JP5572920B2 - SUBSTRATE FOR ORGANIC ELECTROLUMINESCENT ELEMENT, ORGANIC ELECTROLUMINESCENT ELEMENT, AND METHOD FOR PRODUCING THEM - Google Patents

Description

  The present invention has a layer capable of forming a lyophilic region and a liquid repellent region by the action of a photocatalyst accompanying energy irradiation, irradiation with vacuum ultraviolet light, etc., and can pattern a light emitting layer and the like. The present invention relates to an organic electroluminescence (hereinafter, electroluminescence may be abbreviated as EL) element substrate, an organic EL element, and a method for producing them.

  Generally, in manufacturing a display using an EL element, a light emitting layer and the like are patterned. Various patterning methods such as a method of evaporating a luminescent material through a shadow mask, a method of separately coating with an inkjet, a method of destroying a specific luminescent dye by ultraviolet light irradiation, and a screen printing method are proposed as patterning methods of the light emitting layer. Has been. In addition, in the ink-jet coating method, in order to obtain a high-definition fine pattern, it has been proposed to form a bank (partition wall) and perform an ink repellent treatment on the bank surface (for example, Patent Document 1 and Patent Document). 2). Furthermore, as a method for patterning the light emitting layer, a method using a photocatalyst that enables formation of a high-definition pattern (for example, see Patent Document 3 and Patent Document 4) or a method using vacuum ultraviolet light (for example, Patent Document 5). See also).

The light emitting layer patterning method using the photocatalyst uses, for example, a charge injecting and transporting layer whose wettability changes so that the contact angle of the liquid is lowered by the action of the photocatalyst accompanying energy irradiation (see Patent Document 3). ). In this case, when the photocatalyst-containing layer and the charge injection / transport layer are arranged with a predetermined gap and the charge injection / transport layer is irradiated with energy, the wettability of the charge injection / transport layer is reduced due to the action of the photocatalyst accompanying the energy irradiation. Change. The light emitting layer can be formed in a pattern by using a pattern due to the difference in wettability formed on the surface of the charge injecting and transporting layer.
The above method utilizes the fact that the region where the photocatalyst action due to energy irradiation reaches becomes a lyophilic region, and the region where the photocatalyst effect due to energy irradiation does not reach becomes a lyophobic region. Therefore, a light emitting layer or the like is formed on a region where the action of the photocatalyst due to energy irradiation is exerted. Therefore, the hole injection property, hole transport property, etc. of the charge injection / transport layer may be impaired in the region where the action of the photocatalyst accompanying the energy irradiation is exerted.

The light emitting layer patterning method using the photocatalyst uses, for example, a decomposition removal layer that has a different contact angle between the charge injecting and transporting layer and the liquid and is decomposed and removed by the action of the photocatalyst accompanying energy irradiation (patent) Reference 3). In this case, when a decomposition / removal layer is formed on the charge injecting / transporting layer, the photocatalyst-containing layer and the decomposition / removal layer are arranged with a predetermined gap, and the decomposition / removal layer is irradiated with energy, From the action, the decomposition removal layer is decomposed and removed. By using a pattern due to the difference in wettability between the surface of the decomposition removal layer and the exposed surface of the charge injecting and transporting layer, the light emitting layer can be formed in a pattern.
The above method utilizes the fact that the region where the photocatalyst action due to energy irradiation reaches becomes a lyophilic region, and the region where the photocatalyst effect due to energy irradiation does not reach becomes a lyophobic region. Therefore, a light emitting layer or the like is formed on a region affected by the photocatalyst due to energy irradiation, so that hole injection and hole transport are performed in the region affected by the photocatalyst associated with energy irradiation. The device characteristics may be deteriorated due to a decrease in properties and the like.

Furthermore, the patterning method of the light emitting layer using the photocatalyst uses, for example, a hole injection layer that is decomposed and removed by the action of the photocatalyst accompanying energy irradiation, and a liquid repellent convex portion (see Patent Document 4). ). In this case, a hole injection layer is formed on the substrate on which the liquid-repellent convex portions are formed, and the photocatalyst-containing layer and the hole injection layer are arranged with a predetermined gap therebetween, and energy is supplied to the hole injection layer. When irradiated, the hole injection layer is decomposed and removed by the action of the photocatalyst accompanying energy irradiation. By using a pattern based on the wettability difference between the hole injection layer surface and the exposed liquid repellent convex surface, the light emitting layer can be formed in a pattern.
However, as shown in FIGS. 1A to 1F of Patent Document 4, when the top and side portions of the liquid-repellent convex portions are exposed, a coating solution for forming a light-emitting layer or the like is applied. In addition to the top of the liquid-repellent convex part, the light-emitting layer forming coating liquid or the like is difficult to adhere on the side part, and the light-emitting layer peels off from the liquid-repellent convex part, causing a short circuit or emitting light. A thin portion such as a layer or a portion where a light emitting layer or the like is not formed occurs, and so-called color unevenness occurs. In particular, when there is a thin portion such as the light emitting layer or a portion where the light emitting layer or the like is not formed, a short circuit between the electrodes easily occurs in the EL element.

Moreover, the patterning method of the light emitting layer using the above-described vacuum ultraviolet light uses, for example, a wettability changing layer whose wettability changes so that the contact angle of the liquid is reduced by irradiation with vacuum ultraviolet light (Patent Document 5). reference). In this case, the light emitting layer can be formed in a pattern by using a pattern with different wettability formed on the wettability changing layer surface.
This method utilizes the fact that the region irradiated with vacuum ultraviolet light becomes a lyophilic region, and the region not irradiated with vacuum ultraviolet light becomes a lyophobic region. Therefore, since a light emitting layer or the like is formed on the region irradiated with vacuum ultraviolet light, when the wettability changing layer has hole injecting property, hole transporting property, etc., the vacuum ultraviolet light is irradiated. In such a region, the hole injection property, the hole transport property, and the like may be impaired.

Japanese Patent No. 3951445 Japanese Patent No. 3328297 JP 2004-71286 A JP 2004-111220 A JP 2007-178783 A

  The present invention has been made in view of the above problems, and when the layer for forming the lyophilic region and the liquid repellent region has a hole injection property, a hole transport property, etc., the hole injection is performed. Organic EL element substrate capable of patterning a light emitting layer and the like without impairing properties and hole transportability, and suppressing occurrence of color unevenness and short circuit between electrodes, and a method for producing the same The main purpose is to provide

  In order to achieve the above object, the present invention provides a substrate, a first electrode layer formed on the substrate, and a resin formed on the first electrode layer in a pattern and having a liquid repellent surface. A lyophilic hole injection transport layer formed on the bank, on the side of the resin bank and on the first electrode layer in the opening of the resin bank; and on the hole injection transport layer side A pattern disposed on the surface, disposed on the top of the resin bank, the liquid repellent region in which the constituent material of the hole injection transport layer is decomposed, and the side of the resin bank and the above There is provided a substrate for an organic EL element, which is disposed on an opening of a resin bank and has a pattern composed of a lyophilic region which is a region other than the liquid repellent region.

  According to the present invention, the region where the constituent material of the hole injection transport layer is decomposed is defined as a liquid repellent region, and the region other than the liquid repellent region is a region where the constituent material of the hole injection transport layer is not decomposed. Is a lyophilic region. Therefore, it can be set as the organic EL element substrate which can pattern a light emitting layer etc., without impairing hole injection property and hole transport property. In addition, according to the present invention, since the lyophilic region is disposed on the side portion of the resin bank, the light emitting layer is formed when the organic EL element is manufactured using the organic EL element substrate of the present invention. It is also possible to suppress occurrence of a thin portion such as a portion where the light emitting layer or the like is not formed, or physical separation of the light emitting layer at the side portion of the resin bank. Therefore, it is possible to suppress the occurrence of color unevenness and a short circuit between the electrodes.

  In the said invention, the contact angle of the liquid in the said lyophilic area | region and the said liquid repellent area | region may become high toward the top part side from the side part side of the said resin-made banks. This is because, when an organic EL element is produced using the organic EL element substrate of the present invention, a light emitting layer having good flatness can be formed.

  In the present invention, a second hole injecting and transporting layer is formed between the first electrode layer and the resin bank, and the hole injecting and transporting layer. It may be a region where the constituent material of the second hole injecting and transporting layer is decomposed.

  Furthermore, in the present invention, the hole injecting and transporting layer may contain a material having a photocatalytic function. In the process of manufacturing the organic EL device substrate of the present invention, when forming a pattern composed of a liquid repellent region and a lyophilic region, the hole injection transport layer contains a material having a photocatalytic function. This is because, in the liquid repellent region, the decomposition of the constituent material of the hole injecting and transporting layer can be promoted. A high decomposition rate is advantageous because it can improve the tact for manufacturing. For example, since the thickness of the hole injection transport layer can be increased, the thickness of the hole injection transport layer is optimal. It is possible to optimize the performance of the element manufactured in the lyophilic region by adjusting the value.

  In the above case, the material having the photocatalytic function is preferably a metal oxide or an inorganic semiconductor.

  In the above case, the metal oxide may be one in which at least a part of the organometallic complex is oxidized. Unlike metal oxides, organometallic complexes can control hole injectability and hole transportability by the valence and ligand of the metal. In addition, unlike metal oxides of inorganic compounds, organometallic complexes can contain an organic moiety in the ligand, so the compatibility with organic substances contained in the hole injection transport layer is improved, and adjacent light emission Adhesiveness at the interface with an organic layer such as a layer is also improved. Therefore, it is possible to contribute to a long life.

  In this case, the organometallic complex is preferably a molybdenum complex, a titanium complex, or a mixture of a molybdenum complex and a titanium complex. Molybdenum complexes and titanium complexes are considered to have relatively high reactivity and easily form charge transfer complexes. Therefore, it is possible to further improve the element life.

In the above case, the metal oxide or inorganic semiconductor may be nanoparticles.
Furthermore, in the above case, the metal oxide may be one in which at least a part of the metal-containing nanoparticles is oxidized.
In this case, the metal-containing nanoparticles are preferably molybdenum-containing nanoparticles, titanium-containing nanoparticles, or a mixture of molybdenum-containing nanoparticles and titanium-containing nanoparticles. Molybdenum-containing nanoparticles and titanium-containing nanoparticles are considered to have relatively high reactivity and easily form charge transfer complexes. Therefore, it is possible to further improve the element life.

  Moreover, this invention is formed on the lyophilic area | region of the above-mentioned organic electroluminescent element substrate and the said organic electroluminescent element substrate, The EL layer containing at least a light emitting layer, The 2nd formed on the said EL layer. An organic EL element comprising an electrode layer is provided.

  According to the present invention, since the organic EL element substrate described above is used, good element characteristics can be obtained, and color unevenness and short-circuiting between electrodes can be prevented.

  Furthermore, the present invention provides a hole injecting and transporting layer forming step of forming a lyophilic hole injecting and transporting layer on a substrate on which a first electrode layer and a resin bank having a liquid repellent surface are formed. The hole injection / transport layer located on the top of the resin bank is irradiated with energy using a mask, and is disposed on the top of the resin bank and contained in the hole injection / transport layer. A pattern comprising a liquid-repellent region in which the material is decomposed, and a lyophilic region that is disposed on the side of the resin bank and on the opening of the resin bank and is a region other than the liquid-repellent region And a pattern forming process for forming the organic EL element substrate.

  According to the present invention, the hole injection / transport layer is irradiated with energy using a mask to decompose the material contained in the hole injection / transport layer, whereby the constituent material of the hole injection / transport layer is decomposed. A pattern composed of a liquid region and a lyophilic region other than the liquid repellent region can be formed. This lyophilic region is a region where the constituent material of the hole injecting and transporting layer is not decomposed. Therefore, it is possible to obtain an organic EL element substrate capable of patterning the light emitting layer and the like without impairing the hole injection property and the hole transport property. In addition, according to the present invention, since the pattern forming process is performed so that the lyophilic region is disposed on the side portion of the resin bank, it is possible to suppress the occurrence of uneven color and short circuit between the electrodes. An organic EL element substrate can be obtained.

  In the above invention, the mask has a transmissive region and a light shielding region, and when irradiating energy in the pattern formation step, the area of the transmissive region of the mask with respect to the area of the top of the resin bank. By adjusting at least one of the ratio and the distance between the hole injecting and transporting layer and the mask, the liquid contact angle on the surface on the hole injecting and transporting layer side is the side of the resin bank. The liquid repellent region may be formed so as to increase from the top toward the top. This is because a light emitting layer or the like with good flatness can be formed.

  In the present invention, the second hole injection / transport layer is formed on the substrate on which the first electrode layer and the resin bank having liquid repellency are formed before the hole injection / transport layer forming step. A second hole injecting and transporting layer forming step, wherein, in the pattern forming step, the second hole injecting and transporting layer located on the top of the resin bank and the hole injecting and transporting layer are masked You may irradiate energy using. In the present invention, two layers of the hole injection transport layer and the second hole injection transport layer can be decomposed simultaneously.

  Furthermore, in the present invention, the hole injecting and transporting layer contains an organometallic complex or a metal-containing nanoparticle, and at least a part of the organometallic complex or the metal-containing nanoparticle is a metal in the pattern forming step. It may be an oxide. This is because the photocatalytic action of the metal oxide promotes the decomposition of the material contained in the hole injecting and transporting layer in the pattern forming step.

  In the present invention, in the pattern formation step, a photocatalyst-containing layer substrate in which a photocatalyst-containing layer containing at least a photocatalyst is formed on the substrate is used as the mask, and the photocatalyst-containing layer substrate is used as the hole. Energy may be irradiated after the injecting and transporting layer is disposed with a gap where the action of the photocatalyst accompanying the irradiation of energy can be exerted. Moreover, you may irradiate a vacuum ultraviolet light as said energy in the said pattern formation process. This is because according to these methods, the material contained in the hole injecting and transporting layer can be decomposed with high accuracy.

  Moreover, this invention light-emits on the lyophilic area | region of the organic EL element substrate preparation process which prepares the organic EL element substrate by the manufacturing method of the above-mentioned organic EL element substrate, and the said organic EL element substrate. An organic EL comprising: a light emitting layer forming step of forming a light emitting layer by applying a layer forming coating solution; and a second electrode layer forming step of forming a second electrode layer on the light emitting layer. An element manufacturing method is provided.

  According to the present invention, since the organic EL element substrate is prepared by the above-described method for manufacturing an organic EL element substrate, the light emitting layer and the like can be patterned without impairing the hole injection property and the hole transport property. Is possible. Moreover, generation | occurrence | production of the location with thin thickness, such as a light emitting layer, and the location where a light emitting layer etc. are not formed can be suppressed, and color irregularity and the short circuit between electrodes can be prevented.

  In the present invention, a region where the constituent material of the hole injection transport layer is decomposed is defined as a liquid repellent region, and a region other than the liquid repellent region, where the constituent material of the hole injection transport layer is not decomposed or the like. Since the lyophilic region is used, the light-emitting layer and the like can be patterned without impairing the hole injection property and the hole transport property. Furthermore, since the lyophilic region is disposed on the side portion of the resin bank, the light emitting layer can be formed uniformly, and the effect of preventing uneven color and short-circuiting between the electrodes can be achieved.

  Hereinafter, the substrate for organic EL elements, the organic EL element of the present invention, and the production method thereof will be described in detail.

A. First, the organic EL element substrate of the present invention will be described. The organic EL element substrate of the present invention includes a substrate, a first electrode layer formed on the substrate, a resin bank formed in a pattern on the first electrode layer and having a liquid repellent surface. Formed on the side portion of the resin bank and on the first electrode layer in the opening of the resin bank, and has a lyophilic hole injection transport layer and a surface on the hole injection transport layer side. It is an arranged pattern, arranged on the top of the resin bank, the liquid repellent region in which the constituent material of the hole injection transport layer is decomposed, and the side of the resin bank and the resin And a pattern composed of a lyophilic region which is a region other than the liquid repellent region and is disposed on the opening of the bank.

The organic EL element substrate of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of the organic EL element substrate of the present invention. In the organic EL element substrate 1 illustrated in FIG. 1, the first electrode layer 3 is formed in a pattern on the substrate 2, and the resin bank 4 is formed in the opening of the pattern of the first electrode layer 3. A hole injection transport layer 5 is formed on the side P2 of the resin bank 4 and the first electrode layer 3 in the opening P3 of the resin bank 4, and a lyophilic solution is formed on the surface of the hole injection transport layer 5 side. A pattern composed of the conductive region 11 and the liquid repellent region 12 is formed. The surface of the resin bank 4 has liquid repellency, and the hole injection / transport layer 5 has lyophilicity. The liquid repellent region 12 is a region where the constituent material of the hole injection / transport layer 5 is decomposed, and is disposed on the top P1 of the resin bank 4. The lyophilic region 11 is a resin bank. 4 side portions P2 and the opening portion P3 of the resin bank 4 are disposed.

  FIG. 2 is a process diagram showing an example of a method for producing an organic EL element substrate of the present invention. First, as shown in FIG. 2 (a), the first electrode layer 3 is formed in a pattern on the substrate 2, and the resin bank 4 having a liquid repellent surface at the opening of the pattern of the first electrode layer 3 is used. Then, a lyophilic hole injection transport layer 5 a is formed on the first electrode layer 3 and the resin bank 4. Next, as shown in FIG. 2 (b), the substrate 22, the light-shielding portion 23 formed in a pattern on the substrate 22, and the substrate 22 so as to cover the light-shielding portion 23 contain a photocatalyst. A photocatalyst containing layer substrate 21 having a photocatalyst containing layer 24 to be prepared is prepared. Next, the photocatalyst-containing layer substrate 21 is disposed so that the photocatalyst-containing layer 24 and the hole injection / transport layer 5a face each other, and the hole injection / transport layer 5a is irradiated with ultraviolet light 27 through the photocatalyst-containing layer substrate 21. To do. Due to the irradiation of the ultraviolet light 27, as shown in FIG. 2 (c), from the action of the photocatalyst contained in the photocatalyst containing layer 24, it is contained in the hole injecting and transporting layer 5a in the exposed portion of the hole injecting and transporting layer 5a. Material is broken down. On the other hand, in the unexposed portion of the hole injection transport layer 5a, the hole injection transport layer 5b remains as it is.

  FIG. 3 is a process diagram showing another example of the method for producing an organic EL element substrate of the present invention. First, as shown in FIG. 3 (a), the first electrode layer 3 is formed in a pattern on the substrate 2, and the resin bank 4 having a liquid repellent surface at the opening of the pattern of the first electrode layer 3 is formed. Then, a lyophilic hole injection transport layer 5 a is formed on the first electrode layer 3 and the resin bank 4. Next, as shown in FIG. 3B, a metal mask 31 is disposed on the surface of the hole injection transport layer 5a, and the hole injection transport layer 5a is irradiated with vacuum ultraviolet light 37 through the metal mask 31. To do. By the irradiation with the vacuum ultraviolet light 37, as shown in FIG. 3C, the material contained in the hole injection transport layer 5a is decomposed in the exposed portion of the hole injection transport layer 5a. On the other hand, in the unexposed portion of the hole injection transport layer 5a, the hole injection transport layer 5b remains as it is.

  In this way, in the portion that has been subjected to the photocatalyst action due to the energy irradiation or the portion that has been irradiated with the vacuum ultraviolet light, the material contained in the hole injecting and transporting layer is the action of the photocatalyst accompanying the energy irradiation or the vacuum ultraviolet light. By being decomposed by irradiation or the like, a region having liquid repellency can be obtained.

This is because the resin bank is exposed when the material contained in the hole injecting and transporting layer is decomposed by the action of a photocatalyst associated with energy irradiation or irradiation with vacuum ultraviolet light, etc., and the liquid repellent included in this resin bank This is considered to be because the region has liquid repellency. The portion of the hole injection transport layer that has been subjected to the action of the photocatalyst due to the energy irradiation or the portion irradiated with the vacuum ultraviolet light is, for example, a portion that does not contain the constituent material of the hole injection transport layer, the hole injection transport layer Compared with the amount of the material contained, it is a portion containing a small amount of the material, or a portion containing a decomposition product of the constituent material of the hole injection transport layer. As a result, the resin bank is completely or partially exposed in the portion where the photocatalyst action due to energy irradiation or the portion irradiated with vacuum ultraviolet light is irradiated, or the thickness of the hole injection transport layer is very large. It is thought that it will become thinner.
It is also conceivable that the material contained in the hole injecting and transporting layer is modified by the action of a photocatalyst accompanying energy irradiation or irradiation with vacuum ultraviolet light. In this case, the portion that has been subjected to the action of the photocatalyst accompanying the energy irradiation of the hole injection / transport layer or the portion that has been irradiated with the vacuum ultraviolet light is, for example, a portion that contains a modified material of the constituent material of the hole injection / transport layer. It becomes. Even in this case, the resin bank is partially exposed or the hole injecting and transporting layer is very thin in the portion where the photocatalyst action due to energy irradiation or the portion irradiated with vacuum ultraviolet light is irradiated. It is thought to be.

  Therefore, as illustrated in FIG. 2C and FIG. 3C, the liquid repellent region 12 in which the constituent material of the hole injecting and transporting layer is decomposed and the constituent material of the hole injecting and transporting layer are decomposed. It can be set as the organic EL element substrate 1 having the lyophilic region 11 which is a region other than the liquid repellent region 12.

  According to the present invention, the region in which the constituent material of the hole injecting and transporting layer is decomposed is defined as a liquid repellent region, which is a region other than the liquid repellent region, and the constituent material of the hole injecting and transporting layer is decomposed, modified, etc. A region that is not used is defined as a lyophilic region. Therefore, it can be set as the organic EL element substrate which can pattern a light emitting layer etc., without impairing hole injection property and hole transport property.

  In addition, since the liquid repellent region is a region where the constituent material of the hole injection transport layer is decomposed, the hole injection property, hole transport property, etc. provided in the hole injection transport layer are reduced or eliminated. Conceivable. Therefore, the liquid repellent region where the constituent material of the hole injecting and transporting layer is decomposed is considered to be a portion that does not contribute to light emission. On the other hand, since the lyophilic region is a region where the constituent material of the hole injection transport layer is not decomposed, modified, etc., the hole injection property and the hole transport property provided by the hole injection transport layer are maintained. It becomes a part that can contribute to light emission. Therefore, a pattern composed of a liquid repellent region and a lyophilic region has a liquid repellent region in which the hole injecting and transporting properties of the hole injecting and transporting layer are reduced or eliminated, and the hole injecting and transporting. It can also be said that the pattern is composed of a lyophilic region having a hole injection property, a hole transport property, and the like as provided in the layer.

Furthermore, according to the present invention, the liquid-repellent region is disposed on the top of the resin bank, and the lyophilic region is disposed on the side of the resin bank and on the opening of the resin bank. Therefore, when an organic EL element is produced using the organic EL element substrate of the present invention, a light emitting layer or the like is not formed on the liquid-repellent region disposed on the top of the resin bank. Can be patterned with high accuracy.
In addition, since the lyophilic region is arranged on the side of the resin bank, it is possible to suppress occurrence of a thin portion such as a light emitting layer or a portion where a light emitting layer or the like is not formed. It is possible to make short circuit between them difficult to occur.
Hereinafter, each structure of the organic EL element substrate of the present invention will be described.

1. Hole Injecting and Transporting Layer The hole injecting and transporting layer in the present invention is formed on the side portion of the resin bank and on the first electrode layer in the opening of the resin bank and has lyophilicity.

  As the lyophilic property of the hole injecting and transporting layer, the liquid contact angle on the surface of the hole injecting and transporting layer is relatively lower than the liquid contact angle on the surface of the resin bank, and the coating liquid for forming the light emitting layer, etc. It suffices if the wettability with respect to is good. The “liquid” for evaluating the contact angle of the liquid with respect to the lyophilic property of the hole injecting and transporting layer refers to a light emitting layer forming coating liquid that is separately applied by a method such as an ink jet method. The contact angle of the liquid required for the hole injecting and transporting layer depends on the surface tension of the light emitting layer forming coating solution to be used.

Specifically, when the surface tension of the light emitting layer forming coating liquid is 28.5 mN / m, the liquid on the surface of the hole injecting and transporting layer is used when a liquid having a surface tension of 28.5 mN / m is used. The contact angle is preferably 10 ° or more lower than the liquid contact angle on the resin bank surface, more preferably 20 ° or more, and particularly preferably 40 ° or more.
An example of the liquid having a surface tension of 28.5 mN / m is m-xylene at 22 ° C.
Moreover, the coating liquid for light emitting layer formation can adjust surface tension within the range of 10 mN / m-100 mN / m by changing the kind of solvent, or changing temperature. Therefore, it is not limited to the case where a liquid having a surface tension of 28.5 mN / m is used, and even if any liquid having a surface tension in the range of 10 mN / m to 100 mN / m is used, When the liquid is used, it is only necessary to obtain a relative difference in the contact angle of the liquid as described above.

  On the surface of the hole injecting and transporting layer, for example, the contact angle of a liquid having a surface tension of 28.5 mN / m is preferably 20 ° or less, more preferably 10 ° or less, and further preferably 5 ° or less. This is because, when the constituent material of the hole injecting and transporting layer is decomposed and the resin bank is exposed, the light emitting layer and the like can be patterned with high accuracy when the contact angle of the liquid is in the above range.

  In addition, the contact angle of the liquid is measured using a contact angle measuring device (Kyowa Interface Science Co., Ltd. CA-Z type) with a liquid surface having various surface tensions. 30 seconds later) and can be obtained from the result or in the form of a graph. In this measurement, a wetting index standard solution manufactured by Junsei Co., Ltd. is used as the liquid having various surface tensions.

  The hole injection transport layer may have a function of preventing elution of the material contained in the resin bank. Thereby, in the organic EL element using the organic EL element substrate of the present invention, the light emission characteristics can be lowered. Conventionally, when the light emitting layer is formed in the opening of the resin bank, the material contained in the resin bank is eluted into the solvent in the light emitting layer forming coating solution and mixed as an impurity in the light emitting layer. There was a bug to do. In particular, the resin bank has liquid repellency, and when fluorine is contained, there is a problem that fluorine easily elutes in the solvent in the light emitting layer forming coating solution. Impurity reduces the recombination efficiency of the luminescent material by forming a quenching site or emitting light by itself, or the ratio of current used for light emission by deteriorating the film formability of the luminescent layer For example, the light emission characteristics such as current efficiency and lifetime may be reduced. On the other hand, when the hole injection / transport layer has a function of preventing elution of the material contained in the resin bank, a light emitting layer is formed on the hole injection / transport layer. Impurities from the bank can be prevented from being mixed, and good light emission characteristics can be obtained.

  The material used for the hole injecting and transporting layer contains an organic material, is lyophilic, can stabilize the injection of holes from the anode (first electrode layer), Although it will not specifically limit if it is a material which can convey the hole inject | poured from (1st electrode layer) into the light emitting layer stably, Especially, the effect | action of the photocatalyst accompanying energy irradiation, or vacuum ultraviolet light It is preferably one that can be decomposed or easily decomposed by irradiation. As such a material, any of a material having a hole injecting property and a hole transporting property and a material having no hole injecting property and a hole transporting property can be used.

The above material may be a polymer material or a low molecular material. When a polymer material is used, the film strength can be increased. On the other hand, when a low molecular weight material is used, it can be easily decomposed by the action of a photocatalyst accompanying energy irradiation or irradiation with vacuum ultraviolet light.
In the present specification, the polymer material means a material having a weight average molecular weight of 2000 or more. The low molecular weight material means a material having a molecular weight of less than 2000.

  Examples of the polymer material having a hole injecting property and a hole transporting property include arylamine derivatives in addition to the compounds exemplified in the light emitting material used in the light emitting layer described in the section “B. Organic EL device” described later. , Polymers containing repeating units of anthracene derivatives, carbazole derivatives, thiophene derivatives, fluorene derivatives, distyrylbenzene derivatives, spiro compounds and the like.

  As a specific example of a polymer containing an arylamine derivative as a repeating unit, copoly [3,3′-hydroxy-tetraphenylbenzidine / diethylene glycol] carbonate (PC-TPD-DEG) as a non-conjugated polymer has the following structure: Poly [N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) -benzidine] can be given as a conjugated polymer such as PTPDES and Et-PTPDK represented.

Specific examples of the polymer containing anthracene derivatives in the repeating unit include poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (9,10-anthracene)]. it can.
Specific examples of the polymer containing carbazoles in the repeating unit include polyvinyl carbazole (PVK). Specific examples of the polymer containing thiophene derivatives in the repeating unit include poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (bithiophene)].
Specific examples of the polymer containing a fluorene derivative as a repeating unit include poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4 ′-(N- (4-sec- Butylphenyl)) diphenylamine)] (TFB) and the like.
Specific examples of the polymer containing a spiro compound as a repeating unit include poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9′-spiro-bifluorene-2, 7-diyl)] and the like. These hole transporting polymer compounds may be used alone or in combination of two or more.

  In addition, the low molecular material having hole injecting property and hole transporting property is not particularly limited. For example, the light emitting material used in the light emitting layer described in the section of “B. In addition to the exemplified compounds, arylamine derivatives, anthracene derivatives, carbazole derivatives, thiophene derivatives, fluorene derivatives, distyrylbenzene derivatives, spiro compounds, and the like can be given.

Specific examples of the arylamine derivative include N, N′-bis- (3-methylphenyl) -N, N′-bis- (phenyl) -benzidine (TPD), bis (N- (1-naphthyl-N— Phenyl) benzidine) (α-NPD), 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine (MTDATA), 4,4 ′, 4 ″ -tris (N- (2-naphthyl) ) -N-phenylamino) triphenylamine (2-TNATA).
Specific examples of the carbazole derivative include 4,4-N, N′-dicarbazole-biphenyl (CBP).
Specific examples of the fluorene derivative include N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9,9-dimethylfluorene (DMFL-TPD).
Specific examples of the distyrylbenzene derivative include 4- (di-p-tolylamino) -4 ′-[(di-p-tolylamino) styryl] stilbene (DPAVB).
Specific examples of the spiro compound include 2,7-bis (N-naphthalen-1-yl-N-phenylamino) -9,9-spirobifluorene (Spiro-NPB), 2,2 ′, 7,7 ′. -Tetrakis (N, N-diphenylamino) -9,9'-spirobifluorene (Spiro-TAD) and the like.

  On the other hand, as a material having no hole injecting property or hole transporting property, for example, a barrier material for providing a hole injecting and transporting layer with a function of preventing elution of the material contained in the resin bank, In addition, a light emitting layer, a third hole injecting and transporting layer, etc. are formed on the lyophilic region when an organic EL device is produced using the organic EL device substrate of the present invention, and adhesion to the first electrode layer. In this case, an adhesive material for enhancing the adhesion with the light emitting layer, the third hole injecting and transporting layer and the like can be used.

The barrier material is lyophilic, stabilizes the injection of holes from the anode (first electrode layer), and stably emits holes injected from the anode (first electrode layer). Although it will not specifically limit if it is a material which does not have a bad influence on transport in a layer, Especially, it is preferable that it is a polymeric material whose weight average molecular weight is 2000 or more.

  The adhesive material is lyophilic and can stabilize injection of holes from the anode (first electrode layer), and holes injected from the anode (first electrode layer). The material is not particularly limited as long as it can be stably transported into the light emitting layer.

  The hole injecting and transporting layer may contain additives such as a binder resin, a curable resin, and a coating property improving agent, as necessary. Examples of the binder resin include polycarbonate, polystyrene, polyarylate, and polyester.

  Moreover, it is preferable that a positive hole injection transport layer contains a heat | fever and / or photocurable material further. Or it is preferable that the material which has a hole transportability contained in a positive hole injection transport layer has a heat and / or a photocurable functional group. Since the hole injecting and transporting layer can be cured by having heat and / or photocuring properties, even when the adjacent light emitting layer is formed by coating, a light emitting layer forming coating solution is used. When applying, elution of the constituent components of the hole injection transport layer can be reduced. The heat and / or photocurable functional group introduced into the hole transporting material contained in the hole injecting and transporting layer includes acrylic functional groups such as acryloyl group and methacryloyl group, vinyl group, and vinylene. Groups, epoxy groups, isocyanate groups, cinnamate groups, cinnamoyl groups, coumarin groups, carbazole groups and the like.

  The hole injecting and transporting layer may contain a material having a photocatalytic function in addition to the above materials. In the process of manufacturing the organic EL device substrate of the present invention, when forming a pattern composed of a liquid repellent region and a lyophilic region, the hole injection transport layer contains a material having a photocatalytic function. This is because, in the liquid repellent region, the decomposition of the constituent material of the hole injecting and transporting layer can be promoted. A high decomposition rate is advantageous because it can improve the tact for manufacturing. For example, since the thickness of the hole injection transport layer can be increased, the thickness of the hole injection transport layer is optimal. It is possible to optimize the performance of the element manufactured in the lyophilic region by adjusting the value.

  The material having the photocatalytic function is preferably a metal oxide or an inorganic semiconductor.

The metal oxide and the inorganic semiconductor may be nanoparticles. That is, the material having a photocatalytic function may be metal oxide nanoparticles or inorganic semiconductor nanoparticles.
Nanoparticles refer to particles having a diameter on the order of nm (nanometer), that is, less than 1 μm.

  The metal oxide nanoparticles are preferably those in which at least a part of the metal-containing nanoparticles are oxidized. The metal-containing nanoparticle includes a metal and / or a metal compound. That is, the hole injecting and transporting layer may contain metal-containing nanoparticles containing a metal and / or a metal compound. The metal and metal compound contained in the metal-containing nanoparticle are more reactive than the metal oxide of the inorganic compound, and the metal-containing nanoparticle is in contact with the organic material in the hole injection transport layer or metal It is considered that a charge transfer complex is easily formed between the contained nanoparticles. Therefore, it is possible to improve the lifetime of the element.

The formation of a charge transfer complex means that, for example, by ¹ H NMR measurement, when metal-containing nanoparticles are mixed into a solution of an organic material used for a hole injecting and transporting layer, around 6 to 10 ppm of the organic material This is suggested by the observation of a phenomenon in which the shape of the proton signal derived from the aromatic ring and the chemical shift value observed in Fig. 1 change compared to before mixing the metal-containing nanoparticles.

  Examples of the metal-containing nanoparticles include molybdenum-containing nanoparticles, titanium-containing nanoparticles, platinum-containing nanoparticles, palladium-containing nanoparticles, and nickel-containing nanoparticles.

  Among these, the metal-containing nanoparticles are preferably molybdenum-containing nanoparticles, titanium-containing nanoparticles, or a mixture of molybdenum-containing nanoparticles and titanium-containing nanoparticles. Molybdenum-containing nanoparticles and titanium-containing nanoparticles have a relatively high reactivity, and are considered to easily form a charge transfer complex with the organic material in the hole injection transport layer or between the nanoparticles. Therefore, it is possible to further improve the element life. Molybdenum-containing nanoparticles and titanium-containing nanoparticles become photocatalytically active metal oxides when irradiated with energy such as ultraviolet light and vacuum ultraviolet light in the atmosphere containing oxygen and water. Therefore, in the process of manufacturing the organic EL element substrate of the present invention, when forming a pattern composed of a liquid repellent region and a lyophilic region, the structure of the hole injection transport layer is formed from the inside of the hole injection transport layer. The material can be decomposed.

The metal-containing nanoparticle contains a metal and / or a metal compound, and usually contains metal and / or metal compound particles.
The particles of the metal and / or metal compound may have a single structure or a composite structure, and may have a core / shell structure, an alloy, an island structure, or the like.
For example, the molybdenum compound contained in the molybdenum-containing nanoparticle, molybdenum oxide _{(MoO 2, MoO 3),} MoS 2, MoB 2, MoSe 2, MoCl x (x = 3,4,5) , and the like. However, not only the molybdenum compounds having the valences exemplified here are included, but the Mo particles and compounds having various valences, for example, oxides and borides may be mixed in the nanoparticles depending on the processing conditions. .

  Moreover, the said metal containing nanoparticle may contain the protective agent. In this case, unlike the metal oxide of the inorganic compound, since the nanopart contains an organic portion as a protective agent, the compatibility with the organic material in the hole injecting and transporting layer is improved, and the adjacent light emitting layer or the like is used. The adhesion at the interface with the organic layer is also good. Therefore, it is possible to contribute to a long life.

  The type of the protective agent is appropriately selected and is not particularly limited. However, from the viewpoint of surface protection and dispersion stability of the metal and / or metal compound particles, a linking group capable of linking with the metal and / or metal compound, It is preferable that the organic group which has hydrophobicity is contained. Examples of the protective agent include a structure having a hydrophilic group as a linking group at the end of a hydrophobic organic group. The protective agent may be a low molecular compound or a high molecular compound.

  The linking group is not particularly limited as long as it has an effect of linking with a metal and / or a metal compound. The connection includes adsorption and coordination, but is preferably a chemical bond such as an ionic bond or a covalent bond. The number of linking groups in the protective agent may be any number as long as it is one or more in the molecule. When metal-containing nanoparticles are dispersed in an organic material used for the hole injecting and transporting layer, if two or more of the linking groups are present in one molecule of the protective agent, the protective agents are polymerized to be compatible with the organic material. There is a possibility that a bad linking group portion is exposed on the organic material side which is a binder component and the compatibility between the organic material and the metal-containing nanoparticles is inhibited. Therefore, in such a case, it is preferable that there is one linking group in one molecule of the protective agent. When the number of linking groups is one in one molecule, the protective agent binds to the particle or forms a dimer by a bimolecular reaction and stops the reaction. Since this dimer has poor adhesion to the particles, it can be easily removed from the film by applying a washing step.

  Examples of the linking group include a hydrophilic group such as carboxyl group, amino group, hydroxyl group, thiol group, aldehyde group, sulfonic acid group, amide group, sulfonamide group, phosphoric acid group, phosphinic acid group, and P═O group. Can be mentioned. The linking group is preferably at least one selected from functional groups represented by the following general formulas (1a) to (1l).

（式中、Ｚ_１、Ｚ_２およびＺ_３は、各々独立にハロゲン原子、またはアルコキシ基を表す。）

(In the formula, Z ₁ , Z ₂ and Z ₃ each independently represents a halogen atom or an alkoxy group.)

  As the organic group contained in the protective agent, a linear or branched saturated or unsaturated alkyl group having 4 or more carbon atoms, preferably 6 to 30 carbon atoms, more preferably 8 to 20 carbon atoms, aromatic hydrocarbons and And / or a heterocyclic ring. Among them, it is possible that the protective agent contains a linking group capable of linking with a metal and / or a metal compound, and an aromatic hydrocarbon and / or a heterocyclic ring, thereby improving compatibility with an organic material and adjacent organic layers. It is preferable from the viewpoint of improving the dispersion stability of the film and improving the long driving life by improving the adhesion to the film.

Specific examples of the aromatic hydrocarbon and / or heterocyclic ring include benzene, triphenylamine, fluorene, biphenyl, pyrene, anthracene, carbazole, phenylpyridine, trithiophene, phenyloxadiazole, phenyltriazole, benzimidazole, Examples thereof include phenyltriazine, benzodiathiazine, phenylquinoxaline, phenylene vinylene, phenylsilole, and combinations of these structures.
Moreover, unless the effect of this invention is impaired, you may have a substituent in the structure containing an aromatic hydrocarbon and / or a heterocyclic ring. Examples of the substituent include a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a cyano group, and a nitro group. Among linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like are preferable.

  The protective agent preferably has a hole transporting group because it contributes to a longer driving life by improving compatibility with an organic material and hole transporting property. A hole-transporting group is a group whose chemical structural group exhibits the property of having a drift mobility of holes, and as another definition, a known hole-transporting group such as the Time-Of-Flight method can be detected. This method can be defined as a group that can obtain a detection current resulting from hole transport. In the case where the hole transporting group cannot exist by itself, the compound in which a hydrogen atom is added to the hole transporting group may be a hole transporting compound. Examples of the hole transporting group include a residue from which a hydrogen atom has been removed from the organic material (arylamine derivative, carbazole derivative, thiophene derivative, fluorene derivative, distyrylbenzene derivative, etc.).

  In the metal-containing nanoparticles, the content ratio of the metal and / or metal compound and the protective agent is appropriately selected and is not particularly limited, but the protective agent is 10 to 20 weights with respect to 100 parts by weight of the metal and / or metal compound. Part.

The average particle size of the metal-containing nanoparticles is not particularly limited, and can be, for example, in the range of 0.5 nm to 100 nm, particularly in the range of 0.5 nm to 20 nm, particularly in the range of 1 nm to 10 nm. It is preferable that This is because it is difficult to produce a product having a particle size that is too small. On the other hand, if the particle size is too large, the surface area per unit weight (specific surface area) may be small, and the desired effect may not be obtained, and the surface roughness of the thin film may be large, resulting in frequent shorts. Because.
The average particle diameter is a volume average particle diameter or a number average particle diameter measured by a dynamic light scattering method. In the state dispersed in the hole injection transport layer, the average particle diameter is a scanning electron. From an image obtained using a microscope (SEM) or a transmission electron microscope (TEM), a region where 20 or more metal-containing nanoparticles are confirmed to be present is selected, and all the metals in this region are selected. The particle size of the contained nanoparticles is measured, and the average value is obtained.

  The manufacturing method of a metal containing nanoparticle will not be specifically limited if it is a method which can obtain the metal containing nanoparticle mentioned above. For example, the liquid phase method etc. are mentioned.

  The content of the organic material is 10 to 10000 parts by weight with respect to 100 parts by weight of the metal-containing nanoparticles, so that the hole injecting and transporting property is high and the film has high stability and achieves a long life. This is preferable. If the content of the organic material is too small, it is difficult to obtain the effect of the organic material. On the other hand, when there is too much content of the said organic material, it will become difficult to acquire the effect using a metal containing nanoparticle.

The metal oxide may be one in which at least a part of the organometallic complex is oxidized. That is, the hole injecting and transporting layer may contain an organometallic complex and / or a reaction product thereof. Unlike metal oxides, organometallic complexes can control hole injectability and hole transportability by the valence and ligand of the metal. In addition, unlike metal oxides of inorganic compounds, organometallic complexes can contain an organic moiety in the ligand, so that the compatibility with the organic material contained in the hole injecting and transporting layer is good and adjacent. Adhesion at the interface with an organic layer such as a light emitting layer is also improved. Furthermore, the organometallic complex is more reactive than the metal oxide of the inorganic compound, and it is easy to form a charge transfer complex with the organic material in the hole injection transport layer or between the organometallic complexes. Conceivable. Therefore, it is possible to contribute to a long life.
The reaction product of the organometallic complex that may be contained in the hole injecting and transporting layer is a process of forming the hole injecting and transporting layer, for example, in the coating liquid for forming the hole injecting and transporting layer, during heating, A reaction product generated by a reaction of an organometallic complex, which is performed at the time of energy irradiation, element driving, or the like.

  Examples of the organometallic complex include a molybdenum complex, a titanium complex, a palladium complex, a platinum complex, and a nickel complex.

  Among these, the organometallic complex is preferably a molybdenum complex, a titanium complex, or a mixture of a molybdenum complex and a titanium complex. Molybdenum complexes and titanium complexes have relatively high reactivity, and are considered to easily form a charge transfer complex with an organic material in a hole injection transport layer or between complexes. Therefore, it is possible to further improve the element life. Molybdenum complexes and titanium complexes become photocatalytically active metal oxides when irradiated with energy such as ultraviolet light or vacuum ultraviolet light. Therefore, in the process of manufacturing the organic EL element substrate of the present invention, when forming a pattern composed of a liquid repellent region and a lyophilic region, the structure of the hole injection transport layer is formed from the inside of the hole injection transport layer. The material can be decomposed.

It should be noted that the formation of a charge transfer complex means that, for example, by ¹ H NMR measurement, when an organometallic complex is mixed into a solution of an organic material used for a hole injecting and transporting layer, it is around 6 to 10 ppm of the organic material. This is suggested by the observation of a phenomenon in which the shape of the proton signal derived from the observed aromatic ring and the chemical shift value change compared to before mixing the organometallic complex.

  In the present invention, an organometallic complex is a coordination compound containing a metal and contains a ligand in addition to the metal. The type of the ligand is appropriately selected and is not particularly limited. However, it is preferable that an organic part (carbon atom) is included in view of solvent solubility and adhesion with an adjacent organic layer. Among them, the ligand contained in the organometallic complex contains an aromatic ring and / or a heterocyclic ring, which improves solvent solubility, improves compatibility with organic materials, and adherence to adjacent organic layers. It is preferable because the dispersion stability of the film is improved by the improvement and the like and contributes to a long driving life.

Specific examples of the structure containing an aromatic ring and / or a heterocyclic ring include benzene, triphenylamine, fluorene, biphenyl, pyrene, anthracene, carbazole, phenylpyridine, trithiophene, phenyloxadiazole, phenyltriazole, and benzimidazole. , Phenyltriazine, benzodiathiazine, phenylquinoxaline, phenylene vinylene, phenylsilole, and combinations of these structures.
Moreover, unless the effect of this invention is impaired, you may have a substituent in the structure containing an aromatic ring and / or a heterocyclic ring. Examples of the substituent include a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a cyano group, and a nitro group. Among linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like are preferable.

  Moreover, as a ligand, a monodentate ligand or a bidentate ligand is preferable from the point that the reactivity of an organometallic complex becomes high. If the complex itself becomes too stable, the reactivity may be poor.

For example, the molybdenum complex includes a complex having an oxidation number of −2 to +6.
The oxidation number of 0 or less molybdenum complexes, e.g., metal carbonyl _{^{[Mo -II (CO) 5]}} 2-, [(CO) 5 Mo -I Mo -I (CO) 5] 2-, [Mo (CO) ₆ ] and the like.
Examples of the molybdenum (I) complex having an oxidation number of +1 include non-Werner type complexes containing diphosphane and η ⁵ -cyclopentadienide. Specifically, Mo ^I (η ⁶ -C ₆ H ₆ ) ₂ ] ⁺ , [MoCl (N ₂ ) (diphos) ₂ ] (diphos is a bidentate ligand (C ₆ H ₅ ) ₂ PCH ₂ CH ₂ P (C ₆ H ₅ ) ₂ ).

Molybdenum (II) complexes having an oxidation number of +2 include Mo ₂ compounds in which molybdenum becomes a binuclear complex and exists in the state of (Mo ₂ ) ⁴⁺ ions. For example, [Mo ₂ (RCOO) ₄ ] And [Mo ₂ X ₂ L ₂ (RCOO) ₄ ]. Here, R in RCOO is a hydrocarbon group which may have a substituent, and various carboxylic acids can be used. Examples of carboxylic acids include fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, and valeric acid, halogenated alkyl carboxylic acids such as trifluoromethane carboxylic acid, benzoic acid, naphthalene carboxylic acid, anthracene carboxylic acid, and 2-phenylpropanoic acid. And hydrocarbon aromatic carboxylic acids such as cinnamic acid and fluorene carboxylic acid, and heterocyclic carboxylic acids such as furan carboxylic acid, thiophene carboxylic acid and pyridine carboxylic acid. In addition, a carboxylic acid having a carboxyl group in the organic material (arylamine derivative, carbazole derivative, thiophene derivative, fluorene derivative, distyrylbenzene derivative, or the like) may be used. Among these, a structure containing an aromatic ring and / or a heterocyclic ring as described above is preferably used for the carboxylic acid. Carboxylic acid has many choices and is a suitable ligand for optimizing the interaction with the organic material to be mixed, optimizing the hole injection and transport function, and optimizing the adhesion with the adjacent layer. . X is halogen or alkoxide, and chlorine, bromine, iodine, methoxide, ethoxide, isopropoxide, sec-butoxide, and tert-butoxide can be used. L is a neutral ligand, and triarylphosphine such as trialkylphosphine such as P (n-C ₄ H ₉ ) ₃ or P (CH ₃ ) ₃ or triphenylphosphine can be used.
As the molybdenum (II) complex having an oxidation number of +2, other halogen complexes such as [Mo ^II ₂ X ₄ L ₄ ] and [Mo ^II X ₂ L ₄ ] can be used. For example, [Mo ^II Br ₄ (P (n-C ₄ H ₉ ) ₃ ) ₄ ], [Mo ^II I ₂ (diars) ₂ ] (diars are dialucine (CH ₃ ) ₂ As-C ₆ H ₄ -As (CH ₃ ) ₂ ), etc. Is mentioned.

Examples of the molybdenum (III) complex having an oxidation number of +3 include [(RO) ₃ Mo≡Mo (OR) ₃ ] and [Mo (CN) ₇ (H ₂ O)] ⁴⁻ . R is a linear or branched alkyl group having 1 to 20 carbon atoms. Among linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like are preferable.
Examples of the molybdenum (IV) complex having an oxidation number of +4 include [Mo {N (CH ₃ ) ₂ } ₄ ], [Mo (CN) ₈ ] ⁴⁻ , and MoO ²⁺ having an oxo ligand. And a complex of Mo ₂ O ₂ ⁴⁺ double-crosslinked with O ²⁻ .

As the molybdenum (V) complex having an oxidation number of +5, for example, [Mo (CN) ₈ ] ³⁻ or Mo ₂ O ₃ ^{4+ in} which ^Mo═O is cross ^- linked by O ²⁻ in the trans position is used. Examples of the oxo complex having xanthogenic acid complex Mo ₂ O ₃ (S ₂ COC ₂ H ₅ ) ₄ , Mo = O having binuclear Mo ₂ O ₄ ^{2+ in} which cis is double-crosslinked with O ²⁻ Examples of the oxo complex include histidine complex [Mo ₂ O ₄ (L-histidine) ₂ ] · 3H ₂ O.
Examples of the molybdenum (VI) complex having an oxidation number of +6 include MoO ₂ (acetylacetonate) ₂ ]. In the case of a complex having two or more nuclei, there is a mixed valence complex.

  The content of the organic material is 10 to 10,000 parts by weight with respect to 100 parts by weight of the organometallic complex, so that the hole injecting and transporting property is improved and the stability of the film is high and a long life is achieved. It is preferable from the point. If the content of the organic material is too small, it is difficult to obtain the effect of the organic material. On the other hand, when there is too much content of the said organic material, it will become difficult to acquire the effect using an organometallic complex.

Examples of the inorganic semiconductor include cadmium sulfide (CdS) and cadmium selenide (CdSe).
When the inorganic semiconductor is inorganic semiconductor nanoparticles, the average particle size, production method, content, etc. of the inorganic semiconductor nanoparticles can be the same as those of the metal-containing nanoparticles.

  As a formation position of the hole injection transport layer, the hole injection transport layer may be formed on the side portion of the resin bank and on the first electrode layer in the opening of the resin bank.

  In addition, as the formation position of the hole injection transport layer on the side portion of the resin bank, the hole injection transport layer 5 is usually formed on the entire surface of the side portion P2 of the resin bank 4 as illustrated in FIG. It is formed.

  On the other hand, the position where the hole injection / transport layer is formed on the first electrode layer in the opening of the resin bank is, as illustrated in FIG. 1, on the first electrode layer 2 in the opening P3 of the resin bank 4. The hole injecting and transporting layer 5 is preferably formed on the entire surface.

  Especially, it is preferable that the positive hole injection transport layer is not formed on the top part of the resin bank. This is because the light emitting layer and the like can be patterned with high accuracy.

  The thickness of the hole injecting and transporting layer is not particularly limited as long as it can form a pattern composed of a lyophilic region and a liquid repellent region and does not inhibit the hole injecting and transporting. Is not to be done. Specifically, the thickness of the hole injecting and transporting layer is preferably in the range of 0.5 nm to 100 nm, more preferably in the range of 1 nm to 20 nm, and still more preferably in the range of 5 nm to 10 nm. . In particular, considering the process time required for the decomposition of the material, the film thickness is preferably relatively thin within the above range, but if the film thickness is too thin, the device characteristics may deteriorate.

  In addition, since the formation method of a positive hole injection transport layer is described in the term of the "C. manufacturing method of a substrate for organic EL elements" mentioned later, description here is abbreviate | omitted.

2. Resin Bank The resin bank in the present invention is formed in a pattern on the first electrode layer, and the surface has liquid repellency. The resin bank is provided to separately coat the light emitting layer and the like. In the organic EL element using the organic EL substrate of the present invention, the portion where the resin bank is formed is a non-light emitting region.

  The liquid repellency of the resin bank surface is such that the liquid contact angle on the resin bank surface is relatively higher than the liquid contact angle on the hole injecting and transporting layer surface. It only needs to have poor wettability. The contact angle of the liquid required for the resin bank depends on the surface tension of the light emitting layer forming coating solution to be used. The resin bank surface only needs to have liquid repellency with respect to the light emitting layer forming coating liquid, and even if it is lyophilic with respect to the hole injection transport layer forming coating liquid, May be sex. The difference between the contact angle of the liquid on the resin bank surface and the contact angle of the liquid on the surface of the hole injecting and transporting layer is described in the section of the hole injecting and transporting layer, and the description thereof is omitted here.

  On the resin bank surface, for example, the contact angle of a liquid having a surface tension of 28.5 mN / m is preferably 25 ° or more, more preferably 45 ° or more, and further preferably 55 ° or more. This is because, when the constituent material of the hole injecting and transporting layer is decomposed and the resin bank is exposed, the light emitting layer and the like can be patterned with high accuracy when the contact angle of the liquid is in the above range.

  Note that the method for measuring the contact angle of the liquid is described in the section of the hole injecting and transporting layer, and the description thereof is omitted here.

  The resin bank is not particularly limited as long as the surface has liquid repellency. For example, the surface and the inside may have liquid repellency, or only the surface may have liquid repellency. . Examples of the resin bank whose surface and inside have liquid repellency include those containing a liquid repellant. In addition, examples of the resin bank having liquid repellency only on the surface include those subjected to a liquid repellency treatment.

  When the resin bank contains a liquid repellent, as the liquid repellent, when the light emitting layer is formed using the light emitting layer forming coating liquid, etc., the light emitting layer forming coating liquid, etc. For example, a monomer or oligomer having a fluorine-containing group and a hydrophilic group or a lipophilic group, a fluorine-containing polymer compound, fine particles of a fluorine-containing substance, etc. Can be mentioned.

Examples of the fluorine-containing polymer compound include polytetrafluoroethylene, perfluoroethylenepropylene resin, and perfluoroalkoxy resin.
Examples of the fine particles of the fluorine-containing substance include fine particles made of polyvinylidene fluoride, a fluoroolefin vinyl ether copolymer, a trifluoride ethylene-vinylidene fluoride copolymer, and the like.
As a monomer or oligomer which has the said fluorine-containing group and a hydrophilic group or a lipophilic group, the compound represented by following General formula (1)-(6) can be illustrated, for example.

Here, in the general formulas (1) to (6), Rf and Rf ′ represent a fluoroalkyl group, R and R ′ represent an alkylene group, Rf and Rf ′, and R and R ′ are the same or different. Also good. X, X ′ and Y are —COO—, —OCOO—, —CONR ″ —, —OCONR ″ —, —SO ₂ NR ″ —, —SO ₂ —, —SO ₂ O—, — O—, —NR ″ —, —S—, —CO—, OSO ₂ O—, —OPO (OH) O—, and X, X ′ and Y may be the same or different. good. Z is —SO ₃ H, —COOH, —OH, —NH ₂ , —SO ₂ NH ₂ , —CONH ₂ , —SO ₃ —NH ₄ ⁺ , —COO—NH ₄ ⁺ , and R ″ is R represents an alkyl group or hydrogen, and R ′ ″ represents an alkyl group.

  As the lyophobic agent, any of a monomer or oligomer having a fluorine-containing group and a hydrophilic group or a lipophilic group, a fluorine-containing polymer compound, and fine particles of a fluorine-containing substance can be suitably used. Among these, it is preferable to use a monomer or oligomer having a fluorine-containing group and a hydrophilic group or a lipophilic group. These liquid repellents may use only 1 type and may use 2 or more types.

  The content of the liquid repellent is not limited as long as the desired liquid repellency can be imparted to the surface of the resin bank, and varies depending on the type of liquid repellent used, but is 0.005% by mass in the resin bank. It is preferably in the range of ˜50% by mass, and more preferably in the range of 0.01% by mass to 25% by mass. If the content of the liquid repellent is larger than the above range, sufficient strength may not be obtained. If the content of the liquid repellent is less than the above range, sufficient liquid repellent property may not be obtained. Because.

  In the case where the resin bank contains a liquid repellent, the resin bank usually contains a resin in addition to the liquid repellent. Further, the resin bank may contain a photopolymerization initiator, a sensitizer, a coatability improver, a development improver, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, and the like, if necessary. Good.

  As the resin, a resin generally used for forming a bank of an organic EL element can be used. For example, a liquid-repellent resin having liquid repellency may be used. Resin may be used. Usually, a lyophilic resin is used because it is easily available.

  Examples of the lyophilic resin include ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, polymethacrylic acid resin, Ethylene-methacrylic acid resin, polyvinyl chloride resin, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl acetal , Polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide resin, polyamid Imide resins, polyamic acid resins, polyether imide resins, phenolic resins, and urea resins.

  When the resin bank contains a liquid repellent, a method generally used for forming a bank of an organic EL element can be used as a method of forming the resin bank. For example, a photolithography method, The thermal transfer method etc. can be mentioned.

On the other hand, when the resin bank has been subjected to lyophobic treatment, a lyophilic resin having lyophilic properties is usually used for the resin bank. As this lyophilic resin, a lyophilic resin generally used for forming a bank of an organic EL element can be used, and it is appropriately selected according to the lyophobic treatment method. Specifically, a lyophilic resin used for a resin bank containing a liquid repellent can be used.
In this case, the resin bank contains a photopolymerization initiator, a sensitizer, a coatability improver, a development improver, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, and the like as necessary. It may be.

  When the resin bank has been subjected to a lyophobic treatment, the resin bank, after forming a lyophilic bank using the lyophilic resin, by applying a lyophobic treatment to the lyophilic bank, Can be formed.

  As a method of forming a lyophilic bank using the lyophilic resin, a method generally used for forming a bank of an organic EL element can be used. For example, a photolithography method, a thermal transfer method, etc. Can be mentioned.

  The lyophilic bank may be subjected to a lyophobic treatment as long as the desired lyophobic property can be imparted to the surface of the lyophilic bank. Specifically, a fluorine compound is introduced into the gas. A plasma irradiation method of irradiating the plasma as described above can be preferably used.

Examples of the fluorine compound used in the introduced gas include CF ₄ , SF ₆ , CHF ₃ , C ₂ F ₆ , C ₃ H ₈ , and C ₅ F ₈ .

  Further, the introduced gas may be a mixture of fluorine gas and another gas. Examples of other gases include nitrogen, oxygen, argon, helium, etc. Among them, nitrogen is preferably used. Furthermore, when nitrogen is used as the other gas, the mixing ratio of nitrogen is preferably 60% or more.

  The plasma irradiation method is not particularly limited as long as the surface of the lyophilic bank can be lyophobic. For example, a plasma irradiation method under reduced pressure may be used. Alternatively, a plasma irradiation method under atmospheric pressure may be used. Among these, a method of performing plasma irradiation under atmospheric pressure is preferable.

  In addition, the presence of fluorine on the surface of the lyophilic bank at the time of performing the plasma irradiation described above is based on the total amount of elements detected from the surface in the analysis by the X-ray photoelectron spectrometer (XPS: ESCALAB 220i-XL). This can be confirmed by measuring the proportion of fluorine element.

  When the first electrode layer is formed in a pattern, the resin bank is usually formed at the opening of the pattern of the first electrode layer.

  The cross-sectional shape of the resin bank may be a shape generally used for a bank of organic EL elements, and specifically includes a trapezoidal shape, a rectangular shape, and the like.

  In addition, the maximum width of the cross section of the resin bank is that when the organic EL element is produced using the organic EL element substrate of the present invention, the light emitting layer forming coating solution overflows from the opening of the resin bank. If it can prevent coming out, it will not specifically limit, According to the size etc. of an organic EL element, it sets suitably.

The height of the resin bank can be about 0.01 μm to 50 μm.
As will be described later, when the resin bank 4 is formed on the insulating layer 7 as illustrated in FIGS. 4A and 4B, the width of the resin bank is as shown in FIG. 4, the width of the resin bank 4 may be narrower than the width between the patterns of the first electrode layer 3, and as illustrated in FIG. 4B, the width of the resin bank 4 is the first width. It may be wider than the width between the patterns of the electrode layer 3.

3. Lipophilic region and lyophobic region The substrate for an organic EL device of the present invention is a pattern disposed on the surface on the hole injecting and transporting layer side, and is disposed on the top of the resin bank. A liquid-repellent region in which the constituent material of the hole injecting and transporting layer is decomposed, and a lyophilic liquid that is disposed on the side of the resin bank and on the opening of the resin bank and is a region other than the liquid-repellent region It has a pattern consisting of a sex region.

  The “lyophilic region” refers to a region having a smaller liquid contact angle than the liquid repellent region, and is a region having good wettability with respect to the light emitting layer forming coating solution. Further, the “liquid repellency region” refers to a region having a larger liquid contact angle than the lyophilic region, and is a region having poor wettability with respect to the light emitting layer forming coating solution.

  The contact angle of the liquid in the lyophobic region is preferably 10 ° or more higher than the contact angle of the liquid in the lyophilic region when a liquid having a surface tension of 28.5 mN / m is used, and more preferably 20 ° or more. It is preferably high, and particularly preferably 40 ° or higher.

  In the liquid repellent region, the contact angle of a liquid having a surface tension of 28.5 mN / m is preferably 25 ° or more, more preferably 45 ° or more, and further preferably 55 ° or more. Since the liquid repellency region is a portion where liquid repellency is required, if the contact angle of the liquid is too small, the liquid repellency is not sufficient, and the light-repellent region also contains a coating solution for forming a light emitting layer. This is because it may adhere.

  On the other hand, in the lyophilic region, the contact angle of a liquid having a surface tension of 28.5 mN / m is preferably 20 ° or less, more preferably 10 ° or less, and further preferably 5 ° or less. This is because if the contact angle of the liquid is too high, the light emitting layer forming coating solution may not easily spread and the light emitting layer may be lost.

  Note that the method for measuring the contact angle of the liquid is described in the section of the hole injecting and transporting layer, and the description thereof is omitted here.

  Moreover, the contact angle of the liquid in the lyophilic region and the liquid repellent region may increase from the side portion side to the top portion side of the resin bank. When the contact angle of the liquid in the lyophilic region and the liquid repellent region increases from the side of the resin bank toward the top, the coating solution for forming the light emitting layer on the hole injection transport layer This is because a uniform thickness can be applied. That is, a light emitting layer or the like can be formed with a uniform thickness and good flatness.

In the above case, the contact angle of the liquid in the lyophilic region and the liquid repellent region is not particularly limited as long as it increases from the side of the resin bank toward the top, and continuously. It may be higher or may be higher in stages.
Further, in the entire lyophilic region and the lyophobic region, the contact angle of the liquid may be increased from the side of the resin bank toward the top, and a part of the lyophilic region and the lyophobic region In the region, the contact angle of the liquid may increase from the side of the resin bank toward the top. When the liquid contact angle increases from the side of the resin bank toward the top, the liquid contact angle is usually at least near the boundary between the lyophilic region and the liquid repellent region. It becomes higher from the side toward the top side.

  The lyophilic region usually has the same configuration as the hole injecting and transporting layer. That is, the surface of the hole injecting and transporting layer becomes a lyophilic region.

On the other hand, the liquid repellent region is obtained by decomposing the constituent material of the hole injecting and transporting layer.
Note that “the liquid-repellent region is a material in which the constituent material of the hole injection / transport layer is decomposed” means that the constituent material of the hole injection / transport layer is not contained in the liquid-repellent region. Compared to the amount of material contained in the hole injection / transport layer, the liquid repellent region contains a small amount of the material, or the liquid repellent region is a decomposition product of the constituent material of the hole injection / transport layer, etc. Is contained. For example, the photocatalyst action associated with energy irradiation or the irradiation of vacuum ultraviolet light causes the part of the hole injection / transport layer that has undergone the photocatalyst action associated with energy irradiation or the part irradiated with vacuum ultraviolet light to be completely or partially. As a result, the resin bank is exposed.

When the second hole injecting and transporting layer is formed between the first electrode layer and the resin bank and the hole injecting and transporting layer, the liquid repellent region has the structure of the second hole injecting and transporting layer. The material is also decomposed.
“The liquid repellent region is a material obtained by decomposing the constituent material of the second hole injecting and transporting layer” means that the constituent material of the second hole injecting and transporting layer is not contained in the liquid repellent region. Or, the amount of the material contained in the liquid repellent region is smaller than the amount of the material contained in the second hole injecting and transporting layer, or the second hole injecting and transporting in the liquid repellent region. It means that a decomposition product of the constituent material of the layer is contained. For example, the photocatalyst action accompanying the energy irradiation or the irradiation of the vacuum ultraviolet light, or the like, or the part exposed to the photocatalyst action accompanying the energy irradiation of the second hole injection transport layer or the hole injection transport layer or the vacuum ultraviolet light is irradiated. The formed portion is completely or partially decomposed and removed, and the resin bank is exposed.

  The fact that the liquid repellent region is obtained by decomposing the constituent material of the hole injecting and transporting layer and the constituent material of the second hole injecting and transporting layer is decomposed, for example, by hole injecting and transporting. When the constituent material of the layer or the constituent material of the second hole injecting and transporting layer is a fluorescent material, it can be confirmed with a fluorescent microscope. If the constituent material of the hole injection / transport layer or the constituent material of the second hole injection / transport layer is not a fluorescent material, a step is formed after the second hole injection / transport layer is washed with an appropriate solvent. It can be confirmed by measuring the presence.

  The lyophilic region and the liquid repellent region are formed at a position where the liquid repellent region is disposed on the top of the resin bank, and on the side of the resin bank and on the opening of the resin bank. It is only necessary that the sex region is arranged.

  Specifically, the formation position of the liquid repellent region may be on the top of the resin bank. Normally, as illustrated in FIG. 1, the liquid repellent region is formed only on the top P 1 of the resin bank 4. 12 is arranged.

  The lyophilic region may be formed on the side of the resin bank and on the opening of the resin bank, but above all, the lyophilic region is disposed on the top of the resin bank. Preferably not. That is, it is preferable that the liquid repellent region is disposed on the entire top surface of the resin bank. This is because the light emitting layer and the like can be patterned with high accuracy.

  The pattern shape of the lyophilic region and the liquid repellent region is not particularly limited as long as the light emitting layer or the like can be patterned into a desired pattern, and is appropriately selected according to the pattern shape of the resin bank. The

  In addition, since the formation method of a lyophilic area | region and a liquid repellent area | region is described in the term of the "C. manufacturing method of a substrate for organic EL elements" mentioned later, description here is abbreviate | omitted.

4). 1st electrode layer The 1st electrode layer used for this invention is an anode, and is formed on a board | substrate.

The material for forming the first electrode layer is not particularly limited as long as it is a conductive material.
Moreover, as a material which forms a 1st electrode layer, it may have transparency and does not need to have it. For example, in the organic EL element using the organic EL element substrate of the present invention, when light is extracted from the substrate side, or in the process of producing the organic EL element using the organic EL element substrate of the present invention, the lyophilic property is obtained. In the case of irradiating energy from the substrate side when forming a pattern composed of a region and a liquid repellent region, the first electrode layer preferably has transparency. As a material having conductivity and transparency, In—Zn—O (IZO), In—Sn—O (ITO), ZnO—Al, Zn—Sn—O, and the like can be exemplified as preferable examples. On the other hand, for example, in the organic EL element using the organic EL element substrate of the present invention, when light is extracted from the opposite side of the substrate, the first electrode layer is not required to be transparent. In this case, a metal can be used as the conductive material, and specifically, Au, Ta, W, Pt, Ni, Pd, Cr, Al alloy, Ni alloy, Cr alloy, etc. Can do.

The first electrode layer may be formed on the entire surface of the substrate, or may be formed in a pattern on the substrate.
As a method for forming the first electrode layer, a general electrode forming method can be used, and examples thereof include a sputtering method, an ion plating method, and a vacuum deposition method. An example of the patterning method for the first electrode layer is a photolithography method.

5. Substrate The substrate in the present invention supports the first electrode layer, the resin bank, the hole injection transport layer, and the like.
The substrate may be transparent or not transparent. For example, in the organic EL element using the organic EL element substrate of the present invention, when light is extracted from the substrate side, or in the process of producing the organic EL element using the organic EL element substrate of the present invention, the lyophilic property is obtained. In the case of irradiating energy from the substrate side when forming a pattern composed of a region and a liquid repellent region, the substrate is preferably transparent. Examples of the transparent substrate include quartz and glass. On the other hand, for example, in the organic EL element using the organic EL element substrate of the present invention, when light is extracted from the opposite side of the substrate, the substrate is not required to be transparent. In this case, in addition to the above materials, metals such as aluminum and its alloys, plastics, woven fabrics, nonwoven fabrics and the like can be used for the substrate.

6). Second Hole Injecting and Transporting Layer In the present invention, as illustrated in FIG. 5, the second hole injecting and transporting layer is provided between the first electrode layer 3 and the resin bank 4 and the hole injecting and transporting layer 5. 6 may be formed. In this case, the liquid repellent region 12 is a region where the constituent material of the hole injection transport layer 5 is decomposed and a region where the constituent material of the second hole injection transport layer 6 is decomposed.

  The second hole injecting and transporting layer may be lyophilic or lyophobic, but is usually lyophilic.

  When the second hole injecting and transporting layer has a lyophilic property, the lyophilic property of the second hole injecting and transporting layer is preferably the same as the lyophilic property of the hole injecting and transporting layer. .

  The second hole injecting and transporting layer may have a function of preventing elution of the material contained in the resin bank. Thereby, it is possible to prevent impurities from the resin bank from being mixed into the light emitting layer, and in the organic EL element using the organic EL element substrate of the present invention, good light emission characteristics can be obtained. is there.

  In addition, about the formation material of a 2nd positive hole injection transport layer, a formation position, a film thickness, etc., since it can be the same as that of the said positive hole injection transport layer, description here is abbreviate | omitted.

  In the present invention, when the hole injecting and transporting layer contains a material having a photocatalytic function, the second hole injecting and transporting layer may also contain a material having a photocatalytic function. In the process of manufacturing the organic EL element substrate of the present invention, the hole injection transport layer and the second hole injection transport layer have a photocatalytic function when forming a pattern composed of a liquid repellent region and a lyophilic region. This is because the inclusion of the material can promote the decomposition of the constituent materials of the hole injection transport layer and the second hole injection transport layer in the liquid repellent region. Thereby, even the two layers of the hole injecting and transporting layer and the second hole injecting and transporting layer can easily decompose their constituent materials.

  In addition, since the formation method of a 2nd hole injection transport layer is described in the term of the "C. manufacturing method of a board | substrate for organic EL elements" mentioned later, description here is abbreviate | omitted.

7). Other Configurations The organic EL device substrate of the present invention may be any substrate as long as it has a pattern comprising a substrate, a first electrode layer, a hole injecting and transporting layer, a lyophilic region, and a lyophobic region. The second hole injecting and transporting layer may have other configurations.

  In the present invention, as illustrated in FIGS. 4A and 4B, the insulating layer 7 may be formed in a pattern on the substrate 2 on which the first electrode layer 3 is formed. Normally, when the first electrode layer is formed in a pattern, the insulating layer 7 is formed in the opening of the pattern of the first electrode layer 3 and covers the end of the pattern of the first electrode layer. Formed. Usually, as illustrated in FIGS. 4A and 4B, the resin bank 4 is formed on the insulating layer 7.

  The insulating layer is provided to prevent conduction between the patterns of the adjacent first electrode layers and conduction between the first electrode layer and the second electrode layer. In the organic EL element using the organic EL substrate of the present invention, a portion where the insulating layer is formed becomes a non-light emitting region.

The insulating layer forming material is not particularly limited as long as it is lyophilic and has insulating properties, and may be an organic material or an inorganic material. In particular, the material used for the insulating layer in the organic EL element can be used.
As a method for forming the insulating layer, a general method such as a photolithography method or a printing method can be used.
The thickness of the insulating layer can be about 10 nm to 50 μm.

B. Organic EL Element Next, the organic EL element of the present invention will be described. The organic EL element of the present invention is formed on the above-mentioned organic EL element substrate and the lyophilic region of the organic EL element substrate, and is formed on the EL layer including at least a light emitting layer and the EL layer. And a second electrode layer.

The organic EL element of the present invention will be described with reference to the drawings.
FIG. 6 is a schematic cross-sectional view showing an example of the organic EL element of the present invention. In the organic EL element 41 illustrated in FIG. 6, the first electrode layer 3 is formed in a pattern on the substrate 2, and the resin bank 4 is formed in the opening of the pattern of the first electrode layer 3. Hole injection transport layer 5 is formed on the first electrode layer 3 in the opening of the resin bank 4 and on the side portion of the resin, and the lyophilic region 11 and the liquid repellency are formed on the surface on the hole injection transport layer 5 side. It has an organic EL element substrate on which a pattern made of the region 12 is formed. In the organic EL element substrate, the resinous bank 4 has liquid repellency, and the hole injection / transport layer 5 has lyophilicity. The liquid repellent region 12 is a region where the constituent material of the hole injection / transport layer is decomposed, and is disposed on the top of the resin bank 4, and the lyophilic region 11 is formed on the resin bank 4. It is arranged on the side and on the opening of the resin bank 4.
The organic EL element 41 further includes a third hole injection / transport layer 42 formed on the lyophilic region 11 of the organic EL element substrate, and a light emitting layer 43 formed on the third hole injection / transport layer 42. And an EL layer 45 having an electron injecting and transporting layer 44 formed on the light emitting layer 43, and a second electrode layer 46 formed on the EL layer 45.

  According to the present invention, as described in the above section “A. Substrate for organic EL element”, the region where the constituent material of the hole injecting and transporting layer is decomposed is defined as a liquid repellent region, and other than this liquid repellent region. The region where the constituent material of the hole injecting and transporting layer is not decomposed or modified is defined as a lyophilic region. Therefore, an organic EL device in which the light emitting layer and the like are patterned can be obtained without impairing the hole injection property and the hole transport property. Moreover, since the lyophilic area | region is arrange | positioned on the side part of resin-made banks, color irregularity and the short circuit between electrodes can be prevented.

  The organic EL element substrate is described in detail in the above section “A. Organic EL element substrate”, and therefore, the description thereof is omitted here. Hereinafter, the other structure in the organic EL element of this invention is demonstrated.

1. EL layer The EL layer used in the present invention is formed on the lyophilic region of the organic EL element substrate and includes at least a light emitting layer.

Examples of the layer constituting the EL layer other than the light emitting layer include an electron injecting and transporting layer and a third hole injecting and transporting layer. In addition, a layer for improving recombination efficiency by preventing penetration of holes and electrons, such as a carrier block layer, and further confining excitons in the light emitting layer by preventing diffusion of excitons. You can also.
Hereinafter, each structure of the EL layer will be described.

(1) Light-Emitting Layer The light-emitting layer in the present invention has a function of emitting light by providing a recombination field between electrons and holes.
The light emitting material used for the light emitting layer is not particularly limited as long as it emits fluorescence or phosphorescence. In addition, the light emitting material may have a hole transport property or an electron transport property. Examples of the light emitting material include a dye material, a metal complex material, and a polymer material.

  Examples of the dye-based material include arylamine derivatives, anthracene derivatives, phenylanthracene derivatives, oxadiazole derivatives, oxazole derivatives, oligothiophene derivatives, carbazole derivatives, cyclopentadiene derivatives, silole derivatives, distyrylbenzene derivatives, distyrylpyrazine derivatives. , Distyrylarylene derivatives, silole derivatives, stilbene derivatives, spiro compounds, thiophene ring compounds, tetraphenylbutadiene derivatives, triazole derivatives, triphenylamine derivatives, trifumanylamine derivatives, pyrazoloquinoline derivatives, hydrazone derivatives, pyrazoline dimers, pyridine A ring compound, a fluorene derivative, a phenanthroline, a perinone derivative, a perylene derivative, and the like can be given. These dimers, trimers, oligomers, and compounds of two or more derivatives can also be used.

  Examples of the metal complex material include an aluminum quinolinol complex, a benzoquinolinol beryllium complex, a benzoxazole zinc complex, a benzothiazole zinc complex, an azomethylzinc complex, a porphyrin zinc complex, a europium complex, or a central metal such as Al, Zn, Be or the like A metal complex having a rare earth metal such as Tb, Eu, or Dy and having a oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, or the like as a ligand can be used.

  Polymer materials include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, etc., polyfluorene derivatives, polyvinylcarbazole derivatives, polyfluorene derivatives, polyquinoxaline derivatives, copolymers of the above materials And those obtained by polymerizing the above dye-based materials and metal complex-based materials.

A dopant may be added to the light emitting material for the purpose of improving the light emission efficiency and changing the light emission wavelength. Examples of the dopant include anthracene derivatives, perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrene derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacyclene, phenoxazone, quinoxaline derivatives, carbazole derivatives, fluorene derivatives, etc. Can be mentioned. As a phosphorescent dopant, an organometallic complex having heavy metal ions such as platinum and iridium as a center and exhibiting phosphorescence can be used. Specifically, Ir (ppy) ₃ , (ppy) ₂ Ir (acac), Ir (BQ) ₃ , (BQ) ₂ Ir (acac), Ir (THP) ₃ , (THP) ₂ Ir (acac), Ir (BO) ₃ , (BO) ₂ (acac), Ir (BT) ₃ , (BT) ₂ Ir (acac), Ir (BTP) ₃ , (BTP) ₂ Ir (acac), FIr ₆ , PtOEP, etc. Can be used. These materials may be used alone or in combination of two or more.

The light emitting layer is formed only on the lyophilic region.
In addition, since the formation method of a light emitting layer is described in the section of "D. Manufacturing method of organic EL element" mentioned later, description here is abbreviate | omitted.

(2) Electron Injection / Transport Layer The electron injection / transport layer in the present invention may be an electron injection layer having an electron injection function for stably injecting electrons injected from the cathode (second electrode layer) into the light emitting layer. The electron transport layer may have an electron transport function of transporting electrons injected from the cathode (second electrode layer) into the light emitting layer, or may be a laminate of the electron injection layer and the electron transport layer. Well, it may be a single layer having both an electron injection function and an electron transport function.

The material for forming the electron injection layer is not particularly limited as long as it can stabilize the injection of electrons into the light emitting layer. For example, Ba, Ca, Li, Cs, Mg, Sr, etc. Alkali metal or alkaline earth metal simple substance, Alkali metal alloy such as aluminum lithium alloy, Alkali metal or alkaline earth metal oxide such as magnesium oxide, strontium oxide, magnesium fluoride, calcium fluoride, strontium fluoride Alkali metal or alkaline earth metal fluorides such as barium fluoride, lithium fluoride, cesium fluoride, organic complexes of alkali metals such as 8-hydroxyquinolinolato Li (Liq), sodium polymethyl methacrylate polystyrene sulfonate And so on. Moreover, these can also be laminated | stacked and used like Ca / LiF.
Among these, alkaline earth metal fluorides are preferred. This is because the alkaline earth metal fluoride has a high melting point and can improve heat resistance.

The material for forming the electron transport layer is not particularly limited as long as it is a material capable of transporting electrons injected from the cathode (second electrode layer) into the light emitting layer. For example, bathocuproine ( Phenanthroline derivatives such as BCP) and bathophenanthroline (Bpehn), triazole derivatives, oxadiazole derivatives, silole derivatives, and aluminum quinolinol complexes such as tris (8-quinolinol) aluminum complex (Alq ₃ ). These dimers, trimers, oligomers, and compounds of two or more derivatives can also be used.

  Furthermore, as a material for forming a single layer having both an electron injection function and an electron transport function, alkali metals or alkaline earth metals such as Li, Cs, Ba, and Sr, fluorides of alkaline earth metals, 8- An electron transporting material doped with an alkali metal organic complex such as hydroxyquinolinolato Li (Liq) or an alkaline earth metal complex can be given. Examples of the electron transporting material include the light emitting material and the electron transporting material described above. The molar ratio between the electron transporting material and the doped metal is preferably in the range of 1: 1 to 1: 3, and more preferably in the range of 1: 1 to 1: 2. An electron transporting material doped with an alkali metal, an alkaline earth metal, or a fluoride or an organometallic complex thereof has a relatively high electron mobility and a higher transmittance than a single metal.

  Moreover, it is preferable that the material for forming the electron injecting and transporting layer has a relatively high resistance. This is because if the resistance is too low, crosstalk may occur.

The thickness of the electron injection layer is not particularly limited as long as its function is sufficiently exerted, but specifically, it is preferably in the range of 0.1 nm to 200 nm, more Preferably it exists in the range of 0.5 nm-100 nm.
Further, the film thickness of the electron transport layer is not particularly limited as long as its function is sufficiently exerted, but specifically, it is preferably in the range of 1 nm to 200 nm. Preferably it exists in the range of 1 nm-100 nm.
Further, the film thickness of the single layer having both the electron injection function and the electron transport function is not particularly limited as long as the film can sufficiently exhibit the function. It is preferably in the range of 1 nm to 200 nm, more preferably in the range of 0.1 nm to 100 nm.

The electron injecting and transporting layer may be formed only on the lyophilic region, or may be formed on either the lyophilic region or the liquid repellent region. It is selected as appropriate. For example, when the electron injecting and transporting layer is formed by a dry process, the electron injecting and transporting layer is usually formed on both the lyophilic region and the liquid repellent region. On the other hand, when the electron injecting and transporting layer is formed by a wet process, the electron injecting and transporting layer is usually formed only on the lyophilic region.
The method for forming the electron injecting and transporting layer is described in the section of “D. Manufacturing method of organic EL element” which will be described later, and will not be described here.

(3) Third hole injection / transport layer The third hole injection / transport layer used in the present invention preferably has a lyophilic property. In this case, the surface of the third hole injecting and transporting layer is lyophilic, and the region where the third hole injecting and transporting layer is not formed is a liquid repellent region. This is because it can be formed only on the lyophilic region.
The lyophilic property of the third hole injecting and transporting layer is preferably about the same as the lyophilic property of the second hole injecting and transporting layer.

  The material for forming the third hole injecting and transporting layer is not particularly limited as long as it is a material that can stably transport holes injected from the anode (first electrode layer) into the light emitting layer. Any of the materials used for the hole injecting and transporting layer can be used.

  The thickness of the third hole injecting and transporting layer is not particularly limited as long as its function is sufficiently exerted, but specifically, it is in the range of 0.5 nm to 100 nm. Is preferable, and more preferably in the range of 1 nm to 20 nm.

The third hole injecting and transporting layer is formed only on the lyophilic region.
In addition, since the formation method of a 3rd hole injection transport layer is described in the term of the "D. manufacturing method of an organic EL element" mentioned later, description here is abbreviate | omitted.

2. Second Electrode Layer The second electrode layer used in the present invention is a cathode and is formed on the EL layer.

  The material for forming the second electrode layer is not particularly limited as long as it is a conductive material. For example, when the organic EL element shown in FIG. 6 is a top emission type, the second electrode layer preferably has transparency. For example, in the case of the bottom emission type in the organic EL element shown in FIG. 6, the second pole layer does not require transparency. The conductive material is the same as that described in the section of the first electrode layer in the above “A. Organic EL element substrate”, and the description thereof is omitted here.

  The method for forming the second electrode layer is the same as the method for forming the first electrode layer, and a description thereof will be omitted here.

C. Next, a method for producing an organic EL element substrate of the present invention will be described. The method for producing an organic EL device substrate of the present invention is a method for forming a lyophilic hole injecting and transporting layer on a substrate on which a first electrode layer and a resin bank having a liquid repellent surface are formed. The hole injecting and transporting layer forming step and the hole injecting and transporting layer located on the top of the resin bank are irradiated with energy using a mask and disposed on the top of the resin bank. The liquid-repellent region where the material contained in the injecting and transporting layer is decomposed, and the region other than the liquid-repellent region disposed on the side of the resin bank and on the opening of the resin bank And a pattern forming step of forming a pattern composed of a lyophilic region.

The manufacturing method of the organic EL element substrate of the present invention will be described with reference to the drawings.
FIG. 2 is a process diagram showing an example of a method for producing an organic EL element substrate of the present invention. First, as shown in FIG. 2 (a), the first electrode layer 3 is formed in a pattern on the substrate 2, and the resin bank 4 having a liquid repellent surface at the opening of the pattern of the first electrode layer 3 is used. To form a lyophilic hole injection / transport layer 5a on the first electrode layer 3 and the resin bank 4 (hole injection / transport layer forming step).
Next, as shown in FIG. 2 (b), the substrate 22, the light-shielding portion 23 formed in a pattern on the substrate 22, and the substrate 22 so as to cover the light-shielding portion 23 contain a photocatalyst. A photocatalyst containing layer substrate 21 having a photocatalyst containing layer 24 to be prepared is prepared. Next, the photocatalyst-containing layer substrate 21 is arranged so that the photocatalyst-containing layer 24 and the hole injection / transport layer 5a face each other, and the hole injection located on the top of the resin bank 4 is interposed through the photocatalyst-containing layer substrate 21. The portion of the transport layer 5a is irradiated with ultraviolet light 27. Due to the irradiation of the ultraviolet light 27, as shown in FIG. 2 (c), from the action of the photocatalyst contained in the photocatalyst containing layer 24, it is contained in the hole injecting and transporting layer 5a in the exposed portion of the hole injecting and transporting layer 5a. The material is decomposed to form the liquid repellent region 12. On the other hand, in the unexposed portion of the hole injecting and transporting layer 5a, the hole injecting and transporting layer 5b remains as it is, and becomes the lyophilic region 11. Thus, the liquid repellent area 12 is arranged on the top of the resin bank 4 and the lyophilic area 11 is arranged on the side of the resin bank 4 and on the opening of the resin bank 4. A pattern is formed (FIGS. 2B to 2C, pattern forming step).

FIG. 3 is a process diagram showing another example of the method for producing an organic EL element substrate of the present invention. First, as shown in FIG. 3 (a), the first electrode layer 3 is formed in a pattern on the substrate 2, and the resin bank 4 having a liquid repellent surface at the opening of the pattern of the first electrode layer 3 is formed. To form a lyophilic hole injection / transport layer 5a on the first electrode layer 3 and the resin bank 4 (hole injection / transport layer forming step).
Next, as shown in FIG. 3 (b), a metal mask 31 is arranged on the surface of the hole injection transport layer 5a, and the hole injection transport located on the top of the resin bank 4 through the metal mask 31. The layer 5 a is irradiated with vacuum ultraviolet light 37. By the irradiation with the vacuum ultraviolet light 37, as shown in FIG. 3C, the material contained in the hole injection transport layer 5a is decomposed in the exposed portion of the hole injection transport layer 5a, and the liquid repellent region 12 is formed. It is formed. On the other hand, in the unexposed portion of the hole injecting and transporting layer 5a, the hole injecting and transporting layer 5b remains as it is, and becomes the lyophilic region 11. Thus, the liquid repellent area 12 is arranged on the top of the resin bank 4 and the lyophilic area 11 is arranged on the side of the resin bank 4 and on the opening of the resin bank 4. A pattern is formed (FIGS. 3B to 3C, pattern formation step).

  In this way, in the portion that has been subjected to the photocatalyst action due to the energy irradiation or the portion that has been irradiated with the vacuum ultraviolet light, the material contained in the hole injecting and transporting layer is the action of the photocatalyst accompanying the energy irradiation or the vacuum ultraviolet light. By being decomposed by irradiation or the like, a region having liquid repellency can be formed. This is because the resin bank is exposed when the material contained in the hole injecting and transporting layer is decomposed by the action of a photocatalyst associated with energy irradiation or irradiation with vacuum ultraviolet light, etc., and the liquid repellent included in this resin bank This is considered to be because the region has liquid repellency. Therefore, as illustrated in FIG. 2C and FIG. 3C, the liquid repellent region 12 in which the constituent material of the hole injecting and transporting layer is decomposed and the constituent material of the hole injecting and transporting layer are decomposed and modified. A pattern including the lyophilic region 11 which is a region other than the liquid repellent region 12 can be formed.

  According to the present invention, the hole injection / transport layer is irradiated with energy using a mask to decompose the material contained in the hole injection / transport layer, whereby the constituent material of the hole injection / transport layer is decomposed. A pattern composed of a liquid region and a lyophilic region other than the liquid repellent region can be formed. This lyophilic region is a portion where the action of the photocatalyst due to energy irradiation is not exerted or a portion where the vacuum ultraviolet light is not irradiated, and is a region where the constituent material of the hole injection transport layer is not decomposed. Therefore, it is possible to obtain an organic EL element substrate capable of patterning the light emitting layer and the like without impairing the hole injection property and the hole transport property.

In addition, since the hole injection / transport layer is irradiated with energy in the pattern forming process so that the lyophilic region is disposed on the side of the resin bank, the thin portion such as the light emitting layer, the light emitting layer, etc. It is possible to obtain a substrate for an organic EL element that can suppress occurrence of a portion where no is formed and can prevent color unevenness and occurrence of a short circuit between electrodes.
Hereinafter, each process in the manufacturing method of the board | substrate for organic EL elements of this invention is demonstrated.

1. Hole injection / transport layer forming step The hole injection / transport layer forming step in the present invention is a step of injecting lyophilic holes onto a substrate on which a first electrode layer and a resin bank having a liquid-repellent surface are formed. This is a step of forming a transport layer.

  As a method for forming the hole injecting and transporting layer, the first electrode layer and the entire surface on the substrate on which the resin bank having the liquid repellency is formed are described in the above section “A. Substrate for organic EL element”. There is no particular limitation as long as it is a method capable of forming a film of a material used for the hole injecting and transporting layer. For example, it may be a wet process using a hole injection transport layer forming coating solution in which the above-described materials or the like are dissolved or dispersed in a solvent, or may be a dry process. A transfer method can also be used. These methods are appropriately selected depending on the type of material used for the hole injecting and transporting layer, for example, whether the material is a high molecular material or a low molecular material. When a polymer material is used for the hole injecting and transporting layer, a wet process is preferably used. On the other hand, when a low molecular material is used for the hole injecting and transporting layer, a wet process or a dry process is preferably used. From the viewpoint of process superiority, since the light emitting layer is formed by a wet process, it is desirable that the method for forming the hole injecting and transporting layer is a wet process.

  In the case of a wet process, the solvent used in the hole injection transport layer forming coating solution is not particularly limited as long as it can dissolve or disperse the above materials. For example, acetone, methyl ethyl ketone Ketones such as cyclohexanone; alcohols such as methanol, ethanol and butanol; esters such as butyl acetate; ethers such as tetrahydrofuran and dibutyl ether; hydrocarbons such as toluene, xylene and dodecylbenzene; chlorobenzene and carbon tetrachloride Halogenated hydrocarbons such as chloroform, methylene chloride, trichloroethylene, dichloroethane and dichloromethane; glycols such as ethylene glycol and propylene glycol; glycol ethers such as ethylene glycol monomethyl ether; water , Dimethylformamide, dimethyl sulfoxide, N- methyl-2-pyrrolidone; or the like fluorine-based solvent is replaced with fluorine part of the hydrogen and the like. These solvents may be used alone or in combination of two or more.

  In the present invention, a hole injection / transport layer having lyophilicity is formed on the entire surface of the substrate on which a resin bank having a liquid repellency is formed with respect to the light emitting layer forming coating solution. By appropriately selecting the solvent, it is possible to form a hole injection / transport layer having a lyophilic property uniformly on a resin bank having a liquid repellent surface.

  The coating liquid for forming the hole injecting and transporting layer may be any method that can form the above-mentioned material uniformly over the entire surface of the substrate, such as a die coating method, a spin coating method, a dip coating method, a roll coating method, a bead. Examples thereof include a coating method, a spray coating method, a bar coating method, a gravure coating method, a blade coating method, a casting method, an ink jet method, a nozzle printing method, an aerosol method, a flexographic printing method, a screen printing method, and an offset printing method.

  Moreover, after apply | coating the coating liquid for positive hole injection transport layer formation, you may perform a drying process. As a drying method, a general drying method can be used, and for example, a heating method can be mentioned. As a heating method, for example, a method of passing or standing in a device that heats a whole specific space such as an oven, a method of applying hot air, a method of heating directly by far infrared rays, or heating with a hot plate Or the like can be used.

  On the other hand, in the case of the dry process, examples of the method for forming the hole injecting and transporting layer include a sputtering method and a vacuum deposition method.

  Since the substrate, the first electrode layer, the resin bank, and the hole injecting and transporting layer are described in detail in the section “A. Substrate for organic EL element”, description thereof is omitted here.

2. Pattern formation step The pattern formation step in the present invention is to irradiate energy using a mask to the portion of the hole injection transport layer located on the top of the resin bank, and is disposed on the top of the resin bank, The liquid repellent region where the material contained in the hole injecting and transporting layer is decomposed, and disposed on the side of the resin bank and on the opening of the resin bank, other than the liquid repellent region This is a step of forming a pattern composed of a lyophilic region which is a region.

  The liquid repellent region and the lyophilic region are described in detail in the section “A. Substrate for organic EL element”, and thus the description thereof is omitted here. Hereinafter, a method for irradiating energy using a mask for the hole injection transport layer and a mode for irradiating energy using a mask for the hole injection transport layer will be described.

(1) Method of irradiating energy using a mask As a method of irradiating energy using a mask to the portion of the hole injection transport layer located on the top of the resin bank, it is contained in the hole injection transport layer. Although it will not specifically limit if it is a method which can decompose | disassemble material, Usually, the method which can generate | occur | produce active oxygen species, such as an oxygen radical, is used by energy irradiation. This is because the material, particularly organic matter, contained in the hole injecting and transporting layer can be decomposed by the strong oxidizing / reducing power of the active oxygen species.

As such a method, for example, (i) using a photocatalyst containing layer substrate having a photocatalyst containing layer as a mask, the material contained in the hole injecting and transporting layer is decomposed by the action of the photocatalyst accompanying energy irradiation. And (ii) a method of decomposing a material contained in the hole injection / transport layer by irradiation with vacuum ultraviolet light using a vacuum ultraviolet light mask as a mask, and (iii) a photocatalytic function of the hole injection / transport layer. A method of decomposing the material contained in the hole injecting and transporting layer by the action of the material having a photocatalytic function accompanying energy irradiation, and (iv) combining the above (i) and (iii) (V) a method combining (ii) and (iii) above. In addition, for example, a method of irradiating an electron beam or plasma through a mask having a patterned opening, a method of blowing O ₂ radicals in a vacuum through a mask, or the like can be used.

Among them, the method of utilizing the action of the photocatalyst accompanying the energy irradiation of the above (i), the method of irradiating the vacuum ultraviolet light of the above (ii), the action of the material having the photocatalytic function accompanying the energy irradiation of the above (iii) is utilized. A method of combining the method of (iv) using the action of the photocatalyst accompanying energy irradiation and the method of using the action of a material having a photocatalytic function accompanying energy irradiation, and the vacuum ultraviolet light of (v) A method that combines the method of irradiating with the method of utilizing the action of a material having a photocatalytic function accompanying energy irradiation is preferable. This is because according to these methods, the material contained in the hole injecting and transporting layer can be decomposed with high accuracy. In particular, the method combining the method (iv) using the action of the photocatalyst accompanying the energy irradiation and the method using the action of the material having a photocatalytic function accompanying the energy irradiation is preferable because the pattern formation time can be shortened. .
Hereinafter, the methods (i) to (v) will be described separately.

(I) A method utilizing the action of a photocatalyst accompanying energy irradiation A method utilizing the action of a photocatalyst accompanying energy irradiation is a photocatalyst containing layer substrate in which a photocatalyst containing layer containing at least a photocatalyst is formed on a substrate as a mask. And the photocatalyst-containing layer substrate is arranged with a gap that can act as a photocatalyst accompanying the irradiation of energy with respect to the hole injection transport layer, and then irradiated with energy.

The mechanism by which the material contained in the hole injecting and transporting layer is decomposed and removed by the action of the photocatalyst accompanying energy irradiation is not necessarily clear, but the photocatalyst contained in the photocatalyst containing layer causes an oxidation-reduction reaction by energy irradiation. The active oxygen species such as superoxide radical (• O ²⁻ ) and hydroxy radical (• OH) generated thereby act on the organic matter contained in the hole injection transport layer, so that the organic matter is decomposed. Thus, it is considered that a region where the material contained in the hole injecting and transporting layer is decomposed can be formed by volatilizing and removing the decomposition product.

  Hereinafter, a method of causing the photocatalyst to act on the second hole injecting and transporting layer using the photocatalyst-containing layer substrate and the photocatalyst-containing layer substrate will be described.

(Photocatalyst-containing layer substrate)
The photocatalyst-containing layer substrate used in the present invention is such that a photocatalyst-containing layer containing at least a photocatalyst is formed on a substrate.

As the formation position of the photocatalyst containing layer, as illustrated in FIG. 7A, the photocatalyst containing layer 24 may be formed on the entire surface of the substrate 22, and as illustrated in FIG. The photocatalyst containing layer 24 may be formed in a pattern on 22.
When the photocatalyst-containing layer is formed in a pattern, the photocatalyst-containing layer is arranged with a predetermined gap with respect to the hole injecting and transporting layer, and when irradiating energy, a pattern is used using a photomask or the like. Irradiation is unnecessary, and by irradiating the entire surface, a liquid repellent region in which the material contained in the hole injecting and transporting layer is decomposed can be formed in a pattern. In this case, the energy irradiation direction may be any direction as long as the energy is irradiated to the portion where the photocatalyst containing layer and the hole injecting and transporting layer face each other. Furthermore, the energy to be irradiated is not limited to parallel light such as parallel light.

  Moreover, the light-shielding part may be formed in pattern shape in the photocatalyst containing layer substrate. When a photocatalyst-containing layer substrate having a patterned light-shielding portion is used, it is not necessary to use a photomask or perform drawing irradiation with laser light when irradiating energy. Therefore, in this case, since alignment between the photocatalyst-containing layer substrate and the photomask is unnecessary, it can be a simple process, and an expensive apparatus necessary for drawing irradiation is also unnecessary. This is advantageous in terms of cost.

  As for the formation position of the light shielding part, as illustrated in FIG. 2B, the light shielding part 23 may be formed in a pattern on the substrate 22, and the photocatalyst containing layer 24 may be formed on the light shielding part 23. As shown in FIG. 7C, a photocatalyst containing layer 24 may be formed on the substrate 22, and the light shielding portion 23 may be formed in a pattern on the photocatalyst containing layer 24. The light-shielding portion may be formed in a pattern on the surface on which the photocatalyst-containing layer is not formed.

  When the light-shielding part is formed on the substrate and when the light-shielding part is formed on the photocatalyst-containing layer, the photocatalyst-containing layer and the second hole injecting and transporting layer are compared with the case of using a photomask. Since the light-shielding portion is arranged in the vicinity of the portion arranged with a gap, the influence of energy scattering in the substrate or the like can be reduced. For this reason, it becomes possible to perform pattern irradiation of energy very accurately.

  Further, in the case where the light shielding portion is formed on the surface of the base on which the photocatalyst containing layer is not formed, for example, the photomask can be attached to the surface of the light shielding portion so as to be attachable and detachable. This is suitable for a case where the production of a manufacturing substrate is changed in a small lot.

  Specifically, the photocatalyst-containing layer substrate can be the same as the photocatalyst-containing layer side substrate described in JP-A No. 2000-249821.

  In a method using the action of a photocatalyst accompanying energy irradiation, a photocatalyst-containing layer substrate is used as a mask, and energy is irradiated in a pattern. In the case where the photocatalyst containing layer 24 is formed on the entire surface of the substrate 22 as illustrated in FIG. 7A, and energy is irradiated in a pattern form via the photocatalyst containing layer substrate and the photomask. Uses a combination of a photocatalyst-containing layer substrate and a photomask as a mask. On the other hand, as illustrated in FIG. 7A, when the photocatalyst containing layer 24 is formed on the entire surface of the substrate 22 and the pattern is drawn and irradiated using a laser, the photocatalyst containing layer is used as a mask. A layer substrate is used. When the photocatalyst containing layer 24 is formed in a pattern on the substrate 22 as illustrated in FIG. 7B, a photocatalyst containing layer substrate is used as a mask. Furthermore, when the light-shielding part 23 is formed in a pattern as illustrated in FIGS. 2B and 7C, a photocatalyst-containing layer substrate is used as a mask.

(Method of exerting photocatalytic action on hole injection transport layer using photocatalyst-containing layer substrate)
In the present invention, the photocatalyst-containing layer substrate is disposed with a gap where the photocatalyst action accompanying energy irradiation can reach the hole injecting and transporting layer. The gap includes a state where the photocatalyst containing layer and the hole injecting and transporting layer are in contact with each other.

  Specifically, the distance between the photocatalyst-containing layer and the hole injecting and transporting layer is preferably 200 μm or less. This is because by disposing the photocatalyst-containing layer and the hole injecting and transporting layer at a predetermined interval, oxygen, water, and active oxygen species generated by the photocatalytic action are easily desorbed. If the distance between the photocatalyst-containing layer and the hole injecting and transporting layer is wider than the above range, the active oxygen species generated by the photocatalytic action may be difficult to reach the hole injecting and transporting layer, which may slow down the decomposition and removal rate. There is. Conversely, if the distance between the photocatalyst-containing layer and the hole injecting and transporting layer is too narrow, oxygen, water, and active oxygen species generated by the photocatalytic action are difficult to desorb, resulting in a slow decomposition and removal rate. there is a possibility.

  The distance is more preferably in the range of 0.2 μm to 20 μm, more preferably 1 μm, considering that the pattern accuracy is very good, the sensitivity of the photocatalyst is high, and the efficiency of decomposition and removal is good. It is in the range of -10 μm.

  On the other hand, when manufacturing an organic EL device having a large area of, for example, 300 mm × 300 mm, it is extremely difficult to provide the fine gap as described above between the photocatalyst-containing layer substrate and the hole injecting and transporting layer. Therefore, when manufacturing an organic EL device having a relatively large area, the gap is preferably in the range of 5 μm to 100 μm, and more preferably in the range of 10 μm to 75 μm. By setting the gap to the above range, it is possible to suppress a decrease in pattern accuracy such as a blurred pattern, and it is possible to suppress degradation of the efficiency of decomposition and removal due to deterioration of the sensitivity of the photocatalyst. is there.

  Further, when energy irradiation is performed on a relatively large area as described above, the setting of the gap in the positioning device between the photocatalyst-containing layer substrate and the hole injecting and transporting layer in the energy irradiation device is in the range of 10 μm to 200 μm. Especially, it is preferable to set in the range of 25 micrometers-75 micrometers. By setting the set value of the gap in the above range, the pattern accuracy is not significantly reduced and the sensitivity of the photocatalyst is not greatly deteriorated, and the photocatalyst-containing layer substrate and the hole injecting and transporting layer are disposed without being in contact with each other. Because it can be done.

  In the present invention, such an arrangement state with a gap need only be maintained at least during energy irradiation.

  The energy irradiation direction is determined by whether or not the light shielding portion is formed on the photocatalyst-containing layer substrate, or by the light extraction direction of the organic EL element. For example, when the light-shielding part is formed on the photocatalyst-containing layer substrate and the base of the photocatalyst-containing layer substrate is transparent, energy irradiation is performed from the photocatalyst-containing layer substrate side. Further, for example, when the photocatalyst-containing layer is formed in a pattern, the energy irradiation direction is such that, as described above, energy is applied to the portion where the photocatalyst-containing layer and the second hole injection / transport layer face each other. Any direction is acceptable. Further, for example, when a photomask is used, energy is irradiated from the side where the photomask is disposed. In this case, the side on which the photomask is arranged needs to be transparent.

  As a method of exerting a photocatalytic action on the hole injecting and transporting layer using the photocatalyst-containing layer substrate, specifically, the characteristic change using the photocatalyst-containing layer side substrate described in JP-A-2000-249821 The method can be the same as the method of exerting the action of the photocatalyst on the layer.

(Ii) Method of irradiating vacuum ultraviolet light The method of irradiating vacuum ultraviolet light is a method of using vacuum ultraviolet light mask as a mask and irradiating vacuum ultraviolet light as energy.

  The mechanism by which the material contained in the hole injecting and transporting layer is decomposed and removed by irradiation with vacuum ultraviolet light is not necessarily clear, but when the hole injecting and transporting layer is irradiated with vacuum ultraviolet light, hole injection and transporting is performed. The organic substance contained in the layer is broken by the action of vacuum ultraviolet light, or the oxygen atom radical generated by the excitation of oxygen in the presence of oxygen acts on the organic substance. Thus, it is considered that a region where the material contained in the hole injecting and transporting layer is decomposed can be formed by volatilizing and removing the decomposition product.

  The wavelength of the vacuum ultraviolet light is not particularly limited as long as it is within a range in which oxygen radicals can be generated by acting with oxygen, but is preferably within a range of 100 nm to 250 nm, and more preferably within a range of 150 nm to 200 nm. It is preferable to be within. This is because if the wavelength is longer than the above range, the generation efficiency of oxygen radicals is lowered, and the decomposition and removal efficiency of the material contained in the hole injecting and transporting layer may be lowered. In addition, if the wavelength is shorter than the above range, stable irradiation with vacuum ultraviolet light may be difficult.

  Examples of the light source used for the irradiation of vacuum ultraviolet light in the above wavelength range include an excimer lamp, a low-pressure mercury lamp, and other various light sources.

  The irradiation amount of the vacuum ultraviolet light is not particularly limited as long as the material contained in the hole injecting and transporting layer can be decomposed, and the kind of the material contained in the hole injecting and transporting layer and the above What is necessary is just to adjust suitably with the wavelength etc. of a vacuum ultraviolet light.

  The vacuum ultraviolet light mask used in the irradiation of vacuum ultraviolet light may be any mask that can transmit vacuum ultraviolet light in a pattern, for example, a metal mask having a pattern-shaped opening, a vacuum A mask having a transparent base material that can transmit ultraviolet light and a light shielding part that is formed in a pattern on the transparent base material and that can shield vacuum ultraviolet light can be given.

  As a material for the metal mask, any material can be used as long as it can block the vacuum ultraviolet light. For example, a material described in JP 2007-178783 A can be used.

  On the other hand, the transparent substrate may be any material that can transmit vacuum ultraviolet light, and for example, a quartz substrate or the like can be used. In addition, examples of the light shielding material constituting the light shielding part include metals such as chromium and chromium oxide.

  Since vacuum ultraviolet light is dispersed light with no directivity, when irradiating vacuum ultraviolet light through a vacuum ultraviolet light mask, this vacuum ultraviolet light mask is brought as close as possible to the hole injecting and transporting layer. It is preferable to prevent the ultraviolet light from being diffracted between the hole injecting and transporting layer and the vacuum ultraviolet light mask. At this time, a vacuum ultraviolet light mask may be arranged so that the vacuum ultraviolet light mask contacts the hole injection transport layer, and so that the vacuum ultraviolet light mask does not contact the hole injection transport layer, You may arrange | position the mask for vacuum ultraviolet light. When using a vacuum ultraviolet light mask having a light shielding part formed in a pattern on a transparent substrate, the vacuum ultraviolet light mask can be fixed so as to be in close contact with the hole injecting and transporting layer.

(Iii) Method of using the action of a material having a photocatalytic function accompanying energy irradiation The method of using the action of a material having a photocatalytic function accompanying energy irradiation includes a material having a photocatalytic function in the hole injecting and transporting layer. And irradiating energy to the hole injecting and transporting layer through a mask.

The mechanism by which the material contained in the hole injecting and transporting layer is decomposed and removed by the action of the material having a photocatalytic function accompanying energy irradiation is not necessarily clear, but the photocatalyst contained in the hole injecting and transporting layer by energy irradiation is not necessarily clear. A functional material causes an oxidation-reduction reaction, and active oxygen species such as superoxide radicals (• O ²⁻ ) and hydroxy radicals (• OH) generated thereby are converted into organic substances contained in the hole injecting and transporting layer. By acting, the organic matter becomes a decomposed product, and the decomposed product is volatilized and removed, so that it is considered that a region in which the material contained in the hole injecting and transporting layer is decomposed can be formed.

  In particular, when the hole injecting and transporting layer contains an organometallic complex or a metal-containing nanoparticle, the organometallic complex or the metal-containing nanoparticle is oxidized by energy irradiation to generate a metal oxide. This metal oxide becomes a photocatalyst, and it is considered that the material contained in the hole injecting and transporting layer is decomposed and removed by the action of the photocatalyst accompanying energy irradiation.

  The energy to be irradiated can be the same as in the above (i), and the wavelength of the energy can be 450 nm or less, preferably 380 nm or less.

  In addition, about energy irradiation etc., it can specifically be made to be the same as that of the method described in Unexamined-Japanese-Patent No. 2002-274077 etc.

In the case of this method, since the hole injecting and transporting layer contains an organometallic complex or metal-containing nanoparticles, at least a part of the organometallic complex or metal-containing nanoparticles is used as a metal oxide in the pattern forming step. It is preferable. This is because, as described above, the decomposition of the material contained in the hole injecting and transporting layer is promoted by the photocatalytic action of the metal oxide.
In order to make at least a part of the organometallic complex or the metal-containing nanoparticles into a metal oxide, for example, the above-described energy may be simply irradiated, and in addition to the above-described energy irradiation, heating may be performed.

(Iv) A method combining the method of using the action of a photocatalyst accompanying energy irradiation and the method of using the action of a material having a photocatalytic function accompanying energy irradiation A method using the action of a photocatalyst accompanying energy irradiation and energy irradiation The method combined with the method utilizing the action of a material having a photocatalytic function is that the hole injecting and transporting layer contains a material having a photocatalytic function, and a photocatalyst-containing layer containing at least a photocatalyst on a substrate as a mask The photocatalyst-containing layer substrate is used, and the photocatalyst-containing layer substrate is arranged with a gap from which the action of the photocatalyst accompanying the irradiation of energy can be performed with respect to the hole injecting and transporting layer. Irradiation method.
The method using the action of the photocatalyst accompanying the energy irradiation and the method using the action of the material having a photocatalytic function accompanying the energy irradiation are described in the above (i) and (iii), respectively. Is omitted.

(V) A method combining the method of irradiating vacuum ultraviolet light and the method of using the action of a material having a photocatalytic function accompanying energy irradiation The method of irradiating a vacuum ultraviolet light and the action of a material having a photocatalytic function accompanying energy irradiation In combination with the method using the method, a vacuum ultraviolet light mask is used as a mask, the hole injection / transport layer contains a material having a photocatalytic function, and vacuum ultraviolet light is irradiated as energy.
In addition, since the method of irradiating vacuum ultraviolet light and the method of using the action of the material having a photocatalytic function accompanying energy irradiation are described in the above (ii) and (iii), description thereof is omitted here.

(2) Aspect of irradiating energy using a mask In the present invention, energy is irradiated to the portion of the hole injecting and transporting layer located on the top of the resin bank.

  For example, in the case of the method using the action of the photocatalyst accompanying the above-described energy irradiation, as illustrated in FIGS. 2 (b) to 2 (c), the top of the resin bank 4 is placed via the photocatalyst containing layer substrate 21. By irradiating the portion 27 of the hole injection / transport layer 5a with the ultraviolet light 27, the liquid repellent region 12 is formed on the top of the resin bank. Thus, the liquid repellent area 12 is arranged on the top of the resin bank 4 and the lyophilic area 11 is arranged on the side of the resin bank 4 and on the opening of the resin bank 4. A pattern is obtained.

  Further, for example, in the case of the above-described method of irradiating with vacuum ultraviolet light, as illustrated in FIGS. 3B to 3C, hole injection located on the top of the resin bank 4 through the metal mask 31. By irradiating the portion of the transport layer 5a with the vacuum ultraviolet light 37, the liquid repellent region 12 is formed on the top of the resin bank. Thus, the liquid repellent area 12 is arranged on the top of the resin bank 4 and the lyophilic area 11 is arranged on the side of the resin bank 4 and on the opening of the resin bank 4. A pattern is obtained.

  In this way, by irradiating energy to the portion of the hole injecting and transporting layer located on the top of the resin bank, the liquid repellent region disposed on the top of the resin bank, the side of the resin bank, and A pattern consisting of a lyophilic region disposed in the opening can be obtained.

  Further, when the second hole injection / transport layer forming step described later is performed before the hole injection / transport layer forming step, it is located on the top of the resin bank 4 as illustrated in FIG. 8 (a). The portion of the hole injection transport layer 5 a and the second hole injection transport layer 6 a can be irradiated with ultraviolet light 27 through the photocatalyst containing layer substrate 21. As a result, the material contained in the hole injection / transport layer 5a is decomposed, and the material contained in the second hole injection / transport layer 6a is also decomposed. As illustrated in FIG. It is considered that bank 4 is exposed. Further, the hole injection / transport layer 5b and the second hole injection / transport layer 6b remain as they are in a portion where the action of the photocatalyst due to energy irradiation does not reach. As a result, a pattern composed of the liquid repellent region 12 disposed at the top of the resin bank 4 and the lyophilic region 11 disposed at the side and opening of the resin bank 4 is formed.

  Furthermore, in the above case, as illustrated in FIG. 9A, a metal mask 31 is formed on the hole injection transport layer 5 a and the second hole injection transport layer 6 a located on the top of the resin bank 4. Via, the vacuum ultraviolet light 37 can be irradiated. As a result, the material contained in the hole injection / transport layer 5a is decomposed, and the material contained in the second hole injection / transport layer 6a is also decomposed. As illustrated in FIG. It is considered that bank 4 is exposed. Further, the hole injection / transport layer 5b and the second hole injection / transport layer 6b remain as they are in a portion where the vacuum ultraviolet light is not irradiated. As a result, a pattern composed of the liquid repellent region 12 disposed at the top of the resin bank 4 and the lyophilic region 11 disposed at the side and opening of the resin bank 4 is formed.

  When a mask having a transmission region and a light shielding region is used as the mask, at least one of the ratio of the area of the transmission region of the mask to the area of the top of the resin bank and the distance between the hole injection transport layer and the mask By adjusting either of these, the liquid repellent region may be formed so that the contact angle of the liquid on the surface on the hole injecting and transporting layer side increases from the side of the resin bank toward the top. .

  For example, in the case of the method using the action of the photocatalyst accompanying the above-described energy irradiation, and the light-shielding portion is formed in a pattern on the photocatalyst-containing substrate, the substrate 22 as illustrated in FIG. Use of the photocatalyst-containing layer substrate 21 having the light-shielding region 51 provided with the light-shielding part 23 and the transmission region 52 that is a region other than the light-shielding region 51 and provided only with the photocatalyst-containing layer 24 on the substrate 22 is used. it can. In this case, at least one of the ratio of the area S2 of the transmission region 52 of the photocatalyst-containing layer substrate 21 to the area S1 of the top of the resin bank 4 and the distance D between the hole injection transport layer 5a and the photocatalyst-containing layer substrate 21 By adjusting one of them, the liquid repellent region is formed so that the contact angle of the liquid on the surface on the hole injection transport layer 5a side becomes higher from the side of the resin bank 4 toward the top. Can do.

  Further, for example, in the case of the above-described method of irradiating vacuum ultraviolet light, a metal mask 31 having a transmissive region 52 corresponding to an opening and a light shielding region 51 other than the transmissive region 52, as illustrated in FIG. Can be used. In this case, by adjusting the ratio of the area S2 of the transmission region 52 of the metal mask 31 to the area S1 of the top of the resin bank 4, the contact angle of the liquid on the surface on the hole injection transport layer 5a side can be adjusted. The liquid repellent region can be formed so as to increase from the side portion side to the top portion side.

This is due to the effect of light diffraction and solid angle. The former is a ratio of the area of the transmission region of the mask to the area of the top of the resin bank, and by adjusting at least one of the distance between the hole injection transport layer and the mask, due to the light diffraction phenomenon, etc. A gradient occurs in the amount of energy applied to the hole injecting and transporting layer, and as a result, a gradient is generated in the amount by which the material contained in the hole injecting and transporting layer is decomposed. Regarding the latter, the top of the resin bank is perpendicular to the incidence of light, whereas the side of the resin bank has an angle, so the solid angle is small, and the apparent light dose is small, As a result, a gradient is generated in the amount by which the material contained in the hole injecting and transporting layer is decomposed. As a result, the liquid contact angle can be inclined on the surface on the hole injection / transport layer side so that the liquid contact angle increases from the side of the resin bank toward the top. .
Further, when the resin bank is relatively thick, the distance between the hole injection transport layer and the mask gradually increases from the top side to the side of the resin bank. Depending on the distance from the mask, the contact angle of the liquid can be inclined.

Further, in the case of the method using the action of the photocatalyst accompanying the above-described energy irradiation, and the photocatalyst containing layer is formed in a pattern on the photocatalyst containing substrate, the substrate 22 as illustrated in FIG. The photocatalyst-containing layer substrate 21 having the region 53 where the photocatalyst-containing layer 24 is provided and the region 54 where the base 22 is exposed can be used. In this case, at least one of the ratio of the area S3 of the region 53 of the photocatalyst containing layer substrate 21 to the area S1 of the top of the resin bank 4 and the distance D between the hole injection transport layer 5a and the photocatalyst containing layer substrate 21 is used. As in the case described above, the liquid repellency is adjusted so that the contact angle of the liquid on the surface on the hole injecting and transporting layer 5a side increases from the side of the resin bank 4 toward the top. The sex region can be formed.
In this case, the region where the photocatalyst-containing layer is provided on the substrate is referred to as a transmission region as described above, and the region where the substrate is exposed is referred to as a light shielding region as described above.

  If the liquid contact angle is inclined by adjusting the ratio of the area of the mask transmission region to the area of the resin bank top, the area of the mask transmission region is larger than the area of the resin bank top. Are preferably equal or larger. This is because it becomes easy to incline the liquid contact angle in a region located near the boundary between the top and side of the resin bank.

3. Cleaning Step In the present invention, after the pattern formation step, a cleaning step for cleaning the surface on the hole injecting and transporting layer side can be performed. By the cleaning process, it is possible to remove a decomposition product of the material contained in the hole injecting and transporting layer remaining after the pattern forming process. Note that the material contained in the hole injecting and transporting layer may be vaporized or the like when being decomposed, so that the cleaning step may not be performed.

  Examples of the method for cleaning the surface on the hole injecting and transporting layer include a method of cleaning with wind pressure, suction, liquid, or the like.

4). Other Steps In the present invention, a resin bank forming step for forming a resin bank having a liquid repellent surface on the substrate on which the first electrode layer is formed is performed before the hole injection transport layer forming step. May be.
The method for forming the resin bank is described in the section “A. Substrate for organic EL element”, and the description thereof is omitted here.

In addition, before the hole injection / transport layer forming step, the second hole forming the second hole injection / transport layer on the substrate on which the first electrode layer and the resin bank having the liquid repellency are formed. An injection transport layer forming step may be performed.
The method for forming the second hole injecting and transporting layer is the same as the method for forming the hole injecting and transporting layer, and the description thereof is omitted here.

D. Next, a method for manufacturing the organic EL element of the present invention will be described. The organic EL device manufacturing method of the present invention includes an organic EL device substrate preparation step for preparing an organic EL device substrate by the above-described organic EL device substrate manufacturing method, and a lyophilic property of the organic EL device substrate. A light emitting layer forming step of forming a light emitting layer by applying a coating solution for forming a light emitting layer on the region, and a second electrode layer forming step of forming a second electrode layer on the light emitting layer. It is a feature.

  FIG. 13 is a process diagram showing an example of a method for producing an organic EL element of the present invention. First, as shown in FIG. 13A, the substrate 2, the first electrode layer 3 formed in a pattern on the substrate 2, and the first electrode layer 3 by the method for manufacturing an organic EL element substrate described above. The resin bank 4 having a liquid repellency on the surface and the first electrode layer 3 on the side of the resin bank 4 and in the opening of the resin bank 4 An organic EL element substrate 1 having a liquid hole injection / transport layer 5 and a pattern composed of a lyophilic region 11 and a liquid repellent region 12 disposed on the surface on the hole injection / transport layer 5 side is prepared. (Organic EL device substrate preparation step). Next, as shown in FIG. 13 (b), a third hole injection / transport layer forming coating solution is applied onto the lyophilic region 11 of the organic EL element substrate 1, and third hole injection is performed. The transport layer 42 is formed (third hole injection transport layer forming step). Next, as shown in FIGS. 13C to 13D, a light emitting layer forming coating solution 43a is applied on the third hole injection transport layer 42 to form the light emitting layer 43b (light emitting layer formation). Process). Subsequently, as shown in FIG. 13E, an electron injection / transport layer 44 is formed on the light emitting layer 43b (electron injection / transport layer forming step). Next, as shown in FIG. 13F, the second electrode layer 46 is formed on the electron injecting and transporting layer 44 (second electrode layer forming step).

According to the present invention, since the organic EL element substrate is prepared by the above-described method for manufacturing an organic EL element substrate, the liquid repellent region in which the constituent material of the hole injection transport layer is decomposed, and the liquid repellent An organic EL element substrate having a pattern composed of a lyophilic region that is a region other than the luminescent region can be obtained. Therefore, the light emitting layer or the like can be patterned without impairing the hole injection property and the hole transport property.
In addition, since the lyophilic region is disposed on the side of the resin bank, it is possible to suppress occurrence of a thin portion such as a light emitting layer or a portion where a light emitting layer or the like is not formed, and uneven color. It is possible to prevent a short circuit between electrodes.
Hereinafter, each process in the manufacturing method of the organic EL element of this invention is demonstrated.

1. Organic EL Element Substrate Preparation Step The organic EL element substrate preparation step in the present invention is a step of preparing an organic EL element substrate by the above-described method for producing an organic EL element substrate.
The method for preparing the substrate for organic EL elements has been described in detail in the above section “C. Method for producing substrate for organic EL element”, and therefore the description thereof is omitted here.

2. Light emitting layer forming step The light emitting layer forming step in the present invention is a step of forming a light emitting layer by applying a light emitting layer forming coating solution on the lyophilic region of the organic EL device substrate.

  The coating solution for forming the light emitting layer can be prepared by dispersing or dissolving the light emitting material described in the section of the light emitting layer of the “B. Organic EL device” in a solvent. In the case of forming red, green and blue light-emitting layers of the three primary colors, red, green and blue light-emitting layer forming coating solutions are used.

  The solvent used in the light emitting layer forming coating solution is not particularly limited as long as it can dissolve or disperse the light emitting material. For example, ketones such as acetone, methyl ethyl ketone, cyclohexanone; methanol, Alcohols such as ethanol and butanol; esters such as butyl acetate; ethers such as tetrahydrofuran and dibutyl ether; hydrocarbons such as toluene, xylene and dodecylbenzene; chlorobenzene, carbon tetrachloride, chloroform, methylene chloride, trichloroethylene, dichloroethane Halogenated hydrocarbons such as dichloromethane, glycols such as ethylene glycol and propylene glycol; glycol ethers such as ethylene glycol monomethyl ether; or water, dimethylformamide Dimethyl sulfoxide, N- methyl-2-pyrrolidone; and a solvent of the fluorine substituted by fluorine hydrogen some of the above. These solvents may be used alone or in combination of two or more.

  In addition to the light emitting material and the solvent, various additives can be added to the light emitting layer forming coating solution. For example, when the light emitting layer is formed by an ink jet method, a surfactant or the like may be added for the purpose of improving dischargeability.

  As a method for applying the light emitting layer forming coating liquid, the light emitting layer forming coating liquid is applied onto a pattern composed of a lyophilic area and a liquid repellent area, and the wettability of the lyophilic area and the liquid repellent area is determined. The method is not particularly limited as long as the light emitting layer can be formed in a pattern using the difference. Examples of such a coating method include a flexographic printing method, a gravure printing method, an offset printing method, a screen printing method, an aerosol method, a discharge method using a dispenser or an inkjet, a nozzle printing method, and the like. Among these, when a light emitting layer of a plurality of colors such as the three primary colors of red, green and blue is formed, an ejection method, a nozzle printing method, a flexographic printing method, and a gravure printing method are preferably used. A discharge method is particularly preferable, and a nozzle printing method and an ink jet method are more preferable. This is because in these methods, the light emitting layer can be formed in a high-definition pattern using a pattern composed of a lyophilic region and a liquid repellent region.

  The light emitting layer has been described in detail in the above section “B. Organic EL element”, and thus the description thereof is omitted here.

3. Second electrode layer forming step The second electrode layer forming step in the present invention is a step of forming a second electrode layer on the light emitting layer.
In addition, since the formation method of the 2nd electrode layer, etc. were described in the above-mentioned item of "B. Organic EL element", description here is abbreviate | omitted.

4). Other Steps In the present invention, in addition to the above-described organic EL element substrate preparation step, light emitting layer formation step, and second electrode layer formation step, other steps may be included as necessary.

  In the method for producing an organic EL device of the present invention, for example, a third hole injection / transport layer is formed by forming a third hole injection / transport layer on a lyophilic region of the substrate for an organic EL device before the light emitting layer formation step. You may have a process. In this case, first, the third hole injecting and transporting layer is formed only on the lyophilic region using the pattern composed of the new lyophilic region and the lyophobic region. Since the surface of the third hole injecting and transporting layer is lyophilic and the region where the third hole injecting and transporting layer is not formed is a liquid repellent region, the light emitting layer is also lyophilic due to the difference in wettability. It can be formed only on the region.

The method for forming the third hole injecting and transporting layer can be the same as the method for forming the light emitting layer.
Since the third hole injecting and transporting layer is described in the above section “B. Organic EL element”, description thereof is omitted here.

Moreover, the manufacturing method of the organic EL element of this invention may have the electron injection transport layer formation process of forming an electron injection transport layer on a light emitting layer after a light emitting layer formation process, for example.
The method for forming the electron injecting and transporting layer can be the same as the method for forming the hole injecting and transporting layer.
Since the electron injecting and transporting layer is described in the above section “B. Organic EL element”, the description is omitted here.

  Furthermore, in the present invention, after the second electrode layer forming step, in order to protect the light emitting layer and the like from the influence of oxygen and water vapor, a barrier layer forming step for forming a barrier layer on the second electrode layer, light extraction, In order to improve efficiency, a low refractive index layer forming step of forming a low refractive index layer on the second electrode layer may be performed.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Hereinafter, the present invention will be specifically described using examples and comparative examples.
[Example 1]
As shown in FIGS. 14 (a) to 14 (b), a liquid-repellent resin bank (not shown), second film on the glass substrate (2) on which the ITO transparent electrode (anode) (3) is formed. A hole injecting and transporting layer 6a and a hole injecting and transporting layer 5a are sequentially formed, and a photocatalyst containing layer substrate 21 (photomask with a photocatalyst containing layer) in which a light shielding portion 23 and a photocatalyst containing layer 24 are formed on a base 22 is used. The pattern was exposed to light, and the wettability of the exposed part and the non-exposed part was examined by contact angle measurement. And the light emitting layer was formed in the lyophilic area | region, and the light emitting layer was observed with the fluorescence microscope image.

  First, a glass substrate with indium tin oxide (ITO) as a transparent electrode (manufactured by Sanyo Vacuum Co., Ltd.) was patterned in a stripe shape by a photolithography method. The film thickness of ITO was 150 nm, and the stripe pattern was formed so that the ITO electrodes had a width of 70 μm (line) and the space between the electrodes was 30 μm (space). This glass substrate with ITO was subjected to ultrasonic cleaning in the order of neutral detergent and ultrapure water, and then subjected to UV ozone treatment.

  Next, a mixed film of polyimide (PW1001 manufactured by Toray Industries, Inc.), which is a positive photosensitive material, and Modiper F200 (manufactured by NOF Corporation), which is a liquid repellent material, is formed on the substrate and patterned to obtain a liquid repellent property. A flexible resin bank was formed. Polyimide and Modiper F200 were mixed at a solid content concentration ratio of 20: 1, and applied and formed on the entire surface of the substrate to a thickness of 1 μm by spin coating. Next, exposure and development were performed so that a polyimide film having a width of 50 μm remained at the center between the ITO electrodes, and the film was heated on a hot plate at 250 ° C. for 30 minutes. A flat portion where no pattern was formed was selected, and the contact angle of the resin bank surface to xylene was measured to be 55 °.

The synthesis of the molybdenum complex 1 represented by the following formula is described in Inorganic Chemistry, 13, 1974, p. According to the method described in 1824, the following scheme was performed. Using a nuclear magnetic resonance spectrum JNM-LA400WB manufactured by JEOL Ltd., ¹ H NMR spectrum was measured, and it was confirmed that the synthesized molybdenum complex 1 had the following structure.

  Next, a mixed film (film) of copoly [3,3′-hydroxy-tetraphenylbenzidine / diethylene glycol] carbonate (PC-TPD-DEG) and molybdenum complex 1 is formed on the substrate as a second hole injecting and transporting layer. (Thickness: 10 nm) was formed by spin coating. PC-TPD-DEG and molybdenum complex 1 are dissolved in a mixed solvent of chloroform and toluene (weight ratio 9: 1) at a weight ratio of 1: 1 to prepare a coating solution for forming a second hole injection transport layer, The coating solution for forming the second hole injection / transport layer was formed on the cleaned anode by applying by a spin coating method. After forming the coating film, it was dried on a hot plate. The film thickness after drying was 15 nm. A flat portion where no pattern was formed was selected, and the contact angle of the surface of the second hole injecting and transporting layer with respect to xylene was measured and found to be 10 °.

  Next, poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4 ′-(N- (4-sec) is formed on the substrate as a hole injecting and transporting layer. -Butylphenyl)) diphenylamine)]] (TFB) film and molybdenum complex mixed film (film thickness: 5 nm) were formed by spin coating. A TFB and a molybdenum complex were dissolved in cyclohexanone so as to have a weight ratio of 2: 1 to prepare a hole injecting and transporting layer forming coating solution. It formed by apply | coating by the spin coat method on an injection | pouring transport layer. After forming the coating film, it was dried on a hot plate at 150 ° C. for 1 hour. The film thickness after drying was 5 nm. When a flat portion where no pattern was formed was selected and the contact angle of the surface of the hole injecting and transporting layer with respect to xylene was measured, it was 5 ° or less.

  Next, a photomask with a photocatalyst-containing layer was prepared. A photomask having a transmissive region and a light-shielding region formed in a slit pattern on a synthetic quartz substrate was prepared. The width of the transmission region was 30 μm, and the width of the light shielding region was 70 μm. On this photomask, a photocatalyst-containing layer-forming coating solution having the following composition is applied by a spin coater, subjected to a heat drying treatment at 150 ° C. for 10 minutes, and cured by a hydrolysis / polycondensation reaction. Formed a transparent photocatalyst-containing layer having a film thickness of 200 nm firmly fixed in the organosiloxane.

<Photocatalyst-containing layer forming coating solution>
Titanium dioxide (Ishihara Sangyo Co., Ltd., ST-K01) 2 parts by weight Organoalkoxysilane (Toshiba Silicone Co., Ltd., TSL8113) 0.4 part by weight Fluoroalkylsilane (Tochem Products Co., Ltd.) MF-160E) 0.3 parts by weight / isopropyl alcohol 3 parts by weight

Next, the hole injecting and transporting layer and the second hole injecting and transporting layer were exposed to form a pattern composed of a new liquid region and a liquid repellent region. Using an ultraviolet exposure device equipped with a high-pressure mercury lamp, a photomask with a photocatalyst-containing layer and a substrate position adjustment mechanism, adjust the center of the transmission region of the photomask with a photocatalyst-containing layer so that it is located at the center between the ITO electrodes. Further, after adjusting the distance between the photocatalyst containing layer and the hole injecting and transporting layer of the photocatalyst containing layer photomask containing layer to be 20 μm, the exposure amount of 253 nm light from the back side of the photocatalyst containing layer photomask is It was exposed for 3 minutes so that it might become 200 mJ / cm < ² >.

Next, select a portion that was uniformly exposed in a flat area other than the slit pattern (approx. 1 cm ² □) and a portion that was not exposed (non-exposed part, approximately 1 cm ² □). The angle was measured with a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). As the liquid, xylene (surface tension: 28.5 mN / m) was used. The exposed area was 48 ° and the non-exposed area was 5 °.

  Next, a luminescent layer forming coating solution having the following composition was applied to the lyophilic region by an inkjet method to form a luminescent layer. After forming the coating film, it was dried in nitrogen at 80 ° C. for 30 minutes, and the light emitting layer was observed with a fluorescence microscope. The light emitting layer was flat and well formed in the resin bank.

<Light emitting layer forming coating solution>
・ 2-Methyl-9,10-bis (naphthalen-2-yl) anthracene (MADN) 0.99 parts by weight ・ 9,10-bis [N, N-di- (p-tolyl) -amino] anthracene (TTPA) ) 0.01 parts by weight, 99 parts by weight of xylene

[Example 2]
In Example 1, a pattern was formed in the same manner as in Example 1 except that the exposure light source was exposed to vacuum ultraviolet light for 2 minutes instead of 253 nm ultraviolet light, and the wettability was evaluated.
At this time, a pattern composed of a lyophilic region and a lyophobic region was formed by irradiating vacuum ultraviolet light having a wavelength of 172 nm with an illuminance of 10 mW / cm ² from the photomask-containing photomask side.
Subsequently, contact with xylene is selected by selecting a uniformly exposed area (approximately 1 cm ² □) and a non-exposed area (non-exposed area, approximately 1 cm ² □) in a flat area other than the slit pattern. When the angle was measured, the exposed part was 50 ° and the non-exposed part was 5 °.

[Example 3]
In Example 1, instead of setting the width of the transmission region of the photomask with a photocatalyst containing layer to 30 μm and the width of the light shielding region to 70 μm, the width of the transmission region is 52 μm and the width of the light shielding region is 48 μm. A pattern composed of a liquid repellent region and a lyophilic region was formed in the same manner as in 1 to form a light emitting layer.
When the light emitting layer was observed with a fluorescence microscope, the light emitting layer was flat and better formed in the resin bank than in Example 1.

[Comparative Example 1]
In Example 1, the width of the transmission region of the photomask with a photocatalyst containing layer is 30 μm and the width of the light shielding region is 70 μm, except that the width of the transmission region is 60 μm and the width of the light shielding region is 40 μm. A pattern composed of a liquid repellent region and a lyophilic region was formed in the same manner as in 1 to form a light emitting layer.
When the luminescent layer was observed with a fluorescence microscope, peeling of the luminescent layer was observed at the side of the resin bank.

[Evaluation]
For Examples 1 and 2, the liquid contact angles in the regions I to IV shown in FIGS. 14A and 14B are shown in Table 1 below.

  In Example 1, the contact angle of region II (exposure portion, light irradiation in the presence of a photocatalyst) is increased to 48 °. On the other hand, since the contact angle is kept at 5 ° in the region III (unexposed area), it can be seen that the process can be applied separately. As a result, the constituent materials of the hole injection transport layer and the second hole injection transport layer were decomposed by superoxide radicals or hydroxy radicals generated on the photomask, and the liquid repellency of the resin bank was expressed. Conceivable.

  In Example 2, the contact angle of region II (exposure portion, light irradiation in the presence of a photocatalyst) is increased to 50 °. On the other hand, since the contact angle is kept at 5 ° in the region III (unexposed area), it can be seen that the process can be applied separately. The contact angle is also increased in region IV (exposed portion, only light irradiation). This is because the constituent materials of the hole injection transport layer and the second hole injection transport layer were decomposed by oxygen radicals generated by vacuum ultraviolet light. It is considered to be an effect. In the region II, the contact angle is 28 °, the contact angle is higher than that in the region IV, and the hole injection transport layer and the second hole injection transport layer are combined by the synergistic effect of the photocatalyst effect and the oxygen radical by the vacuum ultraviolet light. It is thought that the decomposition of the constituent materials of was promoted.

  In Example 1, Example 3 and Comparative Example 1, patterning was performed by changing the width of the transmissive region of the photomask, and the result of exposure 2 μm wider than the width of the resin bank of Example 3 was the best light emission. A layer could be formed. This is presumed that the wettability of the side of the resin bank has a gradient and is adjusted to the optimum wettability condition. In Comparative Example 1, in the state where the side portion of the resin bank is completely liquid repellent, the adhesion between the liquid repellent resin bank and the light emitting material is weak and peeled off during drying. Guessed. On the other hand, in Examples 1 and 3 in which the side portion of the resin bank is lyophilic, the side portion of the resin bank is lyophilic and has strong adhesion to the light emitting material, and there is no problem of peeling. It is guessed.

It is a schematic sectional drawing which shows an example of the board | substrate for organic EL elements of this invention. It is process drawing which shows an example of the manufacturing method of the board | substrate for organic EL elements of this invention. It is process drawing which shows the other example of the manufacturing method of the board | substrate for organic EL elements of this invention. It is a schematic sectional drawing which shows the other example of the board | substrate for organic EL elements of this invention. It is a schematic sectional drawing which shows the other example of the board | substrate for organic EL elements of this invention. It is a schematic sectional drawing which shows an example of the organic EL element of this invention. It is a schematic sectional drawing which shows an example of the photocatalyst containing layer board | substrate used for this invention. It is a schematic diagram which shows an example of the pattern formation process in the manufacturing method of the board | substrate for organic EL elements of this invention. It is a schematic diagram which shows the other example of the pattern formation process in the manufacturing method of the board | substrate for organic EL elements of this invention. It is a schematic diagram which shows the other example of the pattern formation process in the manufacturing method of the board | substrate for organic EL elements of this invention. It is a schematic diagram which shows the other example of the pattern formation process in the manufacturing method of the board | substrate for organic EL elements of this invention. It is a schematic diagram which shows the other example of the pattern formation process in the manufacturing method of the board | substrate for organic EL elements of this invention. It is process drawing which shows an example of the manufacturing method of the organic EL element of this invention. It is process drawing which shows the manufacturing method of the board | substrate for organic EL elements of an Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Substrate for organic EL elements 2 ... Substrate 3 ... First electrode layer 4 ... Resin bank 5, 5a, 5b ... Hole injection transport layer 6, 6a, 6b ... Second hole injection transport layer 11 ... Lipophilicity Region 12 ... Liquid-repellent region 41 ... Organic EL element 42 ... Third hole injecting and transporting layers 43 and 43b ... Light emitting layer 44 ... Electron injecting and transporting layer 45 ... EL layer 46 ... Second electrode layer

Claims (13)

A substrate,
A first electrode layer formed on the substrate;
A resin bank formed in a pattern on the first electrode layer and having a liquid repellent surface;
A hole injection transport layer having a lyophilic property, formed on the first electrode layer on the side of the resin bank and in the opening of the resin bank;
A pattern disposed on the surface of the hole injecting and transporting layer side, disposed on the top of the resin bank, the liquid repellent region in which the constituent material of the hole injecting and transporting layer is decomposed, and the resin A pattern made of a lyophilic region, which is a region other than the liquid repellent region, disposed on a side of the bank made of resin and on an opening of the resin bank;
The hole injection transport layer contains a material having a photocatalytic function,
The material having the photocatalytic function is at least one of an organometallic complex and a reaction product thereof,
The resin bank contains a monomer or oligomer having a fluorine-containing group and a hydrophilic group or a lipophilic group, a fluorine-containing polymer compound, fine particles of a fluorine-containing substance,
The hole injecting and transporting layer contains a barrier material for giving the hole injecting and transporting layer a function of preventing elution of the material contained in the resin bank ,
The barrier material has no hole-injecting property or hole-transporting property, has lyophilic properties, and also injects holes from the anode and transports holes injected from the anode into the light-emitting layer. A substrate for an organic electroluminescence device, wherein the substrate is a polymer material having a weight average molecular weight of 2000 or more that does not affect the substrate.   2. The organic electroluminescence device according to claim 1, wherein a contact angle of the liquid in the lyophilic region and the liquid repellent region is increased from a side portion side to a top portion side of the resin bank. Substrate.   A second hole injecting and transporting layer is formed between the first electrode layer and the resin bank and the hole injecting and transporting layer, and the liquid repellent region is the second hole injecting and transporting. The organic electroluminescent element substrate according to claim 1, wherein the constituent material of the layer is also a decomposed region.   The organic electroluminescent element substrate according to any one of claims 1 to 3, wherein at least a part of the material having the photocatalytic function is oxidized.   The organic electroluminescent element substrate according to any one of claims 1 to 4, wherein the organometallic complex is a molybdenum complex, a titanium complex, or a mixture of a molybdenum complex and a titanium complex. . A substrate for an organic electroluminescence device according to any one of claims 1 to 5,
An electroluminescence layer formed on the lyophilic region of the organic electroluminescence element substrate and including at least a light emitting layer;
An organic electroluminescence element comprising: a second electrode layer formed on the electroluminescence layer. Hole injection transport for forming a hole injection transport layer containing a lyophilic material having a photocatalytic function on a substrate on which a resin bank having a liquid repellency formed on the first electrode layer A layer forming step;
A material contained in the hole injecting and transporting layer disposed on the top of the resin bank by irradiating the hole of the hole injecting and transporting layer located on the top of the resin bank with a mask. A liquid-repellent region that is decomposed, and a pattern composed of a lyophilic region that is disposed on the side of the resin bank and on the opening of the resin bank and is a region other than the liquid-repellent region. A pattern forming step to be formed,
The material having a photocatalytic function is at least one of an organometallic complex and a reaction product thereof,
The resin bank contains a monomer or oligomer having a fluorine-containing group and a hydrophilic group or a lipophilic group, a fluorine-containing polymer compound, fine particles of a fluorine-containing substance,
The hole injecting and transporting layer contains a barrier material for giving the hole injecting and transporting layer a function of preventing elution of the material contained in the resin bank ,
The barrier material has no hole-injecting property or hole-transporting property, has lyophilic properties, and also injects holes from the anode and transports holes injected from the anode into the light-emitting layer. A method for producing a substrate for an organic electroluminescence device, wherein the polymer material is a polymer material having a weight average molecular weight of 2000 or more that does not affect the process.   The mask has a transmissive region and a light shielding region, and when irradiating energy in the pattern forming step, the ratio of the area of the transmissive region of the mask to the area of the top of the resin bank, and By adjusting at least one of the distance between the hole injecting and transporting layer and the mask, the contact angle of the liquid on the surface on the hole injecting and transporting layer side is directed from the side to the top side of the resin bank. The method of manufacturing a substrate for an organic electroluminescence element according to claim 7, wherein the liquid repellent region is formed so as to be higher.   Prior to the hole injection transport layer forming step, a second hole injection transport layer is formed on the substrate on which the first electrode layer and a resin bank having a liquid repellent surface are formed. A transport layer forming step, and in the pattern forming step, the second hole injection transport layer and the hole injection transport layer located on the top of the resin bank are irradiated with energy using a mask. The manufacturing method of the board | substrate for organic electroluminescent elements of Claim 7 or Claim 8 characterized by the above-mentioned.   The organic electroluminescence element substrate according to any one of claims 7 to 9, wherein at least a part of the material having the photocatalytic function is oxidized in the pattern forming step. Production method.   In the pattern forming step, a photocatalyst-containing layer substrate in which a photocatalyst-containing layer containing at least a photocatalyst is formed on a substrate is used as the mask, and the photocatalyst-containing layer substrate is used with respect to the hole injecting and transporting layer. The organic electroluminescence device according to any one of claims 7 to 10, wherein the energy is irradiated after being arranged with a gap where the action of the photocatalyst accompanying the irradiation of energy can be exerted. Manufacturing method for industrial use.   The method for producing a substrate for an organic electroluminescence element according to any one of claims 7 to 11, wherein in the pattern formation step, vacuum ultraviolet light is irradiated as the energy. A substrate preparation step for an organic electroluminescence element for preparing a substrate for an organic electroluminescence element by the method for producing a substrate for an organic electroluminescence element according to any one of claims 7 to 12,
A light emitting layer forming step of forming a light emitting layer by applying a light emitting layer forming coating liquid on the lyophilic region of the organic electroluminescent element substrate;
And a second electrode layer forming step of forming a second electrode layer on the light emitting layer. A method for manufacturing an organic electroluminescent element, comprising:

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