JP2011171243A - Organic electroluminescent element and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic EL element with a barrier rib, capable of accurately patterning an organic layer such as a light emitting layer using a coating system, and capable of preventing disconnection of an electric wire, and also to provide a method of manufacturing the same. <P>SOLUTION: The organic electroluminescent element includes: a substrate; a first electrode layer formed on the substrate; the barrier rib formed on the substrate; a hole injection transport layer which is formed on the barrier rib and an opening of the barrier rib, and has a wettability change pattern formed of a liquid repellent region arranged on the barrier rib and a lyophilic region arranged on the opening of the barrier rib; an organic layer formed on the lyophilic region and having the light emitting layer; a second electrode layer formed on the organic layer and barrier rib; an extraction electrode for a second electrode layer formed on the substrate and arranged on the opening of the barrier rib. An organic layer forming region and an extraction electrode for a second electrode layer forming region are not overlapped. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a passive matrix organic electroluminescence (hereinafter, electroluminescence may be abbreviated as EL) element having a cathode separator and a method for producing the same.

  In general, in the production of a display using an organic EL element, patterning of an organic layer such as a light emitting layer is performed. As a method for patterning the organic layer, a vapor deposition method and a coating method are known. As a vapor deposition method, a method of vapor-depositing an organic material through a shadow mask is widely used. On the other hand, as an application method, an inkjet method, a screen printing method, or the like has been proposed. In addition, in the ink jet method, it has been proposed to form a partition wall having liquid repellency at least on the surface in order to apply with high precision (see, for example, Patent Document 1 and Patent Document 2). Furthermore, in order to enable formation of a high-definition pattern, a method using a photocatalyst (see, for example, Patent Document 3 and Patent Document 4) and a method using vacuum ultraviolet light (for example, see Patent Document 5) are also proposed. ing. The coating method has been actively developed because it is advantageous for increasing the size of the organic EL element.

  In the production of a passive matrix organic EL device, a cathode separator (a partition wall having a reverse taper shape in cross section) is provided, and an electrode material is deposited on the cathode separator, so that the electrode is divided by the cathode separator. The method is known.

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

  In producing a passive matrix organic EL element, it is considered that a cathode separator having liquid repellency is provided at least on the surface, whereby the electrodes can be divided and the light emitting layer can be finely patterned by a coating method. However, as illustrated in FIG. 15, the opening of the cathode separator 105 is formed on the substrate 102 formed so that the stripe-shaped first electrode layer 103 and the liquid-repellent stripe-shaped cathode separator 105 intersect. When the organic layer forming coating solution 106 is applied, the organic layer forming coating solution 106 flows in the longitudinal direction of the cathode separator 105, and it is difficult to pattern the light emitting layer.

  Therefore, in order to pattern the light emitting layer, a ladder-like cathode separator 105 is formed on the substrate 102 on which the stripe-shaped first electrode layer 103 is formed, as illustrated in FIG. It is conceivable that the organic layer forming coating liquid 106 is applied to the opening of the separator 105. However, as illustrated in FIG. 16B, when the electrode material is deposited from above the cathode separator 105, the second electrode layer 108 is divided by the cathode separator 105, and the second electrode layer take-out electrode 109 and the cathode separator 105 are separated. The second electrode layer 108 formed in the opening portion cannot be electrically connected, resulting in disconnection. Note that FIG. 16B is a cross-sectional view taken along the line II of FIG. 16A, and the second electrode layer is indicated by an alternate long and short dash line in FIG.

  The present invention has been made in view of the above problems, and in a passive matrix type organic EL element having a cathode separator, it is possible to accurately pattern an organic layer such as a light emitting layer by a coating method, An object of the present invention is to provide an organic EL element capable of preventing disconnection of an electrode and a manufacturing method thereof.

  In order to achieve the above object, the present invention provides a substrate, a first electrode layer formed in a stripe shape on the substrate, and the first electrode layer on the substrate on which the first electrode layer is formed. The partition formed in stripes in a direction perpendicular to the longitudinal direction and having a cross-sectional shape of a reverse taper shape, and the action of the photocatalyst formed on the partition and in the opening of the partition and disposed on the partition and accompanying energy irradiation Or from a liquid-repellent region containing a wettability changing material whose wettability can be changed by irradiation with vacuum ultraviolet light, and a lyophilic region in which the wettability of the wettability changing material is changed. A hole injecting and transporting layer having a wettability changing pattern, an organic layer formed on the lyophilic region and having at least a light emitting layer, formed on the organic layer and the partition, and divided by the partition A second electrode layer formed on the substrate and electrically connected to the second electrode layer, wherein the second electrode layer is formed in the opening of the partition wall. The second electrode layer forming region where the second electrode layer is provided overlaps the second electrode layer forming region where the second electrode layer is provided and the second electrode layer extraction electrode forming region where the second electrode layer extraction electrode is provided. The organic EL device is characterized in that the organic layer forming region provided with the organic layer does not overlap with the second electrode layer extraction electrode forming region.

  According to the present invention, it is possible to accurately pattern an organic layer such as a light emitting layer by using a wettability change pattern formed on the surface of a hole injecting and transporting layer. Furthermore, the organic layer such as the light emitting layer can be patterned with high accuracy, and the organic layer, the second electrode layer, and the second electrode layer take-out electrode are formed at predetermined positions, so that the second electrode layer is disconnected. The second electrode layer take-out electrode and the second electrode layer formed in the opening of the partition wall can be electrically connected without any problem.

  In the said invention, it is preferable that the length of the said 2nd electrode layer of the longitudinal direction of the said partition is shorter than the length of the said partition. This is because the second electrode layer is divided by the stripe-shaped partition wall.

  In the present invention, the wettability changing material is preferably a material in which a fluorine-containing organic compound is attached to the surface of a transition metal-containing nanoparticle or transition metal-containing nanocluster containing at least a transition metal oxide. . Transition metal-containing nanoparticles or transition metal-containing nanoclusters containing transition metal oxides with fluorine-containing organic compounds attached to the surface can change wettability by the action of a photocatalyst associated with energy irradiation or irradiation with vacuum ultraviolet light In addition, the process resistance is high, and the hole injecting and transporting layer can be formed by a wet process, the manufacturing process is easy, and the hole injecting characteristics are improved, and the first electrode layer and the organic layer adjacent to each other are improved. This is because the hole injecting and transporting layer having excellent adhesion and high stability is obtained.

  In the above case, the transition metal in the transition metal oxide is preferably at least one metal selected from the group consisting of molybdenum, tungsten, rhenium and vanadium. This is because the driving voltage is lowered and the device life is improved.

  In the above case, the fluorine-containing organic compound preferably contains a fluorinated alkyl group. This is because the action of the photocatalyst accompanying energy irradiation or the change in wettability due to irradiation with vacuum ultraviolet light is good, and excellent patterning characteristics can be obtained.

  Furthermore, in the present invention, it is also preferable that the wettability changing material is a material in which a fluorine-containing organic compound is attached to an organic-transition metal oxide composite that is a reaction product of an organic transition metal complex. The organic-transition metal oxide complex, which is a reaction product of an organic transition metal complex with a fluorine-containing organic compound attached to the surface, changes its wettability due to the action of a photocatalyst associated with energy irradiation or irradiation with vacuum ultraviolet light. In addition, it has high process resistance, and the hole injection / transport layer can be formed by a wet process, and the manufacturing process is easy. However, the hole injection characteristics are improved, and the adjacent first electrode layer and organic layer This is because a highly stable hole injecting and transporting layer having excellent adhesion to the substrate is obtained.

  In the above case, the transition metal in the transition metal oxide is preferably at least one metal selected from the group consisting of molybdenum, tungsten, rhenium and vanadium. This is because the driving voltage is lowered and the device life is improved.

  In the above case, the organic-transition metal oxide complex is preferably a reaction product of the organic transition metal complex and an organic solvent having a carbonyl group and / or a hydroxyl group. This is because the driving voltage is lowered and the device life is improved.

  Furthermore, in the above case, the fluorine-containing organic compound preferably contains a fluorinated alkyl group. This is because the action of the photocatalyst accompanying energy irradiation or the change in wettability due to irradiation with vacuum ultraviolet light is good, and excellent patterning characteristics can be obtained.

  The present invention also provides a substrate on which a striped first electrode layer, a striped partition perpendicular to the longitudinal direction of the first electrode layer, and a second electrode layer take-out electrode located in an opening of the partition are formed. A hole injection / transport layer forming step for forming a hole injection / transport layer having liquid repellency and wettability changeable by the action of the photocatalyst accompanying energy irradiation, and a photocatalyst containing at least a photocatalyst on the substrate After the photocatalyst-containing layer substrate on which the containing layer is formed is arranged with a gap that can act as a photocatalyst upon irradiation of energy with respect to the hole injection / transport layer, a pattern is formed on the hole injection / transport layer. The wettability change pattern comprising a liquid repellent region disposed on the partition wall and a lyophilic region disposed on the opening of the partition wall on the surface of the hole injecting and transporting layer form A wettability changing pattern forming step, and a coating solution for forming an organic layer is applied in a pattern on the hole injecting and transporting layer, and the second electrode layer is provided with a takeout electrode for the second electrode layer An organic layer forming step of forming an organic layer including at least a light-emitting layer on the lyophilic region so as not to overlap with the extraction electrode forming region, and the partition wall and the organic layer are separated by the partition wall, And a second electrode layer forming step of forming a second electrode layer so as to overlap the extraction electrode forming region for the second electrode layer.

  According to the present invention, it is possible to accurately pattern an organic layer such as a light emitting layer by using a wettability change pattern formed on the surface of a hole injecting and transporting layer. Furthermore, the organic layer such as the light emitting layer can be patterned with high precision, and the second electrode layer extraction electrode, the organic layer, and the second electrode layer are formed at predetermined positions, so that the second electrode layer is not disconnected. The second electrode layer take-out electrode and the second electrode layer formed in the opening of the partition wall can be electrically connected.

  Furthermore, the present invention provides a substrate on which a striped first electrode layer, a striped partition perpendicular to the longitudinal direction of the first electrode layer, and a second electrode layer take-out electrode located in an opening of the partition are formed. A hole injection / transport layer forming step for forming a hole injection / transport layer having liquid repellency and wettability that can be changed by irradiation with vacuum ultraviolet light; and a vacuum in a pattern on the hole injection / transport layer. Irradiation with ultraviolet light forms a wettability change pattern consisting of a liquid-repellent region disposed on the partition and a lyophilic region disposed on the opening of the partition on the surface of the hole injecting and transporting layer A wettability changing pattern forming step, and a coating solution for forming an organic layer is applied in a pattern on the hole injecting and transporting layer, and the second electrode layer is provided with a takeout electrode for the second electrode layer Do not overlap the extraction electrode formation area An organic layer forming step of forming an organic layer including at least a light-emitting layer on the lyophilic region, and the second electrode layer take-out electrode forming region separated by the partition on the partition and the organic layer. And a second electrode layer forming step of forming a second electrode layer so as to overlap with the organic EL element.

  According to the present invention, it is possible to accurately pattern an organic layer such as a light emitting layer by using a wettability change pattern formed on the surface of a hole injecting and transporting layer. Furthermore, the organic layer such as the light emitting layer can be patterned with high precision, and the second electrode layer extraction electrode, the organic layer, and the second electrode layer are formed at predetermined positions, so that the second electrode layer is not disconnected. The second electrode layer take-out electrode and the second electrode layer formed in the opening of the partition wall can be electrically connected.

  In the present invention, it is possible to accurately pattern an organic layer such as a light emitting layer by utilizing the wettability change pattern formed on the surface of the hole injecting and transporting layer, and the second electrode layer is disconnected without breaking the second electrode layer. There is an effect that the two-electrode extraction electrode and the second electrode layer formed in the opening of the partition wall can be electrically connected.

It is a schematic plan view which shows an example of the organic EL element of this invention. It is the sectional view on the AA line of FIG. 1, BB sectional drawing, and CC sectional drawing. 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 other example of the manufacturing method of the organic EL element of this invention. It is a schematic plan view which shows the other example of the organic EL element of this invention. It is the schematic plan view and sectional drawing which show the other example of the organic EL element of this invention. It is a schematic plan view which shows the other example of the organic EL element of this invention. It is process drawing which shows the other example of the manufacturing method of the organic EL element of this invention. It is process drawing which shows the other example of the manufacturing method 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 process drawing which shows the other example of the manufacturing method of the organic EL element of this invention. It is process drawing which shows the manufacturing method of the organic EL element of an Example. It is process drawing which shows the manufacturing method of the organic EL element of an Example. It is process drawing which shows the manufacturing method of the organic EL element of an Example. It is a schematic diagram which shows an example of the manufacturing method of an organic EL element. It is the schematic plan view and sectional drawing which show an example of an organic EL element.

  Hereinafter, the organic EL device of the present invention and the manufacturing method thereof will be described in detail.

A. Organic EL Element First, the organic EL element of the present invention will be described.
The organic EL device of the present invention includes a substrate, a first electrode layer formed in a stripe shape on the substrate, and a longitudinal direction of the first electrode layer on the substrate on which the first electrode layer is formed. A partition wall having a reverse taper shape in cross-section, and an action of a photocatalyst or vacuum ultraviolet light that is formed on the partition wall and in the opening of the partition wall and is disposed on the partition wall in response to energy irradiation. Change of wettability comprising a liquid-repellent region containing a wettability-changing material whose wettability can be changed by irradiation of the liquid and a lyophilic region disposed in the opening of the partition wall and having changed wettability of the wettability-changing material A hole injecting and transporting layer having a pattern, an organic layer having at least a light emitting layer formed on the lyophilic region, a second layer formed on the organic layer and on the partition, and divided by the partition A second electrode layer extraction electrode formed on the substrate and electrically connected to the second electrode layer, wherein the second electrode layer extraction electrode is formed in the opening of the partition wall; And the second electrode layer forming region where the second electrode layer is provided and the second electrode layer extraction electrode forming region where the second electrode layer extraction electrode is provided overlap, The organic layer forming region in which the organic layer is provided is not overlapped with the second electrode layer extraction electrode forming region.

The organic EL element of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic plan view showing an example of the organic EL device of the present invention, FIG. 2 (a) is a cross-sectional view taken along line AA in FIG. 1, and FIG. 2 (b) is a cross-sectional view taken along line BB in FIG. 2C is a cross-sectional view taken along the line CC of FIG.
As illustrated in FIGS. 1 and 2A to 2C, the organic EL element 1 includes a substrate 2, a first electrode layer 3 formed in a stripe shape on the substrate 2, and a second electrode on the substrate 2. An insulating layer 4 (not shown in FIG. 1) that is formed so as to cover an end portion of the one electrode layer 3 and defines a light emitting region, and stripes in a direction perpendicular to the longitudinal direction of the first electrode layer 3 on the insulating layer 4 The partition wall 5 having a reverse-tapered cross-sectional shape and the partition wall 5 and the opening of the partition wall 5 are formed, and the liquid-repellent region 11 is formed on the surface (indicated by a one-dot and two-short chain line in FIG. 1). And a hole injection transport layer 6 having a wettability change pattern composed of a lyophilic region 12 (shown by a broken line in FIG. 1) and the lyophilic region 12 of the hole injection transport layer 6 and at least light emission. Formed on the organic layer 7 and the partition wall 5 and divided by the partition wall 5. A second electrode layer 8 (shown by a one-dot chain line in FIG. 1), and a second electrode layer extraction electrode 9 formed on the substrate 2 and electrically connected to the second electrode layer 8. Yes.

  The hole injecting and transporting layer 6 has a wettability change pattern including a liquid repellent region 11 and a lyophilic region 12 on the surface. The liquid repellent region 11 is disposed on the partition wall 5 and contains a wettability changing material whose wettability can be changed by the action of a photocatalyst accompanying energy irradiation or irradiation with vacuum ultraviolet light. On the other hand, the lyophilic region 12 is disposed in the opening of the partition wall 5 and the wettability of the wettability changing material included in the liquid repellent region 11 is changed.

  3A to 3E are process diagrams showing an example of a method for producing an organic EL element of the present invention. First, as shown in FIG. 3A, wettability in which wettability can be changed by the action of a photocatalyst associated with energy irradiation on the substrate 2 on which the first electrode layer 3, the insulating layer 4, and the partition wall 5 are formed. A hole injecting and transporting layer 6 containing a change material is formed. Next, as shown in FIG. 3B, the base 22, the light shielding part 23 formed in a pattern on the base 22, and the base 22 are formed so as to cover the light shielding part 23 and contain a photocatalyst. A photocatalyst containing layer substrate 21 having a photocatalyst containing layer 24 is prepared. Next, the photocatalyst-containing layer substrate 21 is arranged so that the photocatalyst-containing layer 24 and the hole injection / transport layer 6 face each other, and the hole injection / transport layer 6 is irradiated with ultraviolet light 27 through the photocatalyst-containing layer substrate 21. To do. As shown in FIG. 3 (c), the exposed portion of the hole injection / transport layer 6 contains the hole injection / transport layer 6 by the irradiation of the ultraviolet light 27, due to the action of the photocatalyst contained in the photocatalyst containing layer 24. The wettability of the material that changes wettability changes and becomes the lyophilic region 12. On the other hand, in the unexposed portion of the hole injection / transport layer 6, the wettability of the wettability changing material contained in the hole injection / transport layer 6 does not change and becomes the liquid repellent region 11. Next, as shown in FIG. 3D, an organic layer forming coating solution is applied in a pattern on the hole injecting and transporting layer 6 to form the organic layer 7 on the lyophilic region 12. Next, as shown in FIG. 3E, the second electrode layer 8 is formed on the partition walls 5 and the organic layer 7.

  4A to 4E are process diagrams showing another example of the method for producing an organic EL element of the present invention. First, as shown in FIG. 4A, the wettability changing material whose wettability can be changed by irradiation with vacuum ultraviolet light on the substrate 2 on which the first electrode layer 3, the insulating layer 4, and the partition walls 5 are formed. The hole injection transport layer 6 containing is formed. Next, as shown in FIG. 4B, a metal mask 31 is disposed on the surface of the hole injection / transport layer 6 and the hole injection / transport layer 6 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. 4C, the wettability of the wettability changing material contained in the hole injection transport layer 6 changes in the exposed portion of the hole injection transport layer 6, It becomes the lyophilic region 12. On the other hand, in the unexposed portion of the hole injection / transport layer 6, the wettability of the wettability changing material contained in the hole injection / transport layer 6 does not change and becomes the liquid repellent region 11. Next, as shown in FIG. 4 (d), an organic layer forming coating solution is applied in a pattern on the hole injection transport layer 6 to form the organic layer 7 on the lyophilic region 12. Next, as shown in FIG. 4E, the second electrode layer 8 is formed on the partition walls 5 and the organic layer 7.

  Thus, the wettability of the wettability changing material contained in the hole injecting and transporting layer changes from the liquid repellency to the lyophilic liquid in the part that has been affected by the photocatalyst due to energy irradiation or the part that has been irradiated with vacuum ultraviolet light. Change to sex. As a result, a hole injecting and transporting layer having a wettability changing pattern composed of a liquid repellent region and a lyophilic region on the surface can be obtained. In the present invention, an organic layer is formed on the lyophilic region disposed in the opening of the partition wall, and no organic layer is formed on the liquid-repellent region disposed on the partition wall. By using the wettability change pattern on the surface of the layer, it is possible to accurately pattern an organic layer such as a light emitting layer.

Further, as illustrated in FIG. 1 and FIGS. 2A to 2C, the second electrode layer extraction electrode 9 is disposed in the opening of the partition wall 5.
Note that the opening of the partition wall refers to a region defined by adjacent stripe-shaped partition walls. The striped partition means a striped partition perpendicular to the longitudinal direction of the first electrode layer. In the example shown in FIG. 5, a region defined by adjacent stripe-shaped partition walls 5 is an opening 15 of the partition walls.

  Furthermore, as illustrated in FIG. 1 and FIGS. 2A to 2C, the second electrode layer extraction electrode forming region 19 provided with the second electrode layer extraction electrode 9 (two-dot chain line in FIG. 1). Is not overlapped with an organic layer forming region 17 (shown by a broken line in FIG. 1) where the organic layer 7 is provided. On the other hand, the second electrode layer lead-out electrode forming region 19 in which the second electrode layer lead-out electrode 9 is provided is a second electrode layer forming region 18 in which the second electrode layer 8 is provided (in FIG. The second electrode layer extraction electrode 9 is electrically connected to the second electrode layer 8.

  According to the present invention, the organic layer such as the light emitting layer can be accurately patterned using the wettability change pattern on the surface of the hole injecting and transporting layer as described above, and the organic layer, the second electrode layer, and the second electrode layer can be patterned. Since the electrode layer take-out electrode is formed at a predetermined position, the second electrode layer take-out electrode and the second electrode layer formed in the opening of the partition wall are electrically connected without disconnecting the second electrode layer. It is possible to connect to. In the organic EL element, since the hole injection / transport layer and the organic layer are generally thin, the second electrode layer is not disconnected by the hole injection / transport layer and the organic layer.

  Hereinafter, each structure of the organic EL element of this invention is demonstrated.

1. Hole Injecting and Transporting Layer The hole injecting and transporting layer in the present invention is formed on the barrier ribs and the openings of the barrier ribs, and is disposed on the barrier ribs. It has a wettability change pattern composed of a liquid repellent region containing the obtained wettability changing material and a lyophilic region that is disposed in the opening of the partition wall and has changed wettability.
Hereinafter, each structure of a positive hole injection transport layer is demonstrated.

(1) Material In the hole injection / transport layer, the wettability of the wettability changing material contained in the hole injection / transport layer is changed from lyophobic to lyophilic by the action of a photocatalyst accompanying energy irradiation or irradiation with vacuum ultraviolet light. It will change. Therefore, the portion other than the lyophilic region of the hole injecting and transporting layer contains the wettability changing material and has liquid repellency.

The wettability changing material used for the hole injecting and transporting layer has liquid repellency, and the wettability changes from liquid repellency to lyophilicity by the action of a photocatalyst accompanying energy irradiation or vacuum ultraviolet light irradiation. There is no particular limitation as long as it is present. Examples of such a wettability changing material include a material in which a fluorine-containing organic compound is attached to the surface of a transition metal-containing nanoparticle or transition metal-containing nanocluster containing at least a transition metal oxide (first embodiment), organic A material in which a fluorine-containing organic compound is attached to an organic-transition metal oxide complex that is a reaction product of a transition metal complex (second embodiment), organopolysiloxane (third embodiment), or the like can be used.
Hereinafter, each material will be described.

(A) 1st aspect The wettability change material of this aspect is a material in which a fluorine-containing organic compound is attached to the surface of a transition metal-containing nanoparticle or transition metal-containing nanocluster containing at least a transition metal oxide.

  Since the wettability changing material of this embodiment is a transition metal-containing nanoparticle or transition metal-containing nanocluster containing a transition metal oxide having a fluorine-containing organic compound attached to the surface, the action of a photocatalyst accompanying energy irradiation or vacuum It is a material whose wettability changes from lyophobic to lyophilic by allowing the fluorine-containing organic compound attached to the surface to be decomposed and removed by irradiation with ultraviolet light. When the wettability changing material of this embodiment is used, the portion where the photocatalyst action due to energy irradiation or the portion irradiated with vacuum ultraviolet light becomes a lyophilic region, and the portion where the photocatalyst action due to energy irradiation does not reach Alternatively, a portion that is not irradiated with vacuum ultraviolet light becomes a liquid repellent region. The wettability-changing material of this embodiment is capable of decomposing and removing the fluorine-containing organic compound adhering to the surface by the action of a photocatalyst accompanying energy irradiation or irradiation of vacuum ultraviolet light, but contains transition metals including transition metal oxides. Nanoparticles or transition metal-containing nanoclusters themselves are resistant to ultraviolet light and relatively high-temperature heating, so excellent hole injection in transition metal-containing nanoparticles or transition metal-containing nanoclusters including transition metal oxides There is a merit that transportability is not impaired during processes such as energy irradiation, photocatalytic action and heating. Furthermore, the wettability changing material of this embodiment has the merit that it undergoes a treatment such as a photocatalytic treatment for decomposing fluorine to be oxidized to increase the ionization potential and improve the hole injection property.

  In addition, since the wettability changing material of this embodiment contains an organic part containing at least a fluorine-containing organic compound as a protective agent on the surface of the transition metal-containing nanoparticle or transition metal-containing nanocluster, the adhesion between the adjacent organic layers is close. The property is also good. Since the organic layer is formed on the lyophilic region where the fluorine-containing organic compound has been decomposed, there is no influence of the liquid repellency derived from the fluorine-containing organic compound at the interface with the adjacent organic layer, and the adhesion at the interface is excellent. It becomes a thing. In addition, transition metal-containing nanoparticles or transition metal-containing nanoclusters are considered to have a high reactivity of transition metal oxides or transition metal compounds contained therein, and are likely to form a charge transfer complex. Therefore, the wettability changing material of this embodiment can form a hole injecting and transporting layer capable of realizing an organic EL element with low voltage driving, high power efficiency, and long life.

Furthermore, since the transition metal-containing nanoparticle or transition metal-containing nanocluster containing a transition metal oxide used for the wettability changing material of this embodiment contains an organic moiety containing at least a fluorine-containing organic compound as a protective agent on the surface, Dispersibility in solvent. Therefore, since a thin film can be formed by a wet process, the hole injection / transport layer to the organic layer such as the light emitting layer can be sequentially formed only by the wet process, which has a great merit in the manufacturing process.
Hereinafter, the structure of the wettability changing material of this embodiment will be described in order.

(Transition metal-containing nanoparticles and transition metal-containing nanoclusters)
The transition metal-containing nanoparticles contained in the wettability changing material of this embodiment include at least a transition metal oxide. Here, the nanoparticle means a particle having a diameter of the order of nm (nanometer), that is, less than 1 μm.
The transition metal-containing nanoparticles containing at least a transition metal oxide may have a single structure or a composite structure, and may have a core / shell structure, an alloy, an island structure, or the like. The transition metal-containing nanoparticles may contain transition metal atoms and compounds of various valences, such as transition metal carbides, sulfides, borides, selenides, halides, complexes, etc., depending on the processing conditions.

On the other hand, transition metal-containing nanoclusters including transition metal oxides included in the wettability changing material of this embodiment are atomic groups in which a plurality of transition metal atoms and oxygen atoms are gathered to form a specific structural unit, It refers to a compound containing an atomic group or a collection of such compounds. A nanocluster has a shape whose longest part is on the order of nm (nanometer), that is, less than 1 μm.
The transition metal-containing nanocluster is preferably a macromolecule containing a chemically synthesized polyoxometalate (POM). POM has a polyacid structure composed of an oxo acid. This chemically synthesized POM-containing transition metal-containing nanocluster is a large molecule, so its size and weight are defined by molecular weight, and each cluster shape and size has isomers. However, it is basically the same feature. In addition, chemically synthesized POM-containing transition metal-containing nanoclusters are characterized in that the electrical properties are anions and the properties of each cluster are the same. For example, Na ₁₅ [Mo ^VI ₁₂₆ Mo ^V ₂₈ O ₄₆₂ H ₁₄ (H ₂ O) ₇₀ ] _0.5 [Mo ^VI ₁₂₄ Mo ^V ₂₈ O ₄₅₇ H ₁₄ (H ₂ O) ₆₈ ] _0.5・ 400H ₂ O cluster ({Mo ₁₅₄ }), the molecule has a donut shape and a diameter of about 4 nm. Furthermore, this molybdenum oxide nanocluster is a mixed-valence polyoxometalate in which hexavalent (Mo ^VI ) and pentavalent molybdenum (Mo ^V ) coexist in each molecule, and becomes an anion cluster. There are also features.

  The transition metal-containing nanoparticles and transition metal-containing nanoclusters always contain a transition metal oxide. By always including transition metal oxides, the value of ionization potential is optimized, and changes due to oxidation from unstable oxidation number +0 metal are suppressed in advance, so that the drive voltage is reduced and the device lifetime is reduced. It becomes possible to improve. Among these, transition metal-containing nanoparticles and transition metal-containing nanoclusters preferably contain coexisting transition metal oxides having different oxidation numbers. By including transition metal oxides with different oxidation numbers together, the hole transportability and hole injection properties are appropriately controlled by the balance of the oxidation numbers, which improves drive voltage and device life. It becomes possible to make it.

  The transition metal contained in the transition metal-containing nanoparticles and transition metal-containing nanoclusters used in the present invention, or the transition metal contained in the transition metal compound, exists between Group 3 to Group 11 in the periodic table. A generic term for metal elements. Examples of the transition metal include molybdenum, tungsten, vanadium, rhenium, nickel, copper, titanium, platinum, silver, and the like.

  Among them, the transition metal in the transition metal oxide included in the transition metal-containing nanoparticle and the transition metal-containing nanocluster may include at least one metal selected from the group consisting of molybdenum, tungsten, rhenium, and vanadium. Since the reactivity is high, it is preferable from the viewpoint of easily forming a charge transfer complex and reducing the driving voltage and improving the device life.

A single metal may be sufficient as the metal contained in a transition metal containing nanoparticle and a transition metal containing nanocluster, and 2 or more types may be contained. As an aspect in which two or more kinds of metals are contained in the nanoparticles, two or more kinds of metal fine particles or metal oxide fine particles may be contained in combination, or two or more kinds of metals are contained as an alloy. Also good.
In addition, as long as the metal contained in a transition metal containing nanoparticle and a transition metal containing nanocluster contains at least a transition metal, the non-transition metal may be contained. By including two or more metals, hole injection with other functions such as complementing each other with hole transportability and hole injection property, imparting photocatalytic properties, and controlling the refractive index and transmittance of the thin film There is an advantage that a transport layer can be formed.

  The transition metal oxide contained in the transition metal-containing nanoparticle is preferably contained in the transition metal and the transition metal compound in an amount of 30 mol% or more, and more preferably 50 mol% or more in order to reduce the driving voltage or device life. It is preferable from the point of improving.

As the transition metal-containing nanocluster, a polyoxometalate represented by the following formula can be used.
[XxMyOz] ^n-
Here, X is at least one element selected from Group 13-18, at least one element selected from cobalt or rare earth, and M is at least one transition metal selected from Group 4-11 Element or aluminum, and at least one of X and M contains a transition metal element. O represents an oxygen atom.
Examples of M include Mo, W, Cr, V, Nb, Fe, Ta, and Al. Examples of X include P, As, Si, B, and Co. x is an integer of 0 or more, y is an integer of 1 or more, and z is an integer of 1 or more. When x = 0, it is an isopolyacid, and when x is an integer of 1 or more, it is a heteropolyacid. In addition, the above X and M may be independently one kind or two or more kinds may be contained.

Specific examples of the isopolyacid include [Mo ₆ O ₁₉ ] ²⁻ , [Mo ₁₀ O ₃₂ ] ^{4− and the} like. Specific examples of heteropolyacids include [PMo ₁₂ O ₄₀ ] ^3- , [BW ₁₂ O ₄₀ ] ^5- , [SbW ₆ O ₂₄ ] ^8- , [SiV ₂ W ₁₀ O ₄₀ ] ^6- , [V ₁₈ O ₄₄ N ₃ ] ^{n- and the} like. The composition formula of molybdenum oxides such as ordinary MoO ₃ is Mo ^VI _n O _3n, while polyacids such as [Mo ^VI ₆ O ₁₉ ] ^2- are Mo _n O _{3n + m} (m = 1, 2, 3, ...), even in the same hexavalent molybdenum, the polyacid is rich in oxygen and contributes to the anion state. These anion clusters usually exist as hydrates together with counter cations. For example, in the case of [BW ₁₂ O ₄₀ ] ^5- , it is known to exist as K ₅ [BW ₁₂ O ₄₀ ] · 13H ₂ O. It has been.

  As the structure of the metal oxide cluster of the transition metal-containing nanocluster, for example, Keggin type, Dawson type, Anderson type, or the like can be used. POM can coordinate 4 to 6 oxide ions to transition metal ions, and is composed of polyhedrons such as tetrahedrons, quadrangular pyramids, and octahedrons, which are stacked. From the combination of atoms and structures, a large number of molecular structures can be considered, and there are also structural isomers such as α, β, γ, and σ isomers.

As the transition metal-containing nanocluster, a reduced mixed-valence polyoxometalate can also be used. Any POM can easily have a mixed valence state by a reduction reaction. For example, [PMo ^VI ₁₂ O ₄₀ ] ^3- can be reduced to [PMo ^VI ₁₁ Mo ^V O ₄₀ ] ^3- or [PMo ^VI ₁₀ Mo ^V ₂ O ₄₀ ] ^4- and has a different valence in the molecule. Can be taken. POM can be reduced by, for example, a donor guest molecule. The reduced anion is characterized by being stably reduced for each electron, and is different from ordinary molybdenum oxides such as MoO ₃ .

As the transition metal-containing nanocluster, a huge mixed-valence POM combining the above structures can be used. For example, Na ₁₅ [Mo ^VI ₁₂₆ Mo ^V ₂₈ O ₄₆₂ H ₁₄ (H ₂ O) ₇₀ ] _0.5 [Mo ^VI ₁₂₄ Mo ^V ₂₈ O ₄₅₇ H ₁₄ (H ₂ O) ₆₈ ] _0.5 · 400H ₂ O can be mentioned. Since these have a complicated molecular structure, as a simple notation method, a method of representing this structure as {Mo ₁₅₄ }, typically represented by a transition metal contained in the molecule, is generally used. Examples of transition metal-containing nanoclusters include spherical {Mo ₁₃₂ }, ring-shaped {Mo ₁₄₂ }, {Mo ₁₅₄ } and {Mo ₁₇₆ }, wheel-shaped {Mo ₂₄₈ }, and lemon-shaped {Mo ₃₆₈ } is preferably used. In addition, [PMo ₆ O ₁₉ ] ²⁻ , [PMo ₁₂ O ₄₀ ] ^{3− and the} like can be used.
Examples of transition metal-containing nanoclusters containing tungsten and vanadium include [KAs ₄ W ₄₀ (VO) ₂ O ₁₄₀ ] ^23- , Mo ₈ V ₂ O ₂₈ · 7H ₂ O, [alpha-P ₂ W ₁₈ O ₆₂ ] ^6- , [alpha-P ₂ W ₁₇ V (V) O ₆₂ ] ^7- , [alpha-1,2,3-P ₂ W ₁₅ V (V) ₃ O ₆₂ ] ^9- , [[alpha ^{_{-PW 12 O 40] 3- W -}} ), [alpha-PW 11 V (V) O 40] 4-, [alpha-1,2-PW 10 V (V) 2 O 40] 5-, [alpha- 1,2,3-PW ₉ V (V) ₃ O ₄₀ ] ^6- , [alpha-1,4,9-PW ₉ V (V) ₃ O ₄₀ ] ^6- , [V ₁₀ O ₂₈ ] ^6- etc. Is mentioned. In the above description, “V (V)” represents pentavalent vanadium.
In addition to the above, for example, {W ₇₂ Mo ₆₀ } containing two or more transition metal elements in which {Mo ₁₃₂ } is partially substituted with tungsten can be used. In addition, {Mo ₅₇ V ₆ }, {Mo ₅₇ Fe ₆ }, {Mo ₇₂ Cr ₃ 0}, {W ₇₂ Mo ₆₀ }, {Ag ₂ Mo ₈ }, and the like can also be used.

Mixed-valence POMs used as transition metal-containing nanoclusters are synthesized by reducing POM by chemical reaction and introducing metals with different valences (for example, introducing Mo pentavalent into Mo hexavalent). Therefore, a metal having a different valence incorporated (for example, Mo pentavalent) can exist stably. Since different valences exist stably and a stable anion state can be maintained, a hole injecting and transporting layer having excellent lifetime characteristics can be formed. On the other hand, in the case of ordinary molybdenum oxides such as MoO ₃ , most of the molybdenum is Mo ^VI , and the composition formula is Mo _n O _3n . However, it may become Mo _n O _3n-m due to oxygen vacancies at the time of vapor deposition or oxygen defects present on the particle surface caused by physical pulverization at the time of slurry formation, and Mo ^V may be present to some extent. However, Mo ^V introduced by MoO ₃ is caused by oxygen defects and is therefore non-uniform and unstable.

Transition metal-containing nanoclusters can contain counter cations, such as metal oxide clusters containing chemically synthesized POM. As the counter cation, H ⁺ , Na ⁺ and K ⁺ can be preferably used. Cationic organic substances or ionic liquids can also be used.
In transition metal-containing nanoclusters, transition metal atoms and transition metal compounds with various oxidation numbers, such as transition metal sulfides, borides, selenides, halides, ligands, non-transition metal atoms, etc., depending on the synthesis conditions May be included.

(Fluorine-containing organic compound attached to the surface)
In the wettability changing material of this embodiment, the fluorine-containing organic compound is attached to the surface of the transition metal-containing nanoparticle or transition metal-containing nanocluster containing at least a transition metal oxide.
In the wettability changing material of this embodiment, “adhesion” means that the fluorine-containing organic compound is fixed on the surface of the transition metal-containing nanoparticle or transition metal-containing nanocluster to such an extent that it does not peel even when dispersed in an organic solvent. That means. “Adhesion” includes adsorption and coordination, but chemical bonds such as ionic bonds and covalent bonds are preferred. The aspect of “attachment” may be an aspect in which the entire surface of the transition metal-containing nanoparticle or transition metal-containing nanocluster is attached so that the fluorine-containing organic compound is coated, or fluorine may be partially applied to the surface. The aspect to which the containing organic compound has adhered may be sufficient.

  In the wettability changing material of this embodiment, since the organic compound including at least the fluorine-containing organic compound is attached to the surface of the transition metal-containing nanoparticle or the transition metal-containing nanocluster, the transition metal oxide is simply pulverized. Unlike the formed particles, the dispersion stability of the nanoparticles or nanoclusters becomes very high, and a thin film of nm order with high uniformity can be formed. Therefore, the hole injecting and transporting layer is not easily short-circuited because of its high temporal stability and uniformity. Furthermore, it becomes excellent in adhesiveness with the adjacent first electrode layer or organic layer.

  The type of the fluorine-containing organic compound attached to the surface is appropriately selected and is not particularly limited. Examples of the fluorine-containing organic compound include organic compounds in which a part or all of hydrogen contained in a linear, branched, or cyclic saturated or unsaturated hydrocarbon which may contain a heteroatom other than fluorine is substituted with fluorine. Can be mentioned. It may be an organic compound in which part or all of hydrogen contained in an organic compound that may contain a heteroatom conventionally used as a hole injecting and transporting material is substituted with fluorine. Or the compound which introduce | transduced the substituent which contains the fluorine-containing organic compound in the organic compound which may contain the hetero atom conventionally used as a positive hole injection transport material may be sufficient.

  Specific examples of the fluorine-containing organic compound include a linear, branched, or cyclic alkyl group, a fluorinated alkyl group or a fluorinated aryl group in which part or all of the hydrogen of the aryl group is fluorinated, and combinations thereof. Is mentioned. Although carbon number of a fluorinated alkyl group is not specifically limited, 2-10 are preferable and 4-6 are more preferable. Moreover, the carbon number of the combination of a fluorinated aryl group or a fluorinated alkyl group such as a fluorinated arylated alkyl group and a fluorinated aryl group is also not particularly limited, but is preferably 6 to 12, more preferably 6 to 9.

Among _{them, C n F 2n + 1 C} m H 2m - [m is 0 to 20 integer, n is an integer of 1 to 20, m + n is 1-30. The fluorinated alkyl group represented by the above formula maintains a high oil repellency, and when m is 1 or more, it binds to other elements such as an ether bond rather than directly bonding to C _n F _{2n + 1.} It is preferable to use _m H _2m from the viewpoint of increasing the stability of the compound. n is preferably an integer of 2 to 10, more preferably an integer of 4 to 6. m is preferably an integer of 0 to 10, more preferably an integer of 2 to 8.
The fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 50 to 100%, more preferably 80 to 100%, and particularly perfluoroalkyl in which all hydrogen atoms are substituted with fluorine atoms. The group is preferable from the viewpoint of expressing high oil repellency.

In addition, a fluorine-containing organic compound containing an aromatic hydrocarbon and / or a heterocyclic ring is preferable because the boiling point of the fluorine-containing organic compound can be increased. For example, there is an advantage that the restriction on the synthesis temperature of the wettability changing material to which the fluorine-containing organic compound is adhered can be widened, and that the high temperature process temperature when a device is manufactured can be set high.
In addition, since aromatic hydrocarbons and / or heterocycles often have charge transport properties, charge mobility in a hole injecting and transporting layer made of a fluorine-containing organic compound containing aromatic hydrocarbons and / or heterocycles Can be maintained at a high level, which is advantageous for high efficiency including low voltage. Although the fluorine-containing organic compound on the surface of the hole injecting and transporting layer is removed by a treatment that decomposes the fluorine-containing organic compound described later, an aromatic hydrocarbon and / or a heterocyclic ring is formed inside the hole injecting and transporting layer. Since the fluorine-containing organic compound containing is left, higher charge transportability can contribute to higher efficiency.
Further, for example, since each layer of the organic EL element usually contains an aromatic hydrocarbon and / or a heterocyclic charge transport material, considering the improvement in the adhesion between the adjacent organic layer and the hole injection transport layer, the aromatic EL It is preferable from the point which contributes to long drive life to contain the structure of a group hydrocarbon and / or a heterocyclic ring.

Examples of the fluorinated alkyl group include the following structures.
_{CF 3 -, CF 3 CF 2} -, CHF 2 CF 2 -, CF 3 (CF 2) 2 -, CF 3 (CF 2) 3 -, CF 3 (CF 2) 4 -, CF 3 (CF 2) 5 _{-, CF 3 (CF 2)} 6 -, CF 3 (CF 2) 7 -, CF 3 (CF 2) 8 -, CF 3 (CF 2) 9 -, CF 3 (CF 2) 11 -, CF 3 ( _{CF 2) 15 -, CF 3} CH 2 CH 2 -, CF 3 CF 2 CH 2 CH 2 -, CHF 2 CF 2 CH 2 CH 2 -, CF 3 (CF 2) 2 CH 2 CH 2 -, CF 3 ( _{CF 2) 3 CH 2 CH 2} -, CF 3 (CF 2) 4 CH 2 CH 2 -, CF 3 (CF 2) 5 CH 2 CH 2 -, CF 3 (CF 2) 6 CH 2 CH 2 -, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ —, CF ₃ (CF _{2) 8 CH 2 CH 2 -} , CF 3 (CF 2) 9 CH 2 CH 2 -, CF 3 (CF 2) 11 CH 2 CH 2 -, CF 3 (CF 2) 15 CH 2 CH 2 -, CF 3 (CF ₂ ) ₅ O (CF ₃ ) CF-, CF ₃ (CF ₂ ) ₂ O (CF ₃ ) CFCF ₂ O (CF ₃ ) CF-, CF ₃ (CF ₂ ) ₂ O (CF ₃ ) CFCF ₂ O (CF ₃ ) CFCF ₂ O (CF ₃ ) CFCF ₂ O (CF ₃ ) CF—, CF ₃ (CF ₂ ) ₅ O (CF ₃ ) CF—. The straight chain structure is exemplified above, but a branched structure such as an isopropyl group may be used.
Examples of fluorine-containing organic compounds containing aromatic hydrocarbons and / or heterocycles include pentafluorophenyl group, 2,3,5,6-tetrafluorophenyl group, 3,4,5-trifluorophenyl group, 2 , 4-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, nonafluorobiphenyl group, α, α, α, 2,3,5,6-heptafluoro-p-tolyl group, Heptafluoronaphthyl group, (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, pentafluorophenylmethyl group, 2,3,5,6-tetrafluorophenylmethyl group, 3,4, 5-trifluorophenylmethyl group, 2,4-difluorophenylmethyl group, 3,4-difluorophenylmethyl group, 3,5-difluoro Phenylmethyl group, nonafluorobiphenylmethyl group, α, α, α, 2,3,5,6-heptafluoro-p-tolylmethyl group, heptafluoronaphthylmethyl group, (trifluoromethyl) phenylmethyl group, 3,5 -Bis (trifluoromethyl) phenylmethyl group, 4,4 ', 4 "-trifluorotrityl group and the like.

  Fluorine-containing organic compounds include transition metals and / or transitions on the surface of transition metal-containing nanoparticles or transition metal-containing nanoclusters in terms of surface protection and dispersion stability of transition metal-containing nanoparticles or transition metal-containing nanoclusters. It is preferable to attach using the connecting group which produces | generates the effect | action connected with a metal compound. That is, the fluorine-containing organic compound is preferably attached to the surface of the transition metal-containing nanoparticle or transition metal-containing nanocluster by a protective agent containing a linking group at the terminal of the fluorine-containing organic compound.

  The linking group is not particularly limited as long as it has an effect of linking with a transition metal and / or a transition 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. However, in consideration of solubility in a solution, dispersion stability, and oil repellency, 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 the dimer has poor adhesion to transition metal-containing nanoparticles or transition metal-containing nanoclusters, it can be easily removed by adding a washing step to the preparation process of transition metal-containing nanoparticles or transition metal-containing nanoclusters. it can.

  Examples of the linking group include a hydrophilic group such as a carboxyl group, an amino group, a hydroxyl group, a thiol group, an aldehyde group, a sulfonic acid group, an amide group, a sulfonamide group, a phosphoric acid group, a phosphinic acid group, and a P═O group. Alternatively, an ionic liquid such as an ammonium salt, an imidazolium salt, a pyridium salt, a sulfonium salt, a phosphonium salt, a morpholinium salt, or a piperidinium salt can be given. The linking group is preferably at least one selected from functional groups represented by the following formulas (1a) to (1n).

（式中、Ｚ_１、Ｚ_２及びＺ_３は、それぞれ独立にハロゲン原子、又はアルコキシ基を表す。）

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

Examples of the protective agent suitably used for the wettability changing material of this embodiment and containing a linking group at the end of the fluorine-containing organic compound include a protective agent represented by the following general formula (I).
Formula (I)
YQ- (A'-FQ ') _n- (A-FQ)
(In general formula (I), Y represents a linking group. Q is a linear, branched or cyclic aliphatic hydrocarbon group, aromatic hydrocarbon group, aliphatic heterocyclic group, aromatic heterocyclic group, or these. Or A ′ and A ′ each independently represent —NH—, —N═, —S—, —O—, —O— (C═O) —, —O— (SO ₂ ) -, - O- (C = O) -O -, - S- (C = O) -O -, - SiR 2 - (C = O) -O -, - SiR 2 -, or a direct bond R represents hydrogen or a linear, branched or cyclic aliphatic hydrocarbon group, FQ and FQ ′ each independently represents a fluorine-containing organic compound, and n is 0 or an integer of 1 or more. )

A and / or A ′ are —NH—, —N═, —S—, —O—, —O— (C═O) —, —O— (SO ₂ ) —, —O— (C═ O) -O -, - S- ( C = O) -O -, - SiR 2 - (C = O) -O -, - SiR 2 - a If it is, a by the energy irradiation and / or a ' This is preferable because the fluorine organic compound represented by FQ is easily decomposed and the sensitivity at the time of forming the wettability change pattern is improved.

  In addition, when Q contains an aromatic hydrocarbon group or an aromatic heterocyclic group, it can contribute to increasing the charge mobility in the hole injecting and transporting layer, so that high efficiency including low voltage can be achieved. There is an advantage over When A and / or A ′ is cleaved by a treatment that decomposes the fluorine-containing organic compound described later, the fluorine-containing organic compound FQ is decomposed and removed, but the aromatic hydrocarbon and / or the heterocyclic ring is removed. Since the Q part contained remains on the surface of the transition metal-containing nanoparticle or transition metal-containing nanocluster, when Q has a high charge transporting property, it can contribute to high device efficiency.

FQ is a monovalent fluorine-containing organic compound group, and FQ ′ is a divalent fluorine-containing organic compound group.
When n is 1 or more, it is easily cleaved at the A ′ portion by energy irradiation, and the fluorine organic compound represented by FQ is easily decomposed. As when n is 1 or more, for _{example, -O- (CH 2) p -O-} (CH 2) 2 - (CF 2) such as _q -CF ₃ and the like.
n is preferably 5 or less, and more preferably 4 or less from the viewpoint of increasing the decomposition rate.

  Examples of the protective agent represented by the general formula (I) include the following structures, but are not limited thereto.

（ｎ及びｎ′は１〜５の整数、ｍ及びｍ′は０又は１〜５の整数、ｌは０又は１〜５の整
数である。Ｙは、上記式（１ａ）〜（１ｎ）で示される官能基のいずれかである。）

(N and n ′ are integers of 1 to 5, m and m ′ are 0 or an integer of 1 to 5, l is an integer of 0 or 1 to 5. Y is the above formula (1a) to (1n). Any of the functional groups shown.)

  In the wettability changing material of this embodiment, at least a fluorine-containing organic compound is attached to the surface of the transition metal-containing nanoparticle or transition metal-containing nanocluster, but an organic compound that is not a fluorine-containing organic compound is attached. Good. Such organic compounds that are not fluorine-containing organic compounds include a protective agent that was present on the surface of the transition metal-containing nanoparticle or transition metal-containing nanocluster before the replacement of the protective agent containing the fluorine-containing organic compound. , A charge transporting compound containing no fluorine, a compound having crosslinkability, a compound for controlling solubility, and the like.

  In the transition metal-containing nanoparticle or transition metal-containing nanocluster, the content ratio of the transition metal compound and the transition metal to the organic compound including the fluorine-containing organic compound attached to the surface is appropriately selected and is not particularly limited. It is preferable that the organic compound containing the fluorine-containing organic compound adhering to the surface is 10 to 20 parts by weight with respect to 100 parts by weight of the transition metal compound and the transition metal.

  Further, in the wettability changing material of this embodiment, the amount of the fluorine-containing organic compound adhering to the surface may be appropriately selected according to the requirement for the liquid repellency of the liquid repellency region of the hole injection transport layer. .

(Other ingredients)
In the case of the wettability changing material of this embodiment, the hole injecting and transporting layer may be composed of only the wettability changing material of this embodiment, and may further contain other components.
As other components, any hole transporting compound other than the wettability changing material of the present embodiment can be used as long as it has a hole transporting property as long as the effects of the present invention are not impaired. Here, the hole transportability means that an overcurrent due to hole transport is observed by a known photocurrent method.
As the hole transporting compound, in addition to a low molecular compound, a high molecular compound is also preferably used. The hole transporting polymer compound refers to a polymer compound having a hole transporting property and having a weight average molecular weight of 2000 or more according to polystyrene conversion value of gel permeation chromatography. For the purpose of forming a stable film by a coating method, it is preferable to use a high molecular compound capable of forming a stable coating film that is easily dissolved in an organic solvent and hardly aggregates as the hole transporting material.

The hole transporting compound is not particularly limited, and examples thereof include arylamine derivatives, anthracene derivatives, carbazole derivatives, thiophene derivatives, fluorene derivatives, distyrylbenzene derivatives, and spiro compounds. 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) and the like, carbazole derivatives such as 4,4-N, N'-dicarbazole-biphenyl (CBP) and the like, and fluorene derivatives such as N, N'-bis Examples of distyrylbenzene derivatives such as (3-methylphenyl) -N, N′-bis (phenyl) -9,9-dimethylfluorene (DMFL-TPD) include 4 Spiro compounds such as (di-p-tolylamino) -4 '-[(di-p-tolylamino) styryl] stilbene (DPAVB) 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), etc. Can be mentioned.
As the hole transporting polymer compound, for example, polyaniline, polythiophene, polyphenylene vinylene derivative, or the like can be used. Conductive polymers such as polyaniline, polythiophene, and polyphenylene vinylene derivatives may be doped with an acid. Furthermore, a polymer containing an arylamine derivative, anthracene derivative, carbazole derivative, thiophene derivative, fluorene derivative, distyrylbenzene derivative, spiro compound and the like in a repeating unit can be given.

  The content of the hole transporting compound is 10 parts by weight to 10000 parts by weight with respect to 100 parts by weight of the wettability changing material of this embodiment, so that the hole injecting and transporting property is improved and the film is stable. This is preferable from the viewpoint of achieving high life and long life.

  In the case of the wettability changing material of this embodiment, the hole injecting and transporting layer may contain an additive such as a binder resin and a coating property improving agent as long as the effects of the present invention are not impaired. Examples of the binder resin include polycarbonate, polystyrene, polyarylate, and polyester. Moreover, you may contain the binder resin hardened | cured with a heat | fever or light. As the binder resin that is cured by heat, light, or the like, a resin in which a curable functional group is introduced into the molecule in the hole transporting compound, a curable resin, or the like can be used. Specifically, examples of the curable functional group include acrylic functional groups such as acryloyl group and methacryloyl group, vinylene group, epoxy group, and isocyanate group. The curable resin may be a thermosetting resin or a photocurable resin, and examples thereof include an epoxy resin, a phenol resin, a melamine resin, a polyester resin, a polyurethane resin, a silicon resin, and a silane coupling agent. be able to.

(Average particle size)
The average particle diameter of the wettability changing material of the present embodiment is not particularly limited, and is, for example, in the range of 0.5 nm to 999 nm, but in the range of 0.5 nm to 50 nm, particularly in the range of 0.5 nm to 20 nm. It is preferable to be within. The average particle diameter of the wettability changing material is further preferably 15 nm or less, and particularly preferably in the range of 1 nm to 10 nm. This is because, when the particle diameter is 1 nm or less, it exceeds the resolution of the dynamic light scattering method or the like, so that it is difficult to prove the existence of the particles or to stably manufacture them. On the other hand, if the particle size is too large, the surface area per unit weight (specific surface area) will be small, and the desired effect may not be obtained, and the surface roughness of the hole injecting and transporting layer will be large, causing frequent shorts. Because there is a risk of doing.
Here, the average particle diameter is 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 microscope (SEM) or From an image obtained using a transmission electron microscope (TEM), a region in which 20 or more transition metal-containing nanoparticles are confirmed to be present is selected, and all transition metal-containing nanoparticles in this region are selected. The particle diameter is measured and the average value is obtained.
In the non-spherical nanocluster, the particle diameter is the longest diameter, for example, the diameter of the outer circle in the case of a donut shape, and the length of the major axis in the case of a lemon shape.

(Production method)
The method for producing the wettability changing material of the present embodiment is particularly limited as long as it is a method capable of obtaining the above-described transition metal-containing nanoparticles or transition metal-containing nanoclusters having a fluorine-containing organic compound attached thereto. It is not a thing. Examples of the method for producing transition metal-containing nanoparticles having a fluorine-containing organic compound attached to the surface include, for example, a liquid such as a reaction between a transition metal complex and a protective agent having a linking group at the terminal of the fluorine-containing organic compound in an organic solvent. Examples include the phase method. After the transition metal complex is reacted with a protective agent not containing a fluorine-containing organic compound in an organic solvent, a part or all of the protective agent not containing the fluorine-containing organic compound is replaced with a protective agent containing the fluorine-containing organic compound. May be.
In addition, as a method for producing a transition metal-containing nanocluster having a fluorine-containing organic compound attached to the surface, after synthesizing the transition metal-containing nanocluster, a protective agent having a linking group is attached to the end of the fluorine-containing organic compound by cation exchange or the like. And the like. As the salt used for cation exchange, an ionic liquid such as the aforementioned ammonium salt is preferably used. In this case, both an inorganic anion and an organic anion can be used as the counter anion.

(B) 2nd aspect The wettability change material of this aspect is a material in which a fluorine-containing organic compound is attached to an organic-transition metal oxide composite that is a reaction product of an organic transition metal complex.

  Since the wettability changing material of this embodiment is an organic-transition metal oxide composite with a fluorine-containing organic compound attached to the surface, it adheres to the surface by the action of a photocatalyst accompanying energy irradiation or irradiation with vacuum ultraviolet light. It is a material whose wettability changes from lyophobic to lyophilic by being able to decompose and remove the fluorine-containing organic compound. When the wettability changing material of this embodiment is used, the portion where the photocatalyst action due to energy irradiation or the portion irradiated with vacuum ultraviolet light becomes a lyophilic region, and the portion where the photocatalyst action due to energy irradiation does not reach Alternatively, a portion that is not irradiated with vacuum ultraviolet light becomes a liquid repellent region. The wettability changing material of this embodiment is a reaction product of an organic transition metal complex, although the fluorine-containing organic compound adhering to the surface is decomposed and removed by the action of a photocatalyst associated with energy irradiation or irradiation with vacuum ultraviolet light. A certain organic-transition metal oxide composite itself is resistant to ultraviolet light and relatively high-temperature heating, so that the excellent hole injecting and transporting property of the organic-transition metal oxide composite has energy irradiation, There is an advantage that the photocatalyst is not damaged during the process such as the action of the photocatalyst and the heating. Furthermore, the wettability changing material of this embodiment has the merit that it undergoes a treatment such as a photocatalytic treatment for decomposing fluorine to be oxidized to increase the ionization potential and improve the hole injection property.

In addition, the wettability changing material of this embodiment is an organic-transition metal oxide composite and contains an organic portion containing at least a fluorine-containing organic compound on the surface, so that the adhesion between the adjacent organic layers is close. The property is also good. Since the organic layer is formed on the lyophilic region where the fluorine-containing organic compound has been decomposed, there is no influence of liquid repellency derived from the fluorine-containing organic compound at the interface with the adjacent organic layer, and the interface has excellent adhesion It becomes a thing.
In addition, the organic-transition metal oxide complex, which is a reaction product of an organic transition metal complex, is considered to have a high reactivity of the transition metal oxide contained therein and easily form a charge transfer complex. Therefore, the wettability changing material of this embodiment can form a hole injecting and transporting layer capable of realizing an organic EL element with low voltage driving, high power efficiency, and long life.

Furthermore, the organic-transition metal oxide composite used in the wettability changing material of this embodiment is a composite of an organic substance and a transition metal oxide, and contains an organic portion containing at least a fluorine-containing organic compound on the surface. Therefore, it has dispersibility in a solvent. Therefore, since a thin film can be formed by a wet process, the hole injection / transport layer to the organic layer such as the light emitting layer can be sequentially formed only by the wet process, which has a great merit in the manufacturing process.
Hereinafter, the structure of the wettability changing material of this embodiment will be described in order.

(Organic-transition metal oxide complex)
The organic-transition metal oxide composite used in the wettability changing material of this embodiment is a reaction product of an organic transition metal complex and contains a transition metal oxide. The organic-transition metal oxide complex, which is a reaction product of an organic transition metal complex, is a process for forming a hole injection / transport layer, for example, in a coating liquid for forming a hole injection / transport layer, It may be a reaction product generated by a reaction of an organic transition metal complex performed at the time of heating, light irradiation, element driving, etc. after layer formation.
The organic-transition metal oxide composite may contain transition metal atoms and compounds having various valences depending on processing conditions, such as transition metal carbides, sulfides, borides, selenides, halides, and the like. .

  The transition metal in the transition metal oxide contained in the organic-transition metal oxide composite is a generic name for metal elements existing between Group 3 to Group 11 in the periodic table. Specific examples of the transition metal include molybdenum, tungsten, vanadium, rhenium, nickel, copper, titanium, platinum, and silver.

  Among them, the transition metal in the transition metal oxide contained in the organic-transition metal oxide composite contains at least one metal selected from the group consisting of molybdenum, tungsten, rhenium and vanadium. Therefore, it is preferable from the viewpoint of easily forming a charge transfer complex and reducing the driving voltage and improving the device life.

The metal contained in the organic-transition metal oxide composite may be a single metal or two or more kinds. As an aspect in which two or more kinds of metals are contained, two or more kinds of metals or metal oxides may be contained in combination, or two or more kinds of metals may be contained as an alloy. Further, a different binuclear metal complex may be used.
Note that the metal contained in the organic-transition metal oxide composite may contain a non-transition metal as long as at least a transition metal is contained.
By including two or more metals, hole injection with other functions such as complementing each other with hole transportability and hole injection property, imparting photocatalytic properties, and controlling the refractive index and transmittance of the thin film There is an advantage that a transport layer can be formed.

The organic transition metal complex is a coordination compound containing a transition metal, and contains a ligand containing an organic compound in addition to the transition metal described above.
For example, the organic molybdenum complex includes a complex having an oxidation number of −2 to +6. Further, as the organic tungsten complex, there are complexes having an oxidation number of −2 to +6. Tungsten complexes tend to be polynuclear and have oxo ligands, and tend to resemble molybdenum complexes, and the coordination number may be 7 or more. Further, as the organic vanadium complex, there are complexes having an oxidation number of −3 to +5.
The type of the ligand is appropriately selected and is not particularly limited. However, a ligand containing an organic part (carbon atom) is used from the viewpoint of solvent solubility and adhesion with an adjacent organic layer. Moreover, it is preferable that a ligand decomposes | disassembles from a complex at comparatively low temperature (for example, 200 degrees C or less).

  Examples of the monodentate ligand include acyl, carbonyl, thiocyanate, isocyanate, cyanate, halogen atom and the like. Of these, carbonyl which is easily decomposed at a relatively low temperature is preferable. Examples of the bidentate ligand include various carboxylic acids.

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, and phenyltriazole. , 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 organic transition metal complex becomes high. If the complex itself becomes too stable, the reactivity may be poor.

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 ).

Examples of the molybdenum (II) complex 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. Further, a carboxylic acid having a carboxyl group in a hole transporting compound (arylamine derivative, carbazole derivative, thiophene derivative, fluorene derivative, distyrylbenzene derivative, etc.) as described later 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 it is suitable for optimizing the interaction with the mixed hole transporting compound, optimizing the hole injection transport function, and optimizing the adhesion with the adjacent organic layer. It is a rank. X is halogen or alkoxide, and chlorine, bromine, iodine, methoxide, ethoxide, isopropoxide, sec-butoxide, and tert-butoxide can be used. The L is a neutral ligand, it may be used triarylphosphine such as trialkylphosphine or triphenylphosphine, such as _{P (n-C 4 H 9} ) 3 or P _{(CH 3)} 3.
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] and ^{_{[Mo II I 2 (diars)}} 2] (diars is diarsine _{(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⁻ .

Examples of the molybdenum (V) complex having an oxidation number of +5 include [Mo (CN) ₈ ] ³⁻ and binuclear Mo ₂ O ₃ ^{4+ in} which ^Mo═O is bridged by O ²⁻ in the trans position. Examples of the oxo complexes include xanthogenic acid complexes Mo ₂ O ₃ (S ₂ COC ₂ H ₅ ) ₄ , and oxo complexes having a binuclear Mo ₂ O ₄ ^{2+ in} which ^Mo═O is double-crosslinked with O ²⁻ in the cis position. Examples thereof include a 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.

As the oxidation number of 0 or less tungsten complex include a metal carbonyl _{^{[W -II (CO) 5]}} 2-, [(CO) 5 W -I W -I (CO) 5] 2-, [W ( CO) ₆ ] and the like.
Examples of the tungsten (I) complex having an oxidation number of +1 include non-Werner type complexes containing diphosphane and η ⁵ -cyclopentadienide. Specifically, [W ^I (η ⁶ -C ₆ H ₆ ) ₂ ] ⁺ , [WCl (N ₂ ) (diphos) ₂ ] (diphos is a bidentate ligand (C ₆ H ₅ ) 2PCH ₂ CH ₂ P (C ₆ H ₅ ) ₂ ).

The tungsten (II) complex having an oxidation number of +2 includes a W ₂ compound in which tungsten becomes a binuclear complex and exists in the state of (W ₂ ) ⁴⁺ ions. For example, [W ₂ (RCOO) ₄ ] And [W ₂ X ₂ L ₂ (RCOO) ₄ ]. Here, R in the RCOO can be the same as that described for the molybdenum complex. Other examples of the tungsten (II) complex having an oxidation number of +2 include halogen complexes such as [W ^II ₂ X ₄ L ₄ ] and [W ^II X ₂ L ₄ ]. For example, [W ^II Br _{4 (P (n-C 4 H} 9) 3) 4] and ^{_{[W II I 2 (diars)}} 2] (diars is diarsine _{(CH 3) 2 As-C} 6 H 4 -As (CH 3) 2) , etc. Is mentioned.

Examples of the tungsten (III) complex having an oxidation number of +3 include [(RO) ₃ W≡W (OR) ₃ ] and [W (CN) ₇ (H ₂ O)] ⁴⁻ . R is a linear or branched alkyl group having 1 to 20 carbon atoms.
Examples of the tungsten (IV) complex having an oxidation number of +4 include [W {N (CH ₃ ) ₂ } ₄ ], [W (CN) ₈ ] ⁴⁻ , and WO ²⁺ having an oxo ligand. And a complex of W ₂ O ₂ ⁴⁺ double-crosslinked with O ²⁻ .

Examples of the tungsten (V) complex having an oxidation number of +5 include [W (CN) ₈ ] ³⁻ and binuclear W ₂ O ₃ ^{4+ in} which ^W═O is bridged by O ²⁻ in the trans position. Examples of the oxo complexes include xanthogenic acid complexes W ₂ O ₃ (S ₂ COC ₂ H ₅ ) ₄ , and oxo complexes having binuclear W ₂ O ₄ ^{2+ in} which ^W═O is double-bridged with O ²⁻ in the cis position. Examples thereof include a histidine complex [W ₂ O ₄ (L-histidine) ₂ ] · 3H ₂ O.
Examples of the tungsten (VI) complex having an oxidation number of +6 include [WO ₂ (acetylacetonate) ₂ ]. In the case of a complex having two or more nuclei, there is a mixed valence complex.

Examples of vanadium complexes having an oxidation number of 0 or less include metal carbonyl [V ⁰ (CO) ₆ ], and examples of metal oxide complexes include V ^III O oxytriisopropoxide.
Examples of the vanadium (II) complex having an oxidation number of +2 include cyclopentadienyl complex [V ^II (η ⁵ -C ₅ H ₅ ) ₂ ].

Examples of the vanadium (III) complex having an oxidation number of +3 include [V ^III Cl ₃ {N (CH ₃ ) ₃ } ₂ ], and examples of the metal oxide complex include V ^III O acetylacetonate.
Examples of the vanadium (IV) complex having an oxidation number of +4 include [VOCl ₂ {N (CH ₃ ) ₃ } ₂ ], [VCl ₄ (diars)], 8 (decahedral [VCl ₄ (diars) ₂ ]), etc. Is mentioned.

  The organic-transition metal oxide complex that is a reaction product of the organic transition metal complex always contains a transition metal oxide. By always including transition metal oxides, the value of ionization potential is optimized, and changes due to oxidation from unstable oxidation number +0 metal are suppressed in advance, so that the drive voltage is reduced and the device lifetime is reduced. It becomes possible to improve. Among them, it is preferable that transition metal oxides having different oxidation numbers coexist in the organic-transition metal oxide composite. By including transition metal oxides with different oxidation numbers together, the hole transportability and hole injection properties are appropriately controlled by the balance of the oxidation numbers, which improves drive voltage and device life. It becomes possible to make it.

For example, the reaction product of a molybdenum complex or a tungsten complex may be a composite with molybdenum oxidation numbers of +5 and +6 or a composite with tungsten oxidation numbers of +5 and +6. This is preferable from the viewpoint of improving the life. Furthermore, the reaction product of the molybdenum complex or the reaction product of the tungsten complex exists in the anion state of the complex of molybdenum oxidation numbers +5 and +6 or tungsten oxidation numbers +5 and +6, respectively. It is preferable from the viewpoint of lowering and improving the device life.
When the molybdenum oxidation number is +5 and +6 or the tungsten oxidation number is +5 and +6, the oxidation number is +6 molybdenum or tungsten, and the oxidation number is +5 molybdenum or tungsten. Is preferably 10 mol or more from the viewpoint of lowering the driving voltage and improving the element life. On the other hand, in the case of ordinary molybdenum oxides such as MoO ₃ , most of the molybdenum is Mo ^VI , and the composition formula is Mo _n O _3n . However, it may become Mo _n O _3n-m due to oxygen vacancies at the time of vapor deposition or oxygen defects present on the particle surface caused by physical pulverization at the time of slurry formation, and Mo ^V may be present to some extent. However, Mo ^V introduced by MoO ₃ is caused by oxygen defects and is therefore non-uniform and unstable.
In the case of vanadium, the oxidation number +5 is stable (V ₂ O ₅ ), and the oxidation number +4 is unstable (V ₂ O ₄ ). The reaction product of the vanadium complex is preferably present in the anion state of the complex having vanadium oxidation numbers of +5 and +4 from the viewpoint of reducing the driving voltage and improving the device lifetime.

The organic-transition metal oxide complex is preferably a reaction product of an organic transition metal complex and an organic solvent, and further a reaction product of an organic transition metal complex and an organic solvent having a carbonyl group and / or a hydroxyl group It is preferable that Since the organic transition metal complex has high reactivity, it is heated in the process of forming the hole injection / transport layer, for example, in the coating liquid for forming the hole injection / transport layer or at the time of forming the hole injection / transport layer. When irradiation is performed, an oxidation-reduction reaction is performed with the organic solvent contained in the hole injection transport layer forming coating solution, and at least a part of the transition metal complex becomes a transition metal oxide. When the organic solvent is an organic solvent having a carbonyl group and / or a hydroxyl group, the reactivity for producing the transition metal oxide is high.
For example, when an organic molybdenum complex or an organotungsten complex is used, an anion state of a complex having molybdenum oxidation numbers of +5 and +6 or a complex having tungsten oxidation numbers of +5 and +6 is formed. Can be stably maintained even in a relatively large amount of +5 molybdenum or tungsten, which is preferable from the viewpoint of lowering driving voltage and improving element life.

  The organic solvent is not particularly limited as long as it can appropriately perform an oxidation-reduction reaction with an organic transition metal complex. Examples of the organic solvent having a carbonyl group and / or a hydroxyl group that are preferably used include aldehyde-based, ketone-based, carboxylic acid-based, ester-based, amide-based, alcohol-based, and phenol-based solvents, and has a boiling point of 50 ° C to 250 ° C. Those having a temperature of ° C are preferably used. Examples of the organic solvent having a carbonyl group and / or a hydroxyl group include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isopropyl ketone, diisobutyl ketone, acetonyl acetone, Ketone solvents such as isophorone and cyclohexanone; aldehyde solvents such as acetaldehyde, propionaldehyde, furfural and benzaldehyde; carboxylic acid solvents such as acetic acid, propionic acid, butyric acid and valeric acid; ethyl acetate, n-propyl acetate and i-acetate Ester solvents such as propyl, n-butyl acetate, i-butyl acetate, n-amyl acetate, ethyl benzoate and butyl benzoate; amides such as N-methylformamide, N, N-dimethylformamide and N-ethylacetamide Solvent; methyl Alcohol solvents such as alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, glycerin, ethylene glycol, propylene glycol, 1,2-butylene glycol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether; Examples thereof include phenol solvents such as phenol, cresol, xylenol, ethylphenol, trimethylphenol, isopropylphenol, and t-butylphenol.

(Fluorine-containing organic compound attached to the surface)
In the wettability changing material of this embodiment, a fluorine-containing organic compound is attached to the organic-transition metal oxide composite.
In the wettability changing material of this embodiment, “attachment” means that the fluorine-containing organic compound is fixed to the surface of the organic-transition metal oxide composite to the extent that it does not peel even when dispersed in an organic solvent. . “Adhesion” includes adsorption and coordination, but chemical bonds such as ionic bonds and covalent bonds are preferred. The aspect of “attachment” may be an aspect in which the entire surface of the organic-transition metal oxide composite is attached so as to cover the fluorine-containing organic compound, or a part of the surface may contain the fluorine-containing organic compound. It may be an embodiment in which is attached.

  In the wettability changing material of this embodiment, since the organic compound including at least the fluorine-containing organic compound is adhered to the organic-transition metal oxide composite, particles formed simply by pulverizing the transition metal oxide Unlike the case, the dispersion stability is very high, and a thin film of nm order with high uniformity can be formed. Therefore, the hole injecting and transporting layer is not easily short-circuited because of its high temporal stability and uniformity. Furthermore, it becomes excellent in adhesiveness with the adjacent first electrode layer or organic layer.

  Note that the fluorine-containing organic compound is the same as that described in the first embodiment, and thus the description thereof is omitted here.

  In the wettability changing material of this embodiment, the content ratio of the organic-transition metal oxide complex that is a reaction product of the organic transition metal complex and the organic compound including the fluorine-containing organic compound attached to the surface thereof is Although it selects suitably and it does not specifically limit, It is preferable that the fluorine adhering to the surface is 10-200 weight part with respect to 100 weight part of transition metals in an organic-transition metal oxide composite. This ratio can be determined by, for example, X-ray photoelectron spectroscopy.

  Further, in the wettability changing material of this embodiment, the amount of the fluorine-containing organic compound adhering to the surface may be appropriately selected according to the requirement for the liquid repellency of the liquid repellency region of the hole injection transport layer. .

(Other ingredients)
In the case of the wettability changing material of this embodiment, the hole injecting and transporting layer may be composed of only the wettability changing material of this embodiment, and may further contain other components.
In addition, since it is the same as that of what was described in the said 1st aspect about another component, description here is abbreviate | omitted.

(Production method)
The method for producing the wettability changing material according to this aspect is a method capable of obtaining a material in which a fluorine-containing organic compound is attached to the surface of the organic-transition metal oxide complex which is a reaction product of the organic transition metal complex described above. If there is, it will not be specifically limited. Examples of the method for producing an organic-transition metal oxide complex having a fluorine-containing organic compound attached to the surface include, for example, an organic transition metal complex and a protective agent having a linking group at the terminal of the fluorine-containing organic compound in the presence of oxygen. Examples include a method of reacting in a solvent, preferably an organic solvent having a carbonyl group and / or a hydroxyl group. Alternatively, the organic transition metal complex is reacted in the presence of oxygen in an organic solvent, preferably in an organic solvent having a carbonyl group and / or a hydroxyl group to obtain an organic-transition metal oxide complex. An organic-transition metal oxide composite and a protective agent having a linking group at the end of the fluorine-containing organic compound are allowed to act to obtain a material having the fluorine-containing organic compound attached to the surface of the organic-transition metal oxide composite. Also good.

(C) 3rd aspect The wettability change material of this aspect is organopolysiloxane.
The wettability changing material of this embodiment is not particularly limited as long as it is a material having a main chain having a high binding energy that does not deteriorate or decompose due to the action of a photocatalyst accompanying energy irradiation or irradiation with vacuum ultraviolet light. Specific examples include organopolysiloxanes. Among these, the organopolysiloxane is preferably an organopolysiloxane containing a fluoroalkyl group. This is because the wettability of the wettability changing material can be greatly changed by the action of the photocatalyst accompanying energy irradiation or irradiation with vacuum ultraviolet light. In addition, about the organopolysiloxane which has a fluoroalkyl group, it can be set as the thing similar to what is described in Unexamined-Japanese-Patent No. 2000-249821, for example.

  When the wettability changing material is an organopolysiloxane, the hole injecting and transporting layer may contain a photocatalyst. In addition, the photocatalyst used for a positive hole injection transport layer can be made into the same thing as what is described in Unexamined-Japanese-Patent No. 2007-48530, for example.

  The content of the photocatalyst in the hole injecting and transporting layer is an amount that can change the wettability of the wettability changing material contained in the hole injecting and transporting layer and does not inhibit the transport of holes or electrons. There is no particular limitation as long as it is present.

  When the hole injecting and transporting layer contains a wettability changing material and a photocatalyst, the hole injecting and transporting layer may be a single layer containing the wettability changing material and the photocatalyst. A layer containing a property change material may be laminated. In the case of a single layer containing a wettability changing material and a photocatalyst, the wettability of the wettability changing material changes due to the action of the photocatalyst contained in the hole injecting and transporting layer itself. The wettability change pattern can be efficiently formed. On the other hand, when the layer containing the photocatalyst and the layer containing the wettability changing material are laminated, the layers are separated for each function, so the layer configuration, the combination of materials, etc. can be easily changed. be able to.

  In addition to the above-mentioned photocatalyst, the hole injecting and transporting layer may contain, for example, the same surfactants and additives as described in JP-A No. 2000-249821.

(2) Liquid repellent region and lyophilic region The hole injecting and transporting layer has a wet surface consisting of a liquid repellent region disposed on the partition wall and a lyophilic region disposed on the opening of the partition wall. Has a sex change pattern.
The “liquid repellent region” refers to a region having a liquid contact angle larger than that of the lyophilic region, and is a region having poor wettability with respect to the organic layer forming coating solution. 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 an organic layer forming coating solution or the like. The contact angle of the liquid required for the liquid repellent region and the lyophilic region depends on the surface tension of the organic layer forming coating solution used.

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. 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.
An example of the liquid having a surface tension of 28.5 mN / m is m-xylene at 22 ° C.

  The coating liquid for organic 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.

  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 liquid repellent region and the lyophilic region may be formed at any position as long as the liquid repellent region is disposed on the partition and the lyophilic region is disposed at the opening of the partition.
The liquid repellent region is preferably disposed on the entire top surface of the partition wall. This is because the light emitting layer and the like can be patterned with high accuracy.
The lyophilic region may be disposed on the side surface of the partition wall. Active oxygen species such as oxygen radicals are generated by the action of a photocatalyst associated with energy irradiation or irradiation with vacuum ultraviolet light, and the organic groups constituting the wettability changing material are decomposed by the strong oxidation and reduction power of this active oxygen species. As a result, the wettability of the wettability changing material changes. Since reactive oxygen species do not have straightness like light, the wettability changes not only at the opening of the partition wall but also at the side surface of the partition wall due to the action of a photocatalyst accompanying energy irradiation or irradiation with vacuum ultraviolet light. It can be a sex area.

  Moreover, the lyophilic region may be formed between the second electrode layer and the second electrode layer take-out electrode. For example, as shown in FIGS. 6A to 6B, a hole injection transport layer 6 (not shown in FIG. 6A) is formed on the entire surface of the substrate 2, and the second electrode layer 8 (FIG. 6 (a), a one-dot chain line) and the second electrode layer take-out electrode 9 may be formed with a lyophilic region 12 (broken line in FIGS. 6A to 6B). The wettability-changing material is a material in which a fluorine-containing organic compound is attached to the surface of a transition metal-containing nanoparticle or transition metal-containing nanocluster containing at least a transition metal oxide, or an organic that is a reaction product of an organic transition metal complex -In the case where the fluorine-containing organic compound is attached to the transition metal oxide composite, the fluorine-containing organic compound attached to the surface is removed by the action of a photocatalyst associated with energy irradiation or irradiation with vacuum ultraviolet light. It can be disassembled and removed. Accordingly, in the lyophilic region, the fluorine-containing organic compound is decomposed and removed, leaving only the transition metal-containing nanoparticles, transition metal-containing nanoclusters, or organic-transition metal oxide complex. Therefore, the lyophilic region can have conductivity. Therefore, even when a lyophilic region is formed between the second electrode layer and the second electrode layer extraction electrode, the second electrode layer and the second electrode layer extraction electrode are electrically connected. It is possible.

  In addition, since the formation method of a lyophilic area | region and a liquid repellent area | region is described in the term of "B. Manufacturing method of an organic EL element" mentioned later, description here is abbreviate | omitted.

(3) Other points of hole injecting and transporting layer As the film thickness of the hole injecting and transporting layer, it is possible to form a wettability change pattern composed of a lyophilic region and a liquid repellent region, and The film thickness is not particularly limited as long as it does not inhibit the injection / transport, and is appropriately selected according to the type of the wettability changing material, the configuration of the hole injection / transport layer, and the like. Specifically, the thickness of the hole injecting and transporting layer is preferably in the range of 0.1 nm to 1000 nm, more preferably in the range of 1 nm to 500 nm.

  The hole injecting and transporting layer may be formed on the entire surface of the substrate, or may be formed on the substrate excluding the outer edge portion. Especially, as illustrated in FIG. 1 and FIGS. 2A to 2C, the hole injecting and transporting layer 6 is preferably formed on the substrate 2 excluding the outer edge portion. This is because, in order to seal the organic EL element, it is preferable that the hole injecting and transporting layer is not formed on the outer edge portion of the substrate.

  In addition, when the hole injecting and transporting layer is formed on the entire surface of the substrate, the second electrode layer and the second electrode layer are formed in order to allow electrical connection between the second electrode layer and the second electrode layer extraction electrode. The portion of the hole injecting and transporting layer located between the electrode layer extraction electrodes is preferably a lyophilic region. As described above, the wettability changing material is a material in which a fluorine-containing organic compound is attached to the surface of a transition metal-containing nanoparticle or transition metal-containing nanocluster containing at least a transition metal oxide, or a reaction of an organic transition metal complex. When the material is a material in which a fluorine-containing organic compound is attached to the organic-transition metal oxide composite that is the product, the lyophilic region can have conductivity. Therefore, even if the hole injecting and transporting layer is formed on the entire surface of the substrate, when the lyophilic region is formed between the second electrode layer and the second electrode layer take-out electrode, the second The electrode layer and the extraction electrode for the second electrode layer can be electrically connected.

  In addition, since the formation method of a positive hole injection transport layer is described in the term of "B. Manufacturing method of an organic EL element" mentioned later, description here is abbreviate | omitted.

2. Partition Wall The partition wall in the present invention is formed in a stripe shape in a direction perpendicular to the longitudinal direction of the first electrode layer on the substrate on which the first electrode layer is formed, and the cross-sectional shape is an inversely tapered shape.

  The partition walls may be formed in stripes in the direction perpendicular to the longitudinal direction of the first electrode layer. For example, as shown in FIG. 5, the barrier ribs 5 may be formed in stripes in a direction perpendicular to the longitudinal direction of the first electrode layer 3, and as shown in FIG. 7, the barrier ribs 5 are formed in the first electrode layer 3. The barrier ribs 5b formed so as to connect the end portions of the barrier ribs 5a formed on the side where the second electrode layer lead-out electrodes 9 are not formed with the barrier ribs 5a formed in a stripe shape in a direction perpendicular to the longitudinal direction You may have.

The cross-sectional shape of the partition wall may be a reverse taper shape.
The width and angle of the cross section of the partition wall are not particularly limited as long as the cross-sectional shape is an inversely tapered shape and can sever the second electrode layer, and can be a general width or angle, The thickness is appropriately set according to the thickness of each layer, the size of the organic EL element, and the like.
The height of the partition wall can be about 0.01 μm to 50 μm.

  The length of the partition is not particularly limited as long as the second electrode layer can be divided by the partition, and is appropriately set according to the size of the organic EL element. In particular, the length of the stripe-shaped partition perpendicular to the longitudinal direction of the first electrode layer is preferably longer than the length of the second electrode layer in the longitudinal direction of the strip-shaped partition. As illustrated in FIG. 5, when the partition walls 5 are formed only in stripes in the direction orthogonal to the longitudinal direction of the first electrode layer 3, the stripes orthogonal to the longitudinal direction of the first electrode layer 3 are usually used. The length d <b> 2 of the partition wall 5 is set to be longer than the length d <b> 1 of the second electrode layer 8 in the longitudinal direction of the strip-like partition wall 5 (the chain line in FIG. 5). This is because the second electrode layer is divided by the stripe-shaped partition wall. On the other hand, as shown in FIG. 7, the barrier ribs 5a are formed in stripes in a direction perpendicular to the longitudinal direction of the first electrode layer 3, and the stripes on the side where the second electrode layer extraction electrodes 9 are not formed. If the second electrode layer is divided by the stripe-shaped partition wall, the length d2 of the stripe-shaped partition wall 5a is as long as the second partition layer is divided by the stripe-shaped partition wall. The length may be set to be longer than the length d1 of the second electrode layer 8 (the one-dot chain line in FIG. 5) in the longitudinal direction of the stripe-shaped partition wall 5a. Also good. Regardless of the configuration of the barrier ribs, as illustrated in FIGS. 5 and 7, on the side where the second electrode layer extraction electrode 9 is formed, the end e2 of the striped barrier rib is the second electrode layer. Is set to the outside of the end e1. This is because the second electrode layer is divided by the stripe-shaped partition wall.

  The length of the partition wall means the length of the stripe-shaped partition wall orthogonal to the longitudinal direction of the first electrode layer. Further, the longitudinal direction of the partition wall refers to the longitudinal direction of the striped partition wall orthogonal to the longitudinal direction of the first electrode layer. The length of the second electrode layer in the longitudinal direction of the partition refers to the length of the second electrode layer in a direction parallel to the longitudinal direction of the striped partition perpendicular to the longitudinal direction of the first electrode layer.

The wettability of the partition wall surface is not particularly limited as long as a hole injecting and transporting layer can be formed on the partition wall, but is usually lyophilic.
The material used for the partition is not particularly limited as long as a hole injecting and transporting layer can be formed on the partition, and a resin generally used for forming a partition of an organic EL element is used. can do. Examples of the 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, polyethersulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide resin, polyamideimide resin , It can be used polyamic acid resin, polyether imide resin, phenol resin, urea resin and the like.

  As a method for forming the partition wall, a method generally used for forming the partition wall of the organic EL element can be used, and examples thereof include a photolithography method and a thermal transfer method.

3. Organic Layer The organic layer used in the present invention is formed on the lyophilic region of the hole injecting and transporting layer and includes at least a light emitting layer. The organic layer forming region where the organic layer is provided is It does not overlap with the second electrode layer extraction electrode forming region where the two electrode layer extraction electrode is provided.

In the present invention, the organic layer refers to a layer formed on the lyophilic region of the hole injection transport layer by a coating method.
Examples of the organic layer other than the light emitting layer include a second hole injection transport 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.

  As the formation position of the organic layer, the organic layer is formed only on the lyophilic region, the organic layer formation region where the organic layer is provided is the second electrode where the second electrode layer extraction electrode is provided. There is no particular limitation as long as it does not overlap with the electrode layer extraction electrode formation region. Since the organic layer formation region does not overlap with the second electrode layer extraction electrode formation region, the electrical connection between the second electrode layer and the second electrode layer extraction electrode can be ensured.

  Hereinafter, each layer constituting the organic 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 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 "B. Manufacturing method of organic EL element" mentioned later, description here is abbreviate | omitted.

(2) Second hole injecting and transporting layer In the present invention, a second hole injecting and transporting layer may be formed between the hole injecting and transporting layer and the light emitting layer.
The material for forming the second 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. Examples of such materials include arylamine derivatives, anthracene derivatives, carbazole derivatives, thiophene derivatives, fluorene derivatives, distyrylbenzene derivatives, spiro compounds, and the like. Specific examples of the arylamine derivative include bis (N- (1-naphthyl) -N-phenyl) -benzidine (α-NPD), N, N′-bis- (3-methylphenyl) -N, N′-. Bis- (phenyl) -benzidine (TPD), 4,4,4-tris (3-methylphenylphenylamino) triphenylamine (MTDATA), copoly [3,3′-hydroxy-tetraphenylbenzidine / diethylene glycol] carbonate ( PC-TPD-DEG) and the like. Specific examples of the anthracene derivative include 9,10-di-2-naphthylanthracene (DNA), poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (9,10-anthracene). And the like. Specific examples of the carbazole derivative include 4,4-N, N′-dicarbazole-biphenyl (CBP), polyvinyl carbazole (PVK), and the like. Specific examples of the thiophene derivative include poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (bithiophene)]. Specific examples of the fluorene derivative include poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4 ′-(N- (4-sec-butylphenyl)) diphenylamine)] (TFB). Specific examples of the distyrylbenzene derivative include 1,4-bis (2,2-diphenylvinyl) benzene (DPVBi). Specific examples of spiro compounds include poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9′-spiro-bifluorene-2,7-diyl)] and the like. Can be mentioned. These materials may be used alone or in combination of two or more.

  The film thickness of the second 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.

  In addition, since the formation method of a 2nd hole injection transport layer is described in the term of the "B. manufacturing method of an organic EL element" 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 in stripe form 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, when light is extracted from the substrate side, or when energy is irradiated from the substrate side when forming the wettability change pattern in the process of manufacturing the organic EL element of the present invention, the first electrode layer has transparency. It is preferable. 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, when light is extracted from the second electrode layer side, 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 is formed in a stripe shape 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. Examples of the patterning method for the first electrode layer include a photolithography method and a vapor deposition method using a metal mask.

5. Second electrode layer The second electrode layer used in the present invention is a cathode, is formed on the organic layer and the partition, is divided by the partition, and is provided with the second electrode layer. The electrode layer formation region overlaps with the second electrode layer extraction electrode formation region where the second electrode layer extraction electrode is provided.

  As a formation position of the second electrode layer, the second electrode layer is formed on the organic layer and the partition wall, the second electrode layer is divided by the partition wall, and the second electrode layer is provided. The formation region is not particularly limited as long as the formation region overlaps with the second electrode layer extraction electrode formation region in which the second electrode layer extraction electrode is provided. Since the second electrode layer formation region overlaps with the second electrode layer extraction electrode formation region, the electrical connection between the second electrode layer and the second electrode layer extraction electrode can be ensured. .

  The dimension of the second electrode layer is not particularly limited as long as the second electrode layer is divided by the partition wall, and is appropriately set according to the size of the organic EL element. In particular, as described above, the length of the second electrode layer in the longitudinal direction of the partition wall is preferably shorter than the length of the striped partition wall orthogonal to the longitudinal direction of the first electrode layer. As illustrated in FIG. 5, when the partition walls 5 are formed only in stripes in the direction orthogonal to the longitudinal direction of the first electrode layer 3, the stripes orthogonal to the longitudinal direction of the first electrode layer 3 are usually used. The length d1 of the second electrode layer 8 (the alternate long and short dash line in FIG. 5) in the longitudinal direction of the partition wall 5 is set to be shorter than the length d2 of the stripe partition wall 5. This is because the second electrode layer is divided by the stripe-shaped partition wall.

  The material for forming the second electrode layer is not particularly limited as long as it is a conductive material. For example, when extracting light from the second electrode layer side, the second electrode layer preferably has transparency. On the other hand, for example, when the light is extracted from the substrate side, the second electrode layer is not required to be transparent. Note that the conductive material is the same as that described in the section of the first electrode layer, and thus description thereof is omitted here.

  The second electrode layer is formed on the organic layer and the partition so as to be divided by the partition. As a method for forming the second electrode layer, a general electrode forming method can be used, and examples thereof include a sputtering method, an ion plating method, and a vacuum evaporation method.

6). Substrate The substrate in the present invention supports the first electrode layer, the partition walls, the hole injection transport layer, the organic layer, the second electrode layer, and the like.
The substrate may be transparent or not transparent. For example, when light is extracted from the substrate side or when energy is irradiated from the substrate side when forming the wettability change pattern in the process of manufacturing the organic EL element of the present invention, the substrate is preferably transparent. Examples of the transparent substrate include quartz and glass. On the other hand, for example, when light is extracted from the second electrode layer side, 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.

7). Second Electrode Layer Extraction Electrode The second electrode layer extraction electrode in the present invention is formed on the substrate, disposed in the opening of the partition wall, and electrically connected to the second electrode layer. In addition, the second electrode layer extraction electrode formation region where the second electrode layer extraction electrode is provided overlaps with the second electrode layer formation region where the second electrode layer is provided, and an organic layer is provided. It does not overlap with the organic layer forming region.

  As the formation position of the second electrode layer extraction electrode, the second electrode layer extraction electrode is formed on the substrate, the second electrode layer extraction electrode is disposed in the opening of the partition wall, and the second electrode layer extraction electrode is formed. There is no particular limitation as long as the formation region overlaps with the second electrode layer formation region and the second electrode layer extraction electrode formation region does not overlap with the organic layer formation region. The second electrode layer extraction electrode is disposed in the opening of the partition wall, the second electrode layer extraction electrode formation region overlaps the second electrode layer formation region, and the second electrode layer extraction electrode formation region is the organic layer formation region Therefore, the electrical connection between the second electrode layer and the second electrode layer take-out electrode can be ensured without disconnecting the second electrode layer.

  The extraction electrode for the second electrode layer only needs to be electrically connected to the second electrode layer, and the extraction electrode for the second electrode layer and the second electrode layer may be in direct contact as described above. In addition, a lyophilic region may be formed between the second electrode layer take-out electrode and the second electrode layer.

  The material for forming the second electrode layer extraction electrode is not particularly limited as long as it is a conductive material, and materials generally used for the extraction electrode of the organic EL element can be used. Alloys can be used. As metals, silver (Ag), aluminum (Al), gold (Ag), beryllium (Be), calcium (Ca), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), gallium (Ga), hafnium (Hf), indium (In), iridium (Ir), potassium (K), lanthanum (La), lithium (Li), magnesium (Mg), molybdenum (Mo), sodium (Na), niobium (Nb), nickel (Ni), osmium (Os), lead (Pb), palladium (Pd), platinum (Pt), rubidium (Rb), rhenium (Re), rhodium (Rh), ruthenium (Ru), antimony (Sb), silicon (Si), tin (Sn), strontium (St), tantalum (Ta), thorium (Th), titanium (T ), Thallium (Tl), uranium (U), vanadium (V), tungsten (W), yttrium (Y), ytterbium (Yb), zinc (Zn), and zirconium (Zr) and the like. Alloys include silver-palladium-copper (APC), silver-ruthenium-copper (ARC), alumel, brass (brass), constantan, duralumin, bronze, carbon steel, nickel, platinum rhodium, hyperco, hypernic, permalloy, Examples include permenders, platinoids, manganin, monel, foreign silver, and phosphor bronze. Moreover, these can be laminated | stacked and it can also be set as a multilayer film.

  The method for forming the second electrode layer take-out electrode can be the same as the method for forming the first electrode layer, and the description thereof is omitted here.

8). Insulating Layer In the present invention, an insulating layer that defines a light emitting region may be formed on the substrate on which the first electrode layer is formed so as to cover the end of the first electrode layer. The insulating layer is provided to prevent conduction between adjacent first electrode layers and conduction between the first electrode layer and the second electrode layer. The portion where the insulating layer is formed becomes a non-light emitting region. In the case where an insulating layer is formed, a partition wall is formed on the insulating layer.

The material for forming the insulating layer is not particularly limited as long as it has insulating properties, and may be an organic material or an inorganic material. Generally, the insulating layer is used as an insulating layer in an organic EL element. The material used 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.

9. Other Configurations The organic EL device of the present invention may have any structure as long as it has a substrate, a first electrode layer, a hole injection / transport layer, an organic layer, and a second electrode layer. You may have other structures, such as a block layer and the extraction electrode for 1st electrode layers.

(1) Electron injecting and transporting layer In the present invention, an electron injecting and transporting layer may be formed on the light emitting layer. The electron injecting and transporting layer may be an electron injecting layer having an electron injecting function for stably injecting electrons injected from the cathode (second electrode layer) into the light emitting layer, and is injected from the cathode (second electrode layer). It may be an electron transport layer having an electron transport function for transporting the emitted electrons into the light emitting layer, or may be a laminate of an electron injection layer and an electron transport layer. It may be a single layer having both.

  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 and 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. Examples thereof include azoles, triazoles, phenanthrolines, silole derivatives, cyclopentadiene derivatives, aluminum complexes, and the like. Specific examples of oxadiazoles include (2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole) (PBD) and the like, and phenanthroline. Examples thereof include bathocuproin, bathophenanthroline and the like, and examples of aluminum complexes include tris (8-quinolinol) aluminum complex (Alq ₃ ), bis (2-methyl-8-quinolinato) (p-phenylphenolate) aluminum complex (BAlq ) And the like.

  Furthermore, as a material for forming a single layer having both an electron injection function and an electron transport function, for example, an alkali metal organic complex such as 8-hydroxyquinolinolato Li (Liq) or an alkaline earth metal complex is doped. And electron transporting materials. Examples of the electron transporting material include the light emitting material and the material for forming the electron transporting layer. 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.

  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 within the range of 1 nm to 200 nm, more preferably within the range of 0.1 nm to 100 nm.

  As a method for forming the electron injecting and transporting layer, a dry process is usually used, and for example, a vacuum deposition method can be mentioned.

(2) First Electrode Layer Extraction Electrode In the present invention, the first electrode layer extraction electrode may be formed on the substrate. The extraction electrode for the first electrode layer is electrically connected to the first electrode layer.
In addition, since the formation material and formation method of the 1st electrode layer taking-out electrode are the same as that of the said 2nd electrode layer taking-out electrode, description here is abbreviate | omitted.

B. 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 a striped first electrode layer, a striped partition perpendicular to the longitudinal direction of the first electrode layer, and a second electrode layer extraction located in the opening of the partition. Formation of a hole injecting and transporting layer on a substrate on which an electrode is formed to form a hole injecting and transporting layer that has liquid repellency and whose wettability can be changed by the action of a photocatalyst associated with energy irradiation or irradiation with vacuum ultraviolet light A wettability change pattern for forming a wettability change pattern comprising a liquid repellent region disposed on the partition and a lyophilic region disposed in the opening of the partition on the surface of the hole injecting and transporting layer Forming a coating solution for forming an organic layer in a pattern on the hole injecting and transporting layer, and forming a second electrode layer take-out electrode forming region where the second electrode layer take-out electrode is provided; The above so as not to overlap An organic layer forming step of forming an organic layer including at least a light-emitting layer on the liquid region; and the partition on the partition and the organic layer by the partition so as to overlap the extraction electrode formation region for the second electrode layer And a second electrode layer forming step of forming a second electrode layer.

The manufacturing method of the organic EL element of the present invention can be divided into three embodiments by the wettability change pattern forming step.
Each embodiment will be described below.

1. First Embodiment A method of manufacturing an organic EL element according to the present embodiment includes a stripe-shaped first electrode layer, a stripe-shaped partition perpendicular to the longitudinal direction of the first electrode layer, and a first layer located in an opening of the partition. Hole injection transport layer forming step of forming a hole injection transport layer having liquid repellency and wettability changeable by the action of a photocatalyst accompanying energy irradiation on a substrate on which a two-electrode layer extraction electrode is formed And a photocatalyst-containing layer substrate on which a photocatalyst-containing layer containing at least a photocatalyst is formed on a substrate with a gap that allows the photocatalyst to act upon energy irradiation with respect to the hole injecting and transporting layer. After that, by irradiating the hole injection transport layer with energy in a pattern, the liquid repellent region disposed on the partition wall and the opening of the partition wall are disposed on the surface of the hole injection transport layer. Lyophilic A wettability change pattern forming step for forming a wettability change pattern composed of a conductive region, and an organic layer forming coating solution is applied in a pattern on the hole injecting and transporting layer, and the second electrode layer takeout electrode An organic layer forming step of forming an organic layer including at least a light emitting layer on the lyophilic region so as not to overlap with the extraction electrode forming region for the second electrode layer provided with, and on the partition and the organic layer And a second electrode layer forming step of forming a second electrode layer so as to be divided by the partition and overlap the second electrode layer extraction electrode formation region.

The manufacturing method of the organic EL element of this embodiment will be described with reference to the drawings.
3 (a) to (e), FIGS. 8 (a) to (b) and FIGS. 9 (a) to (b) are process diagrams showing an example of a method for producing an organic EL element of the present embodiment. 3A is a cross-sectional view taken along the line EE of FIG. 8A, FIG. 3C is a cross-sectional view taken along the line FF of FIG. 8B, and FIG. 3D is a cross-sectional view of FIG. GG sectional drawing, 3 (e) is the HH sectional drawing of FIG.9 (b).
First, as shown in FIG. 3A and FIG. 8A, a striped first electrode layer 3, an insulating layer 4 that defines a light emitting region, and a striped shape orthogonal to the longitudinal direction of the first electrode layer 3 are used. The substrate 2 on which the partition wall 5 and the second electrode layer extraction electrode 9 located at the opening of the partition wall 5 are formed has liquid repellency, and wettability can be changed by the action of a photocatalyst accompanying energy irradiation. The hole injection transport layer 6 is formed (hole injection transport layer forming step).
Next, as shown in FIG. 3B, the base 22, the light shielding part 23 formed in a pattern on the base 22, and the base 22 so as to cover the light shielding part 23 and containing 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 6 face each other, and the hole injection / transport layer located at the opening of the partition wall 5 through the photocatalyst-containing layer substrate 21. 6 is irradiated with ultraviolet light 27. As shown in FIGS. 3 (c) and 8 (b), as a result of irradiation with ultraviolet light 27, hole injection occurs in the exposed portion of the hole injection transport layer 6 due to the action of the photocatalyst contained in the photocatalyst containing layer 24. The wettability of the material contained in the transport layer 6 changes, and the lyophilic region 12 is formed. On the other hand, in the unexposed portion of the hole injection / transport layer 6, the wettability of the material contained in the hole injection / transport layer 6 remains unchanged and becomes the liquid repellent region 11. Thereby, the wettability change pattern which consists of the liquid repellent area | region 11 arrange | positioned on the partition 5 and the lyophilic area | region 12 arrange | positioned at the opening part of the partition 5 is formed (wetability change pattern formation process). .
Next, as shown in FIGS. 3D and 9A, a coating solution for forming an organic layer is applied in a pattern on the hole injecting and transporting layer 6, and the extraction electrode 9 for the second electrode layer is applied. The organic layer 7 including at least the light emitting layer is formed on the lyophilic region 12 so as not to overlap the second electrode layer extraction electrode formation region 19 provided with (organic layer formation step).
Thereafter, as shown in FIGS. 3 (e) and 9 (b), the second electrode layer extraction electrode forming region 19 is divided on the partition wall 5 and the organic layer 7 by the partition wall 5 so as to overlap. The two-electrode layer 8 is formed (second electrode layer forming step).

According to this embodiment, the hole injection transport layer having liquid repellency and whose wettability can be changed by the action of the photocatalyst accompanying energy irradiation is irradiated with energy using the photocatalyst-containing layer substrate, and hole injection is performed. By changing the wettability of the transport layer, it is possible to form a wettability change pattern including a liquid-repellent region and a lyophilic region in which the wettability of the hole injection transport layer is changed. Therefore, it is possible to pattern an organic layer such as a light emitting layer with high accuracy.
In addition, according to the present embodiment, the organic layer such as the light emitting layer can be accurately patterned using the wettability change pattern formed on the surface of the hole injecting and transporting layer. Since the layer and the second electrode layer are formed at predetermined positions, the second electrode layer take-out electrode and the second electrode layer formed in the opening of the partition wall can be electrically connected without disconnecting the second electrode layer. It is possible to connect.

  Hereinafter, each process in the manufacturing method of the organic EL element of this embodiment is demonstrated.

(1) Hole Injecting and Transporting Layer Forming Step The hole injecting and transporting layer forming step in this embodiment includes a striped first electrode layer, a striped partition perpendicular to the longitudinal direction of the first electrode layer, and the partition A hole injecting and transporting layer having liquid repellency and whose wettability can be changed by the action of a photocatalyst accompanying energy irradiation is formed on the substrate on which the extraction electrode for the second electrode layer located in the opening is formed. It is a process.

  As a method for forming the hole injecting and transporting layer, there are a striped first electrode layer, a striped partition perpendicular to the longitudinal direction of the first electrode layer, and a second electrode layer take-out electrode located in the opening of the partition. There is no particular limitation as long as it is a method capable of forming the material used for the hole injecting and transporting layer described in the above section “A. Organic EL device” on the formed substrate. 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 according to the type of material used for the hole injecting and transporting layer. From the viewpoint of process superiority, since the organic layer including the light emitting layer is formed by a wet process in the organic layer forming step, it is desirable that the method for forming the hole injection transport layer is also a wet process.

  In the case of a wet process, the solvent used in the hole injecting and transporting layer forming coating solution is not particularly limited as long as it can dissolve or disperse the above materials. It is appropriately selected according to the type of material used for the.

  For example, when the hole injecting and transporting layer contains a material in which a fluorine-containing organic compound is attached to the surface of a transition metal-containing nanoparticle or transition metal-containing nanocluster containing at least a transition metal oxide, that is, the above-mentioned “A. In the case of containing the wettability changing material of the first aspect described in the section of “Organic EL device”, as the solvent, transition metal-containing nanoparticles or transition metal-containing nanoclusters and other components contained as necessary are good. It is not particularly limited as long as it dissolves or disperses in the solution. Examples include toluene, xylene, dodecylbenzene, cyclohexanone, cyclohexanol, tetralin, mesitylene, anisole, methylene chloride, tetrahydrofuran, dichloroethane, chloroform, ethyl benzoate, butyl benzoate, and the like. In addition, since a fluorine-containing organic compound is attached to the surface of the transition metal-containing nanoparticle or transition metal-containing nanocluster, a fluorine-based solvent is preferably used. For example, trifluoromethylbenzene, heptafluoro-n-ethyl butyrate, heptafluoro-n-butyrate methyl, or the like obtained by fluorinating all or part of the solvent can be used. These solvents may be used alone, or may be used as a co-solvent obtained by mixing a plurality of these solvents.

In this case, the hole injecting and transporting layer forming coating liquid is prepared by mixing transition metal-containing nanoparticles or transition metal-containing nanoclusters containing at least a transition metal oxide having a fluorine-containing organic compound attached to the surface and a solvent. May be. Also, transition metal-containing nanoparticles or transition metal-containing nanoclusters with fluorine-containing organic compounds attached to the surface are mixed with a solvent, and transition metals and / or transitions contained in transition metal-containing nanoparticles or transition metal-containing nanoclusters are mixed. A metal compound may be oxidized to a transition metal oxide to obtain a coating liquid for forming a hole injection transport layer.
Examples of the oxidation method include heating in the presence of oxygen or light irradiation. In the case of heating as the oxidation method, examples of the heating means include a method of heating on a hot plate and a method of heating in an oven. As heating temperature, 50 to 250 degreeC is preferable. In the case of light irradiation as a method of oxidation, examples of the light irradiation means include a method of exposing to ultraviolet rays. Since the interaction between transition metal-containing nanoparticles or transition metal-containing nanoclusters varies depending on the heating temperature and the amount of light irradiation, it is preferable to adjust appropriately.

  The content of the wettability changing material of the first aspect in the hole injection transport layer forming coating liquid can be appropriately adjusted according to the purpose, and is not particularly limited. About 0.1% by mass to 10.0% by mass is preferable in the total amount of the liquid.

  Further, when the hole injecting and transporting layer contains a material in which a fluorine-containing organic compound is attached to an organic-transition metal oxide complex which is a reaction product of an organic transition metal complex, that is, the above-mentioned “A. Organic EL In the case of containing the wettability changing material of the second aspect described in the section of “device”, the coating liquid for forming the hole injection / transport layer may contain a wettability changing material and a solvent ( A first aspect), an organic-transition metal oxide complex which is a reaction product of an organic transition metal complex, and a fluorine-containing organic compound containing a transition metal and / or a linking group that produces an action of linking to the transition metal oxide; And a solvent (second embodiment), a fluorine-containing organic compound containing an organic transition metal complex, and a linking group capable of linking with a transition metal and / or transition metal oxide; Carbonyl group / Or it may be one which contains a solvent having a hydroxyl group (third aspect).

  The hole injecting and transporting layer forming coating liquid of the second and third aspects is a process for forming a hole injecting and transporting layer, for example, in the hole injecting and transporting layer forming coating liquid Alternatively, after the layer formation, the fluorine-containing organic compound adheres to the organic-transition metal oxide complex, which is a reaction product of the organic transition metal complex, by a reaction performed at the time of heating, light irradiation, element driving, or the like. Can be produced.

  As the solvent used in the coating liquid for forming the hole injecting and transporting layer according to the first and second aspects, the organic-transition which is the wettability changing material according to the second aspect or the reaction product of the organic transition metal complex is used. Especially when the metal oxide composite, the fluorine-containing organic compound containing a linking group that produces an effect of linking to the transition metal and / or the transition metal oxide, and other components contained as required are dissolved or dispersed well. It is not limited. For example, the same solvent as that used when the hole injecting and transporting layer contains the wettability changing material of the first aspect can be used.

  As the solvent having a carbonyl group and / or a hydroxyl group used in the coating liquid for forming a hole injecting and transporting layer according to the third aspect, the term of the wettability changing material according to the second aspect of the above “A. Organic EL element” Organic solvents similar to those described in 1) can be used.

The coating liquid for forming a hole injecting and transporting layer according to the first aspect may be prepared by mixing the wettability changing material according to the second aspect and a solvent. Further, an organic transition metal complex and a fluorine-containing organic compound containing a linking group capable of linking with a transition metal and / or transition metal oxide are dissolved or dispersed in a solvent having a carbonyl group and / or a hydroxyl group, and organic The transition metal in the transition metal complex may be oxidized to obtain a coating liquid for forming a hole injection transport layer.
The organic-transition metal oxide complex in the coating liquid for forming a hole injection / transport layer according to the second aspect is obtained by dissolving or dispersing an organic transition metal complex in a solvent having a carbonyl group and / or a hydroxyl group. It is preferable to obtain by oxidizing the transition metal in the transition metal complex.
The method of oxidizing is as described above.

  The content of the wettability changing material of the second aspect in the hole injection transport layer forming coating liquid can be appropriately adjusted according to the purpose, and is not particularly limited. About 0.1% by mass to 10.0% by mass is preferable in the total amount of the liquid.

  Further, when the hole injecting and transporting layer contains an organopolysiloxane, that is, when the wettability changing material of the third aspect described in the above section “A. Organic EL element” is contained, the organopolysiloxane is used as the solvent. If it does not affect the patterning characteristics due to white turbidity and other phenomena, it is not particularly limited. For example, alcohols such as methanol, ethanol, isopropanol, butanol, acetone, acetonitrile, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, diethyl glycol monomethyl ether, diethyl glycol monoethyl ether , Diethyl glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, methyl acetate, ethyl acetate, butyl acetate, toluene, xylene, methyl lactate, ethyl lactate, ethyl pyruvate, 3- Methyl methoxypropionate, 3-ethoxypropionate Ethyl phosphate, dimethyl formamide, dimethyl sulfoxide, dioxane, ethylene glycol, hexamethylphosphoric triamide, pyridine, tetrahydrofuran, N- methylpyrrolidinone, and the like. Two or more of these solvents may be mixed and used.

  The coating method for forming the hole injecting and transporting layer may be any method that can form the above-mentioned material uniformly on the substrate, for example, a die coating method, a spin coating method, a dip coating method, a roll coating method. Bead coating method, spray coating method, bar coating method, gravure coating method, blade coating method, casting method, inkjet method, nozzle printing method, aerosol method, flexographic printing method, screen printing method, offset printing method, etc. it can.

  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. When the hole injecting and transporting layer contains the wettability changing material of the first or second aspect, when heated in the presence of oxygen, the content of the transition metal oxide in the wettability changing material increases, The injection transportability may be improved.

  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 vacuum deposition method.

  Since the substrate, the first electrode layer, the partition walls, and the hole injecting and transporting layer are described in detail in the above section “A. Organic EL element”, description thereof is omitted here.

(2) Wettability changing pattern forming step In the wettability changing pattern forming step in this embodiment, the photocatalyst-containing layer substrate in which a photocatalyst-containing layer containing at least a photocatalyst is formed on the substrate is used as the hole injection transport layer. On the other hand, the partition wall is formed on the surface of the hole injecting and transporting layer by irradiating the hole injecting and transporting layer with energy in a pattern after being arranged with a gap that can act as a photocatalyst due to energy irradiation. This is a step of forming a wettability change pattern comprising a liquid-repellent region disposed above and a lyophilic region disposed in the opening of the partition wall.

The mechanism by which the wettability of the hole injecting and transporting layer changes due to the action of the photocatalyst associated with energy irradiation is not necessarily clear, but the photocatalyst contained in the photocatalyst containing layer causes an oxidation-reduction reaction due to energy irradiation and is generated by this. Lyophilicity in which wettability has been changed by the action of the active oxygen species such as superoxide radical (• O ²⁻ ) and hydroxy radical (• OH) on the organic substances contained in the hole injection transport layer It is considered that a region can be formed.

  The photocatalyst-containing layer substrate used in this embodiment is one in which 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. 10A, 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. By irradiating the entire surface without irradiation, a lyophilic 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 a formation position of the light shielding portion, as illustrated in FIG. 3B, the light shielding portion 23 may be formed in a pattern on the substrate 22, and the photocatalyst containing layer 24 may be formed on the light shielding portion 23. As shown in FIG. 10C, 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 hole injecting and transporting layer are not spaced as compared with the case of using a photomask. Since the light-shielding portion is disposed in the vicinity of the portion disposed, 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.

  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 this embodiment, the photocatalyst-containing layer substrate is arranged with a gap that can act as a photocatalyst upon energy irradiation with respect to 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.
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 be in the above range, it is possible to suppress a decrease in pattern accuracy such as a blurred pattern, and it is possible to suppress deterioration of the sensitivity of the photocatalyst and deterioration of the wettability change efficiency. It is.
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.
It should be noted that such an arrangement state with a gap may be maintained at least during the energy irradiation.

  In the present invention, a partition is formed, and a liquid-repellent region is disposed on the partition. Therefore, the partition can be used as a spacer for uniformly forming the gap.

  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. Especially, it is preferable to irradiate energy from the photocatalyst containing layer substrate side.

  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.

  Since the liquid repellent region and the lyophilic region are described in detail in the section “A. Organic EL element”, description thereof is omitted here.

(3) Organic layer forming step In the organic layer forming step in this embodiment, the organic layer forming coating liquid is applied in a pattern on the hole injection transport layer, and the second electrode layer take-out electrode is provided. In this step, an organic layer including at least a light emitting layer is formed on the lyophilic region so as not to overlap the second electrode layer extraction electrode formation region.

In the case of a light emitting layer, the light emitting layer forming coating solution is used as the organic layer forming coating solution. 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 above “A. Organic EL element” 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 coating method of the organic layer forming coating solution, the organic layer forming coating solution is formed in a pattern on the hole injecting and transporting layer by utilizing the wettability difference between the lyophilic region and the liquid repellent region. There is no particular limitation as long as it is a method that can be applied to form an organic layer on the lyophilic region. 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 these methods allow the light emitting layer to be patterned with high definition.

  In addition, since it described in detail in the said "A. organic EL element" about the organic layer containing a light emitting layer etc., description here is abbreviate | omitted.

(4) Second electrode layer forming step The second electrode layer forming step in this embodiment is performed so that the second electrode layer forming step is divided on the barrier ribs and on the organic layer by the barrier ribs so as to overlap the extraction electrode forming region for the second electrode layer. This is a step of forming an electrode layer.
In addition, since the formation method of the 2nd electrode layer, etc. were described in the above-mentioned item of "A. Organic EL element", description here is abbreviate | omitted.

(5) Other steps In the present embodiment, in addition to the hole injection transport layer forming step, the wettability change pattern forming step, the organic layer forming step, and the second electrode layer forming step described above, if necessary, other You may have the process of.

  For example, before the hole injecting and transporting layer forming step, a first electrode layer forming step of forming a first electrode layer on the substrate, and a second electrode layer extraction electrode for forming a second electrode layer extraction electrode on the substrate Forming step, first electrode layer extraction electrode forming step for forming a first electrode layer extraction electrode on the substrate, insulating layer forming step for forming an insulating layer on the substrate on which the first electrode layer is formed, first electrode You may perform the partition formation process which forms a partition on the board | substrate with which the layer was formed. Since the first electrode layer, the second electrode layer take-out electrode, the first electrode layer take-out electrode, the insulating layer, and the partition are described in the above section “A. Organic EL element”, the explanation here is as follows. Omitted.

  Moreover, you may perform the electron injection transport layer formation process which forms an electron injection transport layer on an organic layer after the said organic layer formation process. Since the electron injecting and transporting layer is described in the section “A. Organic EL element”, description thereof is omitted here.

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

2. Second Embodiment A method of manufacturing an organic EL element according to this embodiment includes a stripe-shaped first electrode layer, a stripe-shaped partition perpendicular to the longitudinal direction of the first electrode layer, and a first partition located in the opening of the partition. A hole injection transport layer forming step of forming a hole injection transport layer having liquid repellency and wettability that can be changed by irradiation with vacuum ultraviolet light on the substrate on which the two-electrode layer extraction electrode is formed; By irradiating the hole injecting and transporting layer with vacuum ultraviolet light in a pattern, a liquid repellent region disposed on the partition and a parent disposed in the opening of the partition are formed on the surface of the hole injecting and transporting layer. A wettability change pattern forming step for forming a wettability change pattern composed of a liquid region, and an organic layer forming coating liquid is applied in a pattern on the hole injecting and transporting layer to take out the second electrode layer For the second electrode layer provided with electrodes An organic layer forming step of forming an organic layer including at least a light-emitting layer on the lyophilic region so as not to overlap the protruding electrode forming region, and the partition wall and the organic layer are separated by the partition wall; And a second electrode layer forming step of forming a second electrode layer so as to overlap the second electrode layer take-out electrode formation region.

The manufacturing method of the organic EL element of this embodiment will be described with reference to the drawings.
4 (a) to (e), FIGS. 8 (a) to (b) and FIGS. 9 (a) to (b) are process diagrams showing an example of a method for producing an organic EL element of the present embodiment. 4A is a cross-sectional view taken along the line EE of FIG. 8A, FIG. 4C is a cross-sectional view taken along the line FF of FIG. 8B, and FIG. 4D is a cross-sectional view of FIG. GG sectional drawing, FIG.4 (e) is the HH sectional view taken on the line of FIG.9 (b).
First, as shown in FIG. 4A and FIG. 8A, a striped first electrode layer 3, an insulating layer 4 that defines a light emitting region, and a striped shape orthogonal to the longitudinal direction of the first electrode layer 3 are used. Holes that have liquid repellency and whose wettability can be changed by irradiation of vacuum ultraviolet light on the substrate 2 on which the partition walls 5 and the second electrode layer extraction electrodes 9 located in the openings of the partition walls 5 are formed. The injection transport layer 6 is formed (hole injection transport layer forming step).
Next, as shown in FIG. 4B, the metal mask 31 is disposed on the surface of the hole injection / transport layer 6, and the hole injection / transport layer 6 located at the opening of the partition wall 5 through the metal mask 31. This part is irradiated with vacuum ultraviolet light 37. As shown in FIG. 4C and FIG. 8B, the wettability of the material contained in the hole injecting and transporting layer 6 is increased in the exposed portion of the hole injecting and transporting layer 6 by irradiation with the vacuum ultraviolet light 37. The lyophilic region 12 is formed. On the other hand, in the unexposed portion of the hole injection / transport layer 6, the wettability of the material contained in the hole injection / transport layer 6 remains unchanged and becomes the liquid repellent region 11. Thereby, the wettability change pattern which consists of the liquid repellent area | region 11 arrange | positioned on the partition 5 and the lyophilic area | region 12 arrange | positioned at the opening part of the partition 5 is formed (wetability change pattern formation process). .
Next, as shown in FIG. 4D and FIG. 9A, an organic layer forming coating solution is applied in a pattern on the hole injecting and transporting layer 6, and the second electrode layer extraction electrode 9 is applied. The organic layer 7 including at least the light emitting layer is formed on the lyophilic region 12 so as not to overlap the second electrode layer extraction electrode formation region 19 provided with (organic layer formation step).
Thereafter, as shown in FIGS. 4 (e) and 9 (b), the second electrode layer extraction electrode forming region 19 is divided on the partition wall 5 and the organic layer 7 by the partition wall 5 so as to overlap with the second electrode layer extraction electrode formation region 19. The two-electrode layer 8 is formed (second electrode layer forming step).

According to this embodiment, the hole injecting and transporting layer having liquid repellency and whose wettability can be changed by irradiation with vacuum ultraviolet light is irradiated with vacuum ultraviolet light to change the wettability of the hole injecting and transporting layer. By doing so, it is possible to form a wettability change pattern including a liquid repellent region and a lyophilic region in which the wettability of the hole injecting and transporting layer is changed. Therefore, it is possible to pattern an organic layer such as a light emitting layer with high accuracy.
In addition, according to the present embodiment, the organic layer such as the light emitting layer can be accurately patterned using the wettability change pattern formed on the surface of the hole injecting and transporting layer. Since the layer and the second electrode layer are formed at predetermined positions, the second electrode layer take-out electrode and the second electrode layer formed in the opening of the partition wall can be electrically connected without disconnecting the second electrode layer. It is possible to connect.

  In addition, since it is the same as that of what was described in the said 1st embodiment about an organic layer formation process, a 2nd electrode layer formation process, and another process, description here is abbreviate | omitted. Hereinafter, other steps in the method of manufacturing an organic EL element of this embodiment will be described.

(1) Hole Injecting and Transporting Layer Forming Step The hole injecting and transporting layer forming step in this embodiment includes a striped first electrode layer, a striped partition perpendicular to the longitudinal direction of the first electrode layer, and the partition Forming a hole injecting and transporting layer having liquid repellency and wettability that can be changed by irradiation with vacuum ultraviolet light on the substrate on which the second electrode layer take-out electrode located in the opening is formed. is there.
The method for forming the hole injecting and transporting layer is the same as that described in the first embodiment, and the description thereof is omitted here.

(2) Wettability changing pattern forming step In the wettability changing pattern forming step in this embodiment, the hole injecting and transporting layer is irradiated with vacuum ultraviolet light in a pattern to form a surface on the hole injecting and transporting layer. This is a step of forming a wettability change pattern including a liquid repellent region disposed on the partition and a lyophilic region disposed in the opening of the partition.

  The mechanism by which the wettability of the hole injecting and transporting layer changes due to irradiation with vacuum ultraviolet light is not necessarily clear, but when the hole injecting and transporting layer is irradiated with vacuum ultraviolet light, it is contained in the hole injecting and transporting layer. The molecular bond of the organic substance 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, thereby changing the wettability of the parent. It is considered that a liquid region can be formed.

  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. 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.

  As a vacuum ultraviolet light mask used in the irradiation of vacuum ultraviolet light, any mask capable of transmitting vacuum ultraviolet light in a pattern may be used.

  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.

3. Third Embodiment A method of manufacturing an organic EL element according to this embodiment includes a stripe-shaped first electrode layer, a stripe-shaped partition perpendicular to the longitudinal direction of the first electrode layer, and a first positioned at the opening of the partition. Holes that form a hole injecting and transporting layer that contains a photocatalyst, has liquid repellency, and whose wettability can be changed by the action of the photocatalyst accompanying energy irradiation on the substrate on which the two-electrode layer extraction electrode is formed An injection transport layer forming step, and by irradiating the hole injection transport layer with energy in a pattern, a liquid repellent region disposed on the partition wall on the surface of the hole injection transport layer and an opening of the partition wall A wettability change pattern forming step for forming a wettability change pattern composed of a lyophilic region disposed on the substrate, and applying a coating liquid for forming an organic layer on the hole injection transport layer in a pattern, 2-electrode layer extraction power An organic layer forming step of forming an organic layer including at least a light emitting layer on the lyophilic region so as not to overlap with the second electrode layer extraction electrode forming region where the electrode is provided; A second electrode layer forming step of forming a second electrode layer on the layer so as to be divided by the partition and to overlap with the second electrode layer take-out electrode forming region.

The manufacturing method of the organic EL element of this embodiment will be described with reference to the drawings.
11 (a) to (e), FIGS. 8 (a) to (b) and FIGS. 9 (a) to (b) are process diagrams showing an example of a method for producing an organic EL element of the present embodiment. 11A is a cross-sectional view taken along the line EE of FIG. 8A, FIG. 11C is a cross-sectional view taken along the line FF of FIG. 8B, and FIG. 11D is a cross-sectional view of FIG. GG sectional drawing, FIG.11 (e) is the HH sectional view taken on the line of FIG.9 (b).
First, as shown in FIG. 11A and FIG. 8A, a striped first electrode layer 3, an insulating layer 4 that defines a light emitting region, and a striped shape orthogonal to the longitudinal direction of the first electrode layer 3 are used. The substrate 5 on which the partition wall 5 and the second electrode layer extraction electrode 9 located at the opening of the partition wall 5 are formed contains a photocatalyst, has liquid repellency, and is wetted by the action of the photocatalyst upon energy irradiation. The hole injecting and transporting layer 6 whose properties can be changed is formed (hole injecting and transporting layer forming step).
Next, as shown in FIG. 11 (b), a photomask 41 is arranged on the surface of the hole injection / transport layer 6, and the hole injection / transport layer 6 positioned at the opening of the partition wall 5 through the photomask 41. The portion 47 is irradiated with ultraviolet light 47. As shown in FIGS. 11 (c) and 8 (b), the exposed portion of the hole injecting and transporting layer 6 is positively exposed to the ultraviolet light 47 due to the action of the photocatalyst contained in the hole injecting and transporting layer 6. The wettability of the material contained in the hole injecting and transporting layer 6 changes, and the lyophilic region 12 is formed. On the other hand, in the unexposed portion of the hole injection / transport layer 6, the wettability of the material contained in the hole injection / transport layer 6 remains unchanged and becomes the liquid repellent region 11. Thereby, the wettability change pattern which consists of the liquid repellent area | region 11 arrange | positioned on the partition 5 and the lyophilic area | region 12 arrange | positioned at the opening part of the partition 5 is formed (wetability change pattern formation process). .
Next, as shown in FIGS. 11 (d) and 9 (a), a coating solution for forming an organic layer is applied onto the hole injecting and transporting layer 6 in a pattern, and the second electrode layer extraction electrode 9 is applied. The organic layer 7 including at least the light emitting layer is formed on the lyophilic region 12 so as not to overlap the second electrode layer extraction electrode formation region 19 provided with (organic layer formation step).
Thereafter, as shown in FIGS. 11 (e) and 9 (b), the partition wall 5 and the organic layer 7 are divided by the partition wall 5 so as to overlap with the second electrode layer extraction electrode forming region 19. The two-electrode layer 8 is formed (second electrode layer forming step).

According to this embodiment, the hole injection transport layer containing a photocatalyst, having liquid repellency, and capable of changing wettability by the action of the photocatalyst accompanying energy irradiation is irradiated with energy. By changing the wettability, it is possible to form a wettability change pattern including a liquid-repellent region and a lyophilic region in which the wettability of the hole injection transport layer is changed. Therefore, it is possible to pattern an organic layer such as a light emitting layer with high accuracy.
In addition, according to the present embodiment, the organic layer such as the light emitting layer can be accurately patterned using the wettability change pattern formed on the surface of the hole injecting and transporting layer. Since the layer and the second electrode layer are formed at predetermined positions, the second electrode layer take-out electrode and the second electrode layer formed in the opening of the partition wall can be electrically connected without disconnecting the second electrode layer. It is possible to connect.

  In addition, since it is the same as that of what was described in the said 1st embodiment about an organic layer formation process, a 2nd electrode layer formation process, and another process, description here is abbreviate | omitted. Hereinafter, other steps in the method of manufacturing an organic EL element of this embodiment will be described.

(1) Hole Injecting and Transporting Layer Forming Step The hole injecting and transporting layer forming step in this embodiment includes a striped first electrode layer, a striped partition perpendicular to the longitudinal direction of the first electrode layer, and the partition Hole injection that contains a photocatalyst on the substrate on which the extraction electrode for the second electrode layer located in the opening is formed, has liquid repellency, and wettability can be changed by the action of the photocatalyst upon energy irradiation This is a step of forming a transport layer.
The method for forming the hole injecting and transporting layer is the same as that described in the first embodiment, and the description thereof is omitted here.

(2) Wettability change pattern formation process The wettability change pattern formation process in this embodiment is the above-mentioned partition on the surface of the hole injection transport layer by irradiating the hole injection transport layer with energy in a pattern. Forming a wettability change pattern comprising a liquid-repellent region disposed in the substrate and a lyophilic region disposed in the opening of the partition.

  The energy irradiation method is not particularly limited as long as the wettability of the hole injecting and transporting layer can be changed. The energy irradiation may be performed using a mask such as a photomask on which a target pattern is formed. This is because it is possible to irradiate the target pattern with energy, and the wettability of the hole injecting and transporting layer can be changed to the pattern. In this case, the type of the mask used is not particularly limited as long as the target pattern can be irradiated with energy, such as a photomask in which a light shielding portion is formed on a material that transmits energy. Alternatively, a shadow mask or the like in which holes are formed in a desired pattern may be used. Specific examples of materials for these masks include metals, inorganic materials such as glass and ceramics, and organic materials such as plastics.

  Furthermore, when the light shielding part is formed on the base material to be used, the irradiation of energy may be performed by exposing the entire surface from the base material side using the light shielding part. This is because energy can be irradiated only to the hole injecting and transporting layer at the position where the light shielding portion is not formed, and the wettability of the hole injecting and transporting layer can be changed. In this case, since there is no need to perform drawing with the mask, laser, or the like, there is an advantage that alignment or an expensive drawing apparatus is not required.

  Since other points in the wettability change pattern forming step are the same as those in the first embodiment, description thereof is omitted here.

  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 with reference to examples.

  Forming a hole injecting and transporting layer on the ITO substrate on which the insulating layer and the partition are formed, and exposing the hole injecting and transporting layer using a photomask having a photocatalyst containing layer to form a wettability change pattern; A second hole injection transport layer (hole transport layer) and a light emitting layer are applied and formed in the opening of the partition wall, which is a lyophilic region, by an ink jet method, and the hole blocking layer, electron transport layer, electron injection layer, cathode A film was formed and laminated so as to have a basic layer structure, and sealed to produce a green light-emitting organic EL element. And the light emission surface of the organic EL element was observed.

(Synthesis of device material for hole injection transport layer)
The device material for the hole injection transport layer used for forming the hole injection transport layer was synthesized as follows.
First, it is protected with 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecylamine in the following procedure. Molybdenum-containing nanoparticles were synthesized. Weigh out 3.2 g of n-octyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) in a 25 ml three-necked flask, depressurize while stirring, and leave it at room temperature (24 ° C) for 1.5 hours to remove low-volatile components. did. Change from vacuum to atmosphere, molybdenum hexacarbonyl 0.2 g (manufactured by Kanto Chemical Co., Ltd.), 4,4,5,5,6,6,7,7,8,8,9,9,10,10, 11,11,11-heptadecafluoroundecylamine 0.4 g (Fluka) was added. The mixture was placed in an argon gas atmosphere and heated to 250 ° C. with stirring, and the temperature was maintained for 1 hour. Then, after cooling this liquid mixture to room temperature (24 degreeC) and changing from argon gas atmosphere to air atmosphere, ethanol 5g was added and the deposit was isolate | separated from the reaction liquid by centrifugation. Thereafter, the obtained precipitate was washed with chloroform and ethanol, and dried to obtain a purified product of black molybdenum-containing nanoparticles.
As described above, transition metal-containing nanoparticles having a fluorine-containing organic compound attached to the surface, which is a device material for a hole injection transport layer, were obtained.
The primary particle size of the molybdenum-containing nanoparticles was measured using an ultrahigh resolution field emission scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation. A sample for measurement was prepared by dropping a few drops of a molybdenum-containing nanoparticle dispersion solution on a commercially available microgrid with a supporting film and drying the solvent under reduced pressure. The particle image observation was performed in a scanning transmission electron microscopy (STEM) mode. The average value of 20 observed bright particles was defined as the average particle size. The observed particle size is considered to be the average particle size of the transition metal-containing nanoparticles excluding the protective agent. The particle size of the compound produced in this synthesis example was about 7 nm.
In this example, transition metal-containing nanoparticles having a fluorine-containing organic compound attached to the surface were used as the device material for the hole injecting and transporting layer, but the present invention is not limited to this. .Organic EL Element As described in the section “Hole Injection Transport Layer”, a known material such as an organopolysiloxane such as fluoroalkylsilane may be used.

(Formation of insulating layer and partition)
First, a substrate 2 (FIG. 12A) on which ITO (first electrode layer 3 and second electrode layer take-out electrode 9) is formed in a pattern is prepared, and an insulating layer 4 having a grid-like opening ( 12 (b)) and a linear partition 5 (FIG. 13 (a)) were formed in this order. The substrate was subjected to ultrasonic cleaning in the order of neutral detergent and ultrapure water, and finally subjected to UV ozone treatment.

(Formation of hole injection transport layer)
Next, a Mo-containing nanoparticle thin film was applied and formed as a hole injection / transport layer on the substrate by spin coating using a hole injection / transport layer forming ink. The hole injection transport layer forming ink is obtained by dissolving 0.012 g of the above hole injection transport layer device material in 3.0 g of heptafluoro-n-ethyl butyrate to prepare a 0.4 wt% solution. It was. After forming the coating film, the outer peripheral portion and the extraction electrode portion were wiped off with a solvent and dried at 200 ° C. on a hot plate. The film thickness after drying was 10 nm. When the contact angle of the hole injection / transport layer 6 (flat portion) located at the opening of the partition wall 5 was measured, the contact angle of the surface of the hole injection / transport layer 6 with respect to xylene was 58 ° (FIG. 13B). )).

(Formation of wettability change pattern)
Next, a photomask having a photocatalyst-containing layer in which a line-shaped light-shielding portion was formed so that the width of the opening was 90 μm was prepared. The light-shielding portion of the photomask is adjusted so as to be positioned on the line-shaped partition wall 5 and exposed to the hole injecting and transporting layer 6. The liquid-repellent region 11 and the lyophilic property having high liquid-repellent contrast. A wettability change pattern composed of the region 12 was formed (FIG. 14A). At this time, after adjusting the distance between the photocatalyst containing layer of the photomask and the hole injecting and transporting layer to 100 μm using an ultraviolet exposure apparatus including a high pressure mercury lamp and a photomask and substrate position adjusting mechanism. The film was exposed for 3 minutes so that the exposure amount of 254 nm light was 5 J / cm ² from the back side of the photomask. When the contact angle was measured at the hole injection / transport layer 6 (flat portion) located at the opening of the partition wall 5 as an exposed portion, the contact angle of the surface of the hole injection / transport layer 6 with respect to xylene was 5 ° or less. Yes, it was lyophilic (FIG. 14 (a)).

(Formation of hole transport layer and light emitting layer)
Next, a hole transport layer was formed by applying a coating liquid for forming a hole transport layer having the following composition to the lyophilic region formed in the opening of the partition wall by an inkjet method. At this time, the amount of ink applied was adjusted so that the film thickness after drying was 30 nm. After forming the coating film, it was dried in nitrogen at 200 ° C. for 60 minutes.
<Hole transport layer forming coating solution>
Poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4 ′-(N- (4-sec-butylphenyl)) diphenylamine)] (TFB) 1.8 wt. Parts / Methylanisole 98.2 parts by weight

Next, on the positive hole transport layer formed in the opening part of the partition, the green light emitting layer forming coating liquid of the following composition was apply | coated by the inkjet method, and the light emitting layer was formed. At this time, the amount of ink applied was adjusted so that the film thickness after drying was 40 nm. After forming the coating film, it was dried in nitrogen at 100 ° C. for 30 minutes.
<Coating liquid for green light emitting layer formation>
・ 1.8 parts by weight of 2-methyl-9,10-bis (naphthalen-2-yl) anthracene (MADN) ・ 9,10-bis [N, N-di- (p-tolyl) -amino] anthracene (TTPA) ) 0.02 parts by weight / ethyl benzoate 98 parts by weight

(Formation of hole blocking layer, electron transport layer, electron injection layer and cathode)
Next, a hole blocking layer was uniformly deposited on the light emitting layer. The hole blocking layer uses a bis (2-methyl-8-quinolato) (p-phenylphenolate) aluminum complex (BAlq) and is a deposited film in vacuum (pressure: 1 × 10 ⁻⁴ Pa) by resistance heating. The film was formed by vapor deposition so that the film thickness was 15 nm.

Next, an electron transport layer was deposited on the hole blocking layer. The electron transport layer was formed by vapor deposition of tris (8-quinolinolato) aluminum complex (Alq3) in a vacuum (pressure: 1 × 10 ⁻⁴ Pa) by a resistance heating method so that the film thickness of the deposited film was 20 nm.

Next, an electron injection layer and a cathode were sequentially deposited on the electron transport layer. LiF (thickness: 0.5 nm) for the electron injection layer and Al (thickness: 100 nm) for the cathode (second electrode layer 8) were sequentially deposited in a vacuum (pressure: 1 × 10 ⁻⁴ Pa) by resistance heating. (FIG. 14 (b)).

  After forming the cathode, it was sealed using a non-alkali glass and a UV curable epoxy adhesive in a low oxygen, low humidity glove box.

(Evaluation)
When the light emitting layer was observed with a fluorescence microscope after application of the light emitting layer forming coating solution, it was confirmed that the light emitting layer was applied without overflowing to the adjacent line. Moreover, when the light emission surface of the produced organic EL element was observed with the microscope, it was confirmed that the element which emitted green light was able to be produced. It was confirmed that the light emission within each pixel was uniform, the light emission variation between the pixels was small, and the coating could be performed with very high accuracy.
In this embodiment, one color light emitting layer forming coating solution is applied. However, according to the method of this embodiment, in principle, for example, when a three or four color light emitting layer forming coating solution is used. It can be easily expanded and can be easily applied to the production of RGB separate panels.

DESCRIPTION OF SYMBOLS 1 ... Organic EL element 2 ... Substrate 3 ... 1st electrode layer 4 ... Insulating layer 5 ... Partition 6 ... Hole injection transport layer 7 ... Organic layer 8 ... 2nd electrode layer 9 ... Extraction electrode 11 for 2nd electrode layer 11 ... Repellency Liquid region 12 ... lyophilic region 15 ... partition opening 17 ... organic layer formation region 18 ... second electrode layer formation region 19 ... second electrode layer extraction electrode formation region d1 ... second electrode in the longitudinal direction of the partition wall Layer length d2 ... Partition length

Claims (11)

A substrate,
A first electrode layer formed in a stripe shape on the substrate;
A partition wall formed in a stripe shape in a direction perpendicular to the longitudinal direction of the first electrode layer on the substrate on which the first electrode layer is formed, and having a cross-sectional shape of a reverse taper shape;
A liquid-repellent region containing a wettability changing material formed on the partition and the opening of the partition, the wettability changing material being disposed on the partition and capable of changing wettability by the action of a photocatalyst accompanying irradiation of energy or irradiation of vacuum ultraviolet light And a hole injecting and transporting layer having a wettability change pattern composed of a lyophilic region disposed in the opening of the partition wall and having changed wettability of the wettability changing material,
An organic layer formed on the lyophilic region and having at least a light emitting layer;
A second electrode layer formed on the organic layer and on the partition and separated by the partition;
A second electrode layer extraction electrode formed on the substrate and electrically connected to the second electrode layer;
The second electrode layer extraction electrode is disposed in the opening of the partition wall, the second electrode layer formation region in which the second electrode layer is provided, and the second electrode layer extraction electrode is provided in the second An organic electrode characterized in that the electrode layer extraction electrode formation region overlaps, and the organic layer formation region where the organic layer is provided and the second electrode layer extraction electrode formation region do not overlap. Luminescence element.   2. The organic electroluminescence device according to claim 1, wherein a length of the second electrode layer in a longitudinal direction of the partition is shorter than a length of the partition.   The wettability changing material is a material in which a fluorine-containing organic compound is attached to the surface of a transition metal-containing nanoparticle or transition metal-containing nanocluster containing at least a transition metal oxide. The organic electroluminescent element according to claim 2.   The organic electroluminescent device according to claim 3, wherein the transition metal in the transition metal oxide is at least one metal selected from the group consisting of molybdenum, tungsten, rhenium, and vanadium.   The organic electroluminescent device according to claim 3 or 4, wherein the fluorine-containing organic compound contains a fluorinated alkyl group.   The wettability changing material is a material in which a fluorine-containing organic compound is attached to an organic-transition metal oxide composite that is a reaction product of an organic transition metal complex. 2. The organic electroluminescence device according to 2.   The organic electroluminescence device according to claim 6, wherein the transition metal in the transition metal oxide is at least one metal selected from the group consisting of molybdenum, tungsten, rhenium, and vanadium.   8. The organic-transition metal oxide complex is a reaction product of the organic transition metal complex and an organic solvent having a carbonyl group and / or a hydroxyl group. Organic electroluminescence device.   The organic electroluminescence device according to any one of claims 6 to 8, wherein the fluorine-containing organic compound contains a fluorinated alkyl group. On the substrate on which the striped first electrode layer, the striped partition perpendicular to the longitudinal direction of the first electrode layer, and the second electrode layer extraction electrode located in the opening of the partition are formed, the liquid repellent property A hole injecting and transporting layer forming step for forming a hole injecting and transporting layer having wettability that can be changed by the action of a photocatalyst accompanying energy irradiation,
After arranging a photocatalyst-containing layer substrate on which a photocatalyst-containing layer containing at least a photocatalyst is formed on the substrate with a gap that can act as a photocatalyst upon irradiation of energy with respect to the hole injection transport layer By irradiating the hole injection / transport layer with energy in a pattern, a liquid-repellent region disposed on the partition wall on the surface of the hole injection / transport layer and a lyophilic solution disposed in the opening of the partition wall A wettability change pattern forming process for forming a wettability change pattern composed of a conductive region;
An organic layer forming coating solution is applied in a pattern on the hole injecting and transporting layer so as not to overlap with the second electrode layer extraction electrode forming region where the second electrode layer extraction electrode is provided. An organic layer forming step of forming an organic layer including at least a light emitting layer on the lyophilic region;
A second electrode layer forming step of forming a second electrode layer on the partition wall and the organic layer so as to be divided by the partition wall and to overlap the extraction electrode formation region for the second electrode layer. A method for producing an organic electroluminescent element. On the substrate on which the striped first electrode layer, the striped partition perpendicular to the longitudinal direction of the first electrode layer, and the second electrode layer extraction electrode located in the opening of the partition are formed, the liquid repellent property A hole injection transport layer forming step for forming a hole injection transport layer having wettability and wettability can be changed by irradiation with vacuum ultraviolet light;
By irradiating the hole injection / transport layer with vacuum ultraviolet light in a pattern, a liquid repellent region disposed on the partition and a parent disposed at the opening of the partition are formed on the surface of the hole injection / transport layer. A wettability change pattern forming process for forming a wettability change pattern composed of a liquid region;
An organic layer forming coating solution is applied in a pattern on the hole injecting and transporting layer so as not to overlap with the second electrode layer extraction electrode forming region where the second electrode layer extraction electrode is provided. An organic layer forming step of forming an organic layer including at least a light emitting layer on the lyophilic region;
A second electrode layer forming step of forming a second electrode layer on the partition wall and the organic layer so as to be divided by the partition wall and to overlap the extraction electrode formation region for the second electrode layer. A method for producing an organic electroluminescent element.

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