive resin layer pattern ( (3rd photoreactive resin layer pattern), 10: dye stamp, 20: pixel electrode substrate, 25: light emitting layer, 26r, 2
6g, 26b: pixel, 29: transparent cathode layer (counter electrode),
101 ... R dye stamp (first dye stamp), 102
... G dye stamp (second dye stamp), 103 ... B dye stamp (third dye stamp)

Claims (3)

[Claims] 1. A step of forming a pixel electrode substrate provided with a light emitting layer made of an organic material on pixels provided in a matrix, and forming a photoreactive resin layer pattern having a predetermined shape containing at least a dye at predetermined intervals. Forming a dye stamp comprising: providing the pixel and the photoreactive resin layer pattern to face each other; positioning and positioning the pixel electrode substrate and the dye stamp; Heating at least one of the pixel electrode substrate and the dye stamp at a predetermined temperature for a predetermined time, and diffusing at least the dye among the substances contained in the photoreactive resin layer pattern into the light emitting layer; Forming an opposing electrode; and a method for manufacturing an organic electroluminescent element. 2. The pixel according to claim 1, wherein the pixels are arranged in a matrix with three types of pixels relating to three primary colors on a substrate, and the dye stamp is provided on another substrate. Are provided in the form of a matrix as a set of first, second, and third photoreactive resin layer patterns each individually containing, and the pixels and the photoreactive resin layer pattern of corresponding colors are positioned with respect to each other. 2. The method for manufacturing an organic electroluminescent device according to claim 1, wherein the method is performed. 3. The pixel according to claim 1, wherein three types of pixels related to the three primary colors are arranged in a matrix on a substrate, and the dye stamp is arranged on another substrate in a matrix. 1
A first dye stamp provided with a first photoreactive resin layer pattern of a predetermined shape containing at least a dye at predetermined intervals;
A second dye stamp having a predetermined shape of a second photoreactive resin layer pattern containing at least a dye at a predetermined interval, and a predetermined shape of a third photoreactive resin layer pattern containing at least a third dye at a predetermined interval. A third dye stamp provided, wherein the first dye stamp and the pixel electrode substrate are opposed to each other, and the first photoreactive resin layer pattern and the pixel of the corresponding color are positioned and arranged; A step of diffusing and transferring at least the first dye among the substances contained in the reactive resin layer pattern into the light emitting layer; and a step of repeating the above steps individually for the second and third dye stamps. The method for manufacturing an organic electroluminescent device according to claim 1, comprising: