Inkjet recording medium for organic semiconductor device and member for organic semiconductor device

Abstract

An organic semiconductor device inkjet recording medium and an organic semiconductor device member for manufacturing an organic semiconductor device with high precision using a simple process are provided. In addition, a method for manufacturing an organic semiconductor device using the organic semiconductor device inkjet recording medium is provided, which can manufacture an organic semiconductor device with high precision using a simple process. The organic semiconductor device inkjet recording medium of the present invention is an organic semiconductor device inkjet recording medium in which a substrate, an electrode, and an ink receiving layer are sequentially stacked, and is characterized in that the ink receiving layer has an ink penetration prevention region on the electrode side, and the ink penetration prevention region prevents ink that penetrates from a surface away from the electrode to the electrode from reaching the electrode.

Description

Technical Field

[0001] The present invention relates to an inkjet recording medium for an organic semiconductor device, a member for an organic semiconductor device, and a method for producing an organic semiconductor device. Background Art

[0002] In recent years, development of organic semiconductor devices utilizing the semiconductor properties of organic thin films, such as organic electroluminescence (hereinafter abbreviated as “EL”) elements and organic thin film solar cells, has been actively advanced.

[0003] As an example of a method for manufacturing such an organic semiconductor device, a technique for forming pixels containing organic semiconductor materials by inkjet method is known. When forming pixels by inkjet method, the following method is applied: a bank serving as a partition is formed between each pixel in advance, and ink containing organic semiconductor materials is applied by inkjet method to the pixel area separated by the bank. However, in this method, the complexity of the device and process and the increase in cost due to low yield are problems.

[0004] In order to solve the above-mentioned problems, a so-called "self-integration process" is known as a method for manufacturing an organic semiconductor device using a simple process. In the self-integration process, for example, an insulating resin layer serving as an ink receiving layer is formed on an electrode of a substrate with an electrode, and an ink containing an organic semiconductor material is pattern-printed on the ink receiving layer by an inkjet method. At this time, the solvent used in the ink containing the organic semiconductor material dissolves the ink receiving layer and replaces it with the organic semiconductor material as a solute, thereby being able to form a bank and an organic semiconductor layer at the same time.

[0005] As an organic semiconductor device manufactured using a self-integration process, for example, non-patent document 1 discloses: "An organic EL element, which includes a light-emitting layer formed by inkjet discharging a light-emitting ink (ink containing a charge-transporting main compound and a light-emitting compound) from an ink-receiving layer composed of an insulating polymer, and causing a current to flow between a pair of anodes and cathodes, thereby causing a discharged pattern image to emit light."

[0006] Furthermore, Non-Patent Document 2 discloses: “An organic EL element including a light-emitting layer formed by inkjet-discharging an ink containing a light-emitting compound into an ink receiving layer containing a hole transporting material in advance”.

[0007] However, in the self-integration process, the organic semiconductor layer is formed in the form of penetrating the ink receiving layer, thereby forming a contact portion where the organic semiconductor layer and the electrode are connected. As for the organic semiconductor layer formed by the inkjet method, it is difficult to control the electrode interface, and the interface cannot be formed with high precision. Therefore, due to the disorder (defect) of the contact portion between the organic semiconductor layer and the electrode, a leakage current is generated through it, for example, in the organic EL element, the yield is reduced due to poor light emission of the device, and poor light emission during re-application, etc., which is a problem.

[0008] Prior art literature

[0009] Non-patent literature

[0010] Non-patent document 1: K.Matsui, J.Yanagi, M.Shibata, S.Naka, H.Okada, T.Miyabayashi, T.Inoue: "Multi-Color Organic Light Emitting Panels Using Self-Aligned Ink-JetPrinting Technology", Mol.Cryst.Liq.Cryst., 471(1), pp. 261-268 (2007).

[0011] Non-patent document 2: R.Satoh, S.Naka, M.Shibata, H.Okada, T.Inoue, T.Miyabayashi: "Self-Aligned Organic Light-Emitting Diodes with Color Changing by Ink-JetPrinting Dots", Japanese Journal of Applied Physics, 50, page 01BC09-1-4 (2011) Summary of the invention

[0012] Problems to be solved by the invention

[0013] The present invention has been made in view of the above problems and circumstances, and the problem to be solved is to provide an inkjet recording medium for an organic semiconductor device and a member for an organic semiconductor device for manufacturing an organic semiconductor device with high precision by a simple process. In addition, the present invention is to provide a method for manufacturing an organic semiconductor device by using the inkjet recording medium for an organic semiconductor device, which can manufacture an organic semiconductor device with high precision by a simple process.

[0014] Means for solving problems

[0015] The present inventors have studied the causes of the above problems in order to solve the above problems. As a result, the present inventors have solved the above problems by designing the ink receiving layer formed on the electrode of the substrate with the electrode in the self-integration process so that the ink containing the organic semiconductor material discharged by the inkjet device does not penetrate the ink receiving layer and reach the electrode. That is, the above problems related to the present invention are solved by the following means.

[0016] 1. An inkjet recording medium for an organic semiconductor device, which is an inkjet recording medium for an organic semiconductor device in which a substrate, an electrode, and an ink receiving layer are stacked in sequence, characterized in that the ink receiving layer has an ink penetration prevention area on the electrode side, and the ink penetration prevention area prevents ink that penetrates from a surface away from the electrode to the electrode from reaching the electrode.

[0017] 2. The inkjet recording medium for an organic semiconductor device according to item 1, wherein the ink receiving layer has an ink permeable layer including a surface away from the electrode, and has an ink insoluble layer as the ink permeation preventing region on the electrode side.

[0018] 3. The inkjet recording medium for an organic semiconductor device according to item 2, wherein the ink-insoluble layer contains a cross-linked resin as a main component.

[0019] 4. The inkjet recording medium for an organic semiconductor device according to item 2, wherein the ink-poorly soluble layer comprises an interpenetrating polymer network structure.

[0020] 5. The inkjet recording medium for an organic semiconductor device according to item 2, wherein the absolute value of the difference between the SP value of the constituent component of the ink permeable layer and the SP value of the ink is 3.0 (J / cm 3 ) 1 / 2 Hereinafter, the absolute value of the difference between the SP value of the constituent component of the ink insoluble layer and the SP value of the ink is 3.1 (J / cm 3 ) 1 / 2 above.

[0021] 6. The inkjet recording medium for an organic semiconductor device according to item 2 or 5, wherein the ink permeable layer contains a polystyrene resin, and the ink insoluble layer contains a resin containing tetraphenylbenzidine or a derivative thereof as a main polymer unit.

[0022] 7. The inkjet recording medium for an organic semiconductor device according to any one of items 1 to 6, further comprising a release film on the ink receiving layer.

[0023] 8. A component for an organic semiconductor device, which is a component for an organic semiconductor device formed by stacking a substrate, an electrode, and an organic semiconductor layer in sequence, characterized in that the organic semiconductor layer comprises: an ink receiving layer that exists continuously over the entire area of ​​the formation area of ​​the organic semiconductor layer on the electrode; and a region containing an organic semiconductor material that is a discontinuous region surrounded by the ink receiving layer and has a pattern-shaped exposed portion on the surface of the organic semiconductor layer away from the electrode and has no interface with the electrode.

[0024] 9. The organic semiconductor device member according to item 8, wherein the maximum thickness of the ink receiving layer is within a range of 3 nm to 5 μm.

[0025] 10. The organic semiconductor device member according to item 8 or 9, wherein the constituent material of the ink receiving layer mainly contains a resin having a weight average molecular weight in the range of 1,000 to 1,000,000.

[0026] 11. The member for an organic semiconductor device according to any one of items 8 to 10, wherein the region containing the organic semiconductor material is a region formed using an ink containing the organic semiconductor material, and the absolute value of the difference between the SP value of the constituent material of the ink receiving layer and the SP value of the ink is 3.0 (J / cm 3 ) 1 / 2 the following.

[0027] 12. The component for an organic semiconductor device according to item 8, characterized in that the region containing the organic semiconductor material is a region formed using ink containing the organic semiconductor material, and the ink receiving layer has an ink permeable layer including a surface away from the electrode and an ink insoluble layer on the electrode side.

[0028] 13. A method for manufacturing an organic semiconductor device, which is a method for manufacturing an organic semiconductor device using an inkjet recording medium for an organic semiconductor device according to any one of items 1 to 6, characterized in that it comprises: a step of dropping ink onto the above-mentioned ink receiving layer; and a step of forming a film of an electrode that forms a pair with the above-mentioned electrode on the ink receiving layer after the above-mentioned dropping.

[0029] 14. The method for producing an organic semiconductor device according to item 13, wherein the organic semiconductor device is selected from an organic electroluminescent element, an organic thin film transistor or an organic photoelectric conversion element.

[0030] Effects of the Invention

[0031] According to the above means of the present invention, an inkjet recording medium for an organic semiconductor device and a member for an organic semiconductor device can be provided for manufacturing an organic semiconductor device with high precision by a simple process. In addition, a method for manufacturing an organic semiconductor device using the inkjet recording medium for an organic semiconductor device can be provided, which can manufacture an organic semiconductor device with high precision by a simple process. The manifestation mechanism or action mechanism of the effect of the present invention is presumed to be as follows.

[0032] By using the inkjet recording medium for an organic semiconductor device and the member for an organic semiconductor device of the present invention, by applying a self-integration process in the manufacture of an organic semiconductor device, it is possible to simultaneously manufacture pixels as an organic semiconductor layer and banks separating the pixels, thereby simplifying the manufacturing process.

[0033] Furthermore, in the obtained organic semiconductor device, the organic semiconductor layer hardly reaches the electrode of the substrate with the electrode. Therefore, a high-quality organic semiconductor device can be manufactured with high precision in which the occurrence of disorder (defect) at the contact point between the organic semiconductor layer and the electrode is suppressed.

[0034] According to the method for manufacturing an organic semiconductor device using the inkjet recording medium for an organic semiconductor device of the present invention, in addition to obtaining the above-mentioned effects, process division becomes possible, which is advantageous in terms of labor saving in production management, efficiency improvement due to parallelization, and shortening of product completion time due to the use of intermediate materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is a cross-sectional view of an example of the inkjet recording medium for an organic semiconductor device of the present invention.

[0036] Figure 2 This is a plan view of an example of the member for an organic semiconductor device of the present invention.

[0037] Figure 3 for Figure 2 A cross-sectional view of the organic semiconductor device member taken along line III-III shown in FIG.

[0038] Figure 4 This is a cross-sectional view of another example of the organic semiconductor device member of the present invention.

[0039] Figure 5 This is a cross-sectional view for explaining an ink dropping step in one example of the method for manufacturing an organic semiconductor device of the present invention.

[0040] Figure 6 This is a cross-sectional view of an example of an organic semiconductor device obtained by the production method of the present invention.

[0041] Description of Reference Numerals

[0042] 1 Inkjet recording media for organic semiconductor devices

[0043] 2. Substrate

[0044] 3 Electrodes

[0045] 4A, 4B Ink receiving layer

[0046] 41 ink penetration area (ink penetration layer)

[0047] 42 Ink penetration prevention area (ink insoluble layer)

[0048] 5 Region containing organic semiconductor material

[0049] 6 Organic semiconductor layer

[0050] 7 Electrode (counter electrode)

[0051] 10A, 10B Organic semiconductor device components

[0052] 11 Inkjet device

[0053] 12 Inkjet Head

[0054] 100 Organic semiconductor devices DETAILED DESCRIPTION

[0055] The inkjet recording medium for an organic semiconductor device of the present invention is an inkjet recording medium for an organic semiconductor device in which a substrate, an electrode, and an ink accommodating layer are stacked in sequence, and is characterized in that the ink accommodating layer has an ink penetration prevention area on the electrode side, and the ink penetration prevention area prevents ink that penetrates from a surface away from the electrode to the electrode from reaching the electrode.

[0056] In an embodiment of the inkjet recording medium for an organic semiconductor device of the present invention, from the viewpoint of showing the effect of the present invention, the ink accommodating layer preferably has an ink permeable layer including a surface away from the electrode, and as the ink permeation prevention area, has an ink insoluble layer on the electrode side.

[0057] In an embodiment of the inkjet recording medium for an organic semiconductor device of the present invention, the ink-resistant layer preferably contains a crosslinked resin as a main component from the viewpoint of improving ink permeation prevention performance on the electrode side. Alternatively, the ink-resistant layer preferably contains an interpenetrating polymer network structure.

[0058] In an embodiment of the inkjet recording medium for an organic semiconductor device of the present invention, from the viewpoint of improving the ink permeability of the surface layer away from the electrode, it is preferred that the absolute value of the difference between the SP value of the constituent component of the ink permeable layer and the SP value of the ink is 3.0 (J / cm 3 )1 / 2 From the viewpoint of improving the ink penetration prevention performance on the electrode side, it is preferred that the absolute value of the difference between the SP value of the constituent component of the ink insoluble layer and the SP value of the ink is 3.1 (J / cm 3 ) 1 / 2 It is to be noted that the measurement of the SP value in the present invention can be performed as described below.

[0059] In an embodiment of the inkjet recording medium for an organic semiconductor device of the present invention, from the viewpoint of improving the ink permeability at the surface layer away from the above-mentioned electrode, it is preferred that the above-mentioned ink permeable layer contains a polystyrene resin, and from the viewpoint of improving the ink penetration prevention performance on the electrode side, it is preferred that the above-mentioned ink insoluble layer contains a resin containing tetraphenylbenzidine or its derivatives as the main polymerization unit.

[0060] In an embodiment of the inkjet recording medium for an organic semiconductor device of the present invention, it is preferred that the inkjet recording medium for an organic semiconductor device further comprises a release film on the ink receiving layer from the viewpoint that the inkjet recording medium for an organic semiconductor device can stably maintain the effects of the present invention.

[0061] The component for an organic semiconductor device of the present invention is a component for an organic semiconductor device formed by stacking a substrate, an electrode, and an organic semiconductor layer in sequence, and is characterized in that the organic semiconductor layer has an ink receiving layer that exists continuously over the entire area of ​​the formation area of ​​the organic semiconductor layer on the electrode; and a region containing an organic semiconductor material that has an exposed portion in a pattern shape on the surface of the organic semiconductor layer away from the electrode and has no interface with the electrode as a discontinuous region surrounded by the ink receiving layer.

[0062] In the embodiment of the member for an organic semiconductor device of the present invention, from the viewpoint of showing the effect of the present invention, the maximum thickness of the ink receiving layer is preferably in the range of 3 nm to 5 μm. In addition, the constituent material of the ink receiving layer is preferably mainly composed of a resin having a weight average molecular weight in the range of 1,000 to 1,000,000.

[0063] In an embodiment of the member for an organic semiconductor device of the present invention, from the viewpoint of expressing the effect of the present invention, it is preferred that the region containing the organic semiconductor material is a region formed using an ink containing the organic semiconductor material, and the absolute value of the difference between the SP value of the constituent material of the ink receiving layer and the SP value of the ink is 3.0 (J / cm 3 ) 1 / 2 the following.

[0064] In an embodiment of a component for an organic semiconductor device of the present invention, from the viewpoint of showing the effect of the present invention, it is preferred that the region containing the organic semiconductor material is a region formed using an ink containing the organic semiconductor material, and the ink receiving layer has an ink permeable layer including a surface away from the electrode, and an ink insoluble layer on the electrode side.

[0065] The method for manufacturing an organic semiconductor device of the present invention is a method for manufacturing an organic semiconductor device using the above-mentioned inkjet recording medium for an organic semiconductor device of the present invention, and is characterized in that it comprises: a step of dropping ink onto the above-mentioned ink receiving layer, and a step of forming a film of an electrode that forms a pair with the above-mentioned electrode on the ink receiving layer after the above-mentioned dropping.

[0066] In the method for producing an organic semiconductor device of the present invention, the organic semiconductor device is preferably, for example, an organic electroluminescent element, an organic thin film transistor, or an organic photoelectric conversion element.

[0067] The present invention and its constituent elements and modes and methods for implementing the present invention are described in detail below with reference to the accompanying drawings. However, the scope of the present invention is not limited to the illustrated examples. The inkjet recording medium for organic semiconductor devices, the components for organic semiconductor devices and the organic semiconductor devices illustrated in the drawings can be appropriately changed without departing from the gist of the present invention. It should be noted that in this application, "to" is used to mean the lower limit and upper limit values ​​including the numerical values ​​recorded before and after it. In this specification, "with... as the main component", "mainly contains", "with... as the main body" means that the main component accounts for more than 50% by mass, preferably more than 70% by mass, and more preferably more than 90% by mass relative to the whole.

[0068] [Inkjet recording medium for organic semiconductor devices]

[0069] The inkjet recording medium for an organic semiconductor device of the present invention (hereinafter also referred to as "inkjet recording medium") is an inkjet recording medium in which a substrate, an electrode, and an ink receiving layer are sequentially stacked. The inkjet recording medium of the present invention is characterized in that the ink receiving layer has an ink penetration prevention region on the electrode side, and the ink penetration prevention region prevents ink that penetrates from a surface away from the electrode to the electrode from reaching the electrode.

[0070] The inkjet recording medium of the present invention is used for manufacturing an organic semiconductor device. As an organic semiconductor device, specifically, an organic EL element, an organic thin film transistor (hereinafter also referred to as "organic TFT") and an organic photoelectric conversion element can be listed. The ink of the present invention is an ink for an inkjet method, and contains an organic semiconductor material for manufacturing an organic semiconductor device.

[0071] Figure 1 This is a cross-sectional view showing an example of the ink jet recording medium of the present invention. Figure 2and Figure 3 A plan view of an example of the organic semiconductor device member of the present invention and a cross-sectional view taken along line III-III are respectively shown. Figure 2 The organic semiconductor device member shown in FIG. Figure 1 An example of an organic semiconductor device member obtained by using the inkjet recording medium shown in FIG. Figure 4 This is a cross-sectional view showing another example of the organic semiconductor device member of the present invention. Figure 5 This is a cross-sectional view for explaining an ink droplet landing step in one example of the method for manufacturing an organic semiconductor device of the present invention. Figure 6 This is a cross-sectional view of an example of an organic semiconductor device obtained by the method for producing an organic semiconductor device of the present invention.

[0072] Figure 5 For illustration purposes Figure 1 An example of the ink droplet landing process of the inkjet recording medium shown in FIG. Figure 5 The ink drop process shown in FIG. is completed, and the ink drop process shown in FIG. Figure 2 and Figure 3 The organic semiconductor device member of the present invention is shown in . Figure 6 For use Figure 1 The inkjet recording medium shown in Figure 2 and Figure 3 ] is a diagram of an example of an organic semiconductor device finally obtained by the member for an organic semiconductor device of the present invention shown in FIG.

[0073] Figure 1 The inkjet recording medium 1 shown in the figure has a substrate 2, an electrode 3 arranged on the substrate 2, and an ink receiving layer 4A arranged on the electrode 3. The ink receiving layer 4A has an ink penetration prevention region 42 on the electrode 3 side. The ink penetration prevention region 42 is a region that prevents ink that penetrates from the surface S of the ink receiving layer 4A away from the electrode 3 toward the electrode 3 from reaching the electrode 3. In the ink receiving layer 4A, the region from the surface S to the upper side of the ink penetration prevention region 42 is an ink penetration region 41 into which ink penetrates. It should be noted that in Figure 1 In the description, the substrate 2 side is sometimes indicated as "lower" and the ink receiving layer 4A side is sometimes indicated as "upper".

[0074] Inkjet recording medium is a recording medium for printing by inkjet method. Figure 5 As shown in FIG. 1 , the ink In is dropped onto the surface S of the ink receiving layer 4A by an inkjet method, thereby forming a Figure 2 and Figure 3The organic semiconductor device member 10A shown in FIG. 1 is further manufactured by forming an electrode 7 (hereinafter referred to as "counter electrode 7" to distinguish it from the electrode 3) on the ink receiving layer 4A of the organic semiconductor device member 10A. Figure 6 The organic semiconductor device 100 shown in FIG.

[0075] The inkjet recording medium of the present invention may have additional layers other than the substrate, the electrode and the ink receiving layer as required. Examples of the additional layers include a release film provided on the ink receiving layer, a gas barrier film provided on the substrate, a reflective film for light extraction, a scattering film, etc. The following describes the various components of the inkjet recording medium of the present invention.

[0076] <Base material>

[0077] The substrate 2 may be made of any material such as glass or plastic, and may be transparent or opaque. The substrate 2 is preferably in the form of a film or a substrate. The thickness of the substrate 2 is not particularly limited, and may be, for example, in the range of 1 to 1000 μm.

[0078] In the case where the obtained organic semiconductor device is, for example, an organic semiconductor device having a mechanism of taking out light from the substrate side, the substrate is preferably transparent. As a transparent substrate preferably used, a glass substrate, a quartz substrate, and a transparent resin film can be cited. A particularly preferred substrate is a resin film that can give flexibility to the organic semiconductor device.

[0079] Examples of the resin constituting the resin film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin resins such as polyethylene and polypropylene, cellulose esters such as cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate (CAP), cellulose acetate phthalate, and cellulose nitrate, or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene-vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, polyether sulfone (PES), polyphenylene sulfide, polysulfones, polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate resins, and cycloolefin resins such as Atone (registered trademark) (manufactured by JSR Corporation) and APEL (registered trademark) (manufactured by Mitsui Chemicals, Inc.).

[0080] A gas barrier film composed of an inorganic substance or an organic substance or a mixed gas barrier film of the two can be formed on the surface of the resin film on the side away from the electrode and / or on the electrode side. These gas barrier films preferably have a water vapor permeability (25±0.5°C, relative humidity (90±2)% RH) of 0.01 g / (m 2 · 24h) or less, more preferably has an oxygen permeability of 10 as measured by the method according to JIS K 7126-1987. - 3 mL / (m 2 ·24h·atm) or less, water vapor permeability is 10 -5 g / (m 2 ·High barrier property below 24h).

[0081] As for the material forming the gas barrier film, any material having the function of inhibiting the infiltration of substances such as moisture and oxygen that cause degradation of the element can be used, for example, silicon oxide, silicon dioxide, silicon nitride, etc. can be used. In order to further improve the fragility of the film, it is more preferable to have a stacked structure of these inorganic layers and layers composed of organic materials. There is no particular restriction on the stacking order of the inorganic layer and the organic functional layer, and it is preferred that the two are alternately stacked multiple times.

[0082] The method for forming the gas barrier film is not particularly limited, and examples thereof include vacuum evaporation, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam method, ion plating method, plasma polymerization, atmospheric pressure plasma polymerization, plasma CVD (chemical vapor deposition), laser CVD, thermal CVD, coating, and the like. In particular, the atmospheric pressure plasma polymerization described in Japanese Patent Application Laid-Open No. 2004-68143 is preferably used.

[0083] Examples of the opaque substrate include metal plates such as aluminum and stainless steel, metal films, opaque resin films, and ceramic substrates.

[0084] <Electrode>

[0085] The electrode 3 disposed on the substrate 2 is composed of an electrode material that is a conductor. The inkjet recording medium 1 is used as an organic semiconductor device such as an organic semiconductor device 100, for example, via the organic semiconductor device member 10A. The organic semiconductor device 100 includes the electrode 3 and a counter electrode 7 that is a pair therewith. One of the electrode 3 and the counter electrode 7 is an anode, and the other is used as a cathode.

[0086] As for the electrode 3, when an organic semiconductor device is made, it can function as an anode or a cathode. For example, when the organic semiconductor device is an organic EL element, when the electrode 3 is used as an anode, the electrode 3 preferably uses a metal, alloy, conductive compound and a mixture thereof with a large work function (4 eV or more, preferably 4.5 eV or more) as an electrode material. As specific examples of such electrode materials, conductive transparent materials such as Au, CuI, indium tin oxide (ITO: Indium Tin Oxide), SnO2, and ZnO can be listed. In addition, amorphous materials such as IDIXO (In2O3-ZnO) that can be used to make transparent conductive films can be used.

[0087] In addition, a conductive polymer can be used for the anode. As the conductive polymer, for example, PEDOT:PSS, polypyrrole, polyaniline, polythiophene, polythienyl vinylene, polyazulene, polyisothionaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene, polynaphthalene and their derivatives can be listed. These electrode materials can be used alone or in combination of two or more materials. In addition, two or more layers composed of each material can be stacked to form an electrode.

[0088] For example, when the organic semiconductor device is an organic EL element, when the electrode 3 is used as a cathode, an electrode using a metal (called an electron injecting metal) with a small work function (5 eV or less), an alloy, a conductive compound, and a mixture thereof as an electrode material is used for the electrode 3. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, silver, a magnesium / copper mixture, a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al2O3) mixture, indium, a lithium / aluminum mixture, aluminum, and a rare earth metal.

[0089] Among these, from the aspects of electron injectability and durability against oxidation, etc., a mixture of an electron injectable metal and a second metal having a work function value larger than that of the second metal and being more stable is preferred, such as a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al2O3) mixture, a lithium / aluminum mixture, aluminum, etc.

[0090] In addition, as a cathode, after the above-mentioned metal is formed into a film with a specified thickness, such as 1 to 20 nm, a conductive transparent material is formed thereon, thereby making a transparent or semi-transparent cathode. By applying this, an element in which both the anode and the cathode are transparent can be made.

[0091] In the organic semiconductor device, the counter electrode 7 is a cathode when the electrode 3 is an anode, and is an anode when the electrode 3 is a cathode.

[0092] The electrode 3, in the case of either the anode or the cathode, is obtained by, for example, forming an electrode material as a thin film on the substrate 2 by a method such as evaporation or sputtering. The electrode 3 may be provided as a flat film with uniform thickness on the entire surface of the upper side of the substrate 2, or may be provided in a desired pattern shape. For example, the pattern-shaped electrode 3 may be formed by photolithography to form a pattern of a desired shape, or, in the case where the pattern accuracy is not required (about 100 μm or more), the pattern may be formed through a mask of a desired shape during evaporation or sputtering of the electrode material.

[0093] When using a coatable substance such as an organic conductive compound or metal nanoparticle, a wet film forming method such as a printing method or a coating method can also be used. In an organic EL element, the sheet resistance of the electrode is preferably below several hundred Ω / sq. The thickness of the electrode 3 also depends on the material, and is usually selected in the range of 10 nm to 5 μm, preferably 10 to 200 nm.

[0094] In an organic EL element, in order to transmit emitted light, it is advantageous if either the anode or cathode is transparent or semi-transparent, since the emission brightness is improved. When light is extracted from the electrode, the transmittance is preferably greater than 10%.

[0095] <Ink receiving layer>

[0096] The ink receiving layer 4A is a layer stacked on the electrode 3. Figure 1 In the cross section shown in , the electrode 3 is formed over the entire upper surface of the substrate 2. In this case, the ink receiving layer 4A is formed so that the entirety is in contact with the upper surface of the electrode 3. However, as described above, the electrode 3 may be formed in a pattern shape. Therefore, the lower surface of the ink receiving layer 4A may not be in contact with only the upper surface of the electrode 3, but may be formed so that part of the upper surface of the substrate 2 is in contact.

[0097] In other words, the ink receiving layer 4A is a layer formed on the electrode 3 forming surface of the substrate 2 with the electrode 3, and is formed in a region including at least the electrode 3. The formation region of the ink receiving layer 4A may be, for example, a region covering the entire surface of the substrate 2 with the electrode 3, or a region covering a specific region of the substrate 2 with the electrode 3. The ink receiving layer 4A is usually provided as a continuous layer.

[0098] The formation region of the ink receiving layer 4A on the substrate 2 with the electrode 3 is, for example, a region including a region containing an organic semiconductor material formed in a pattern by ink dripping, and is appropriately selected according to the type and purpose of the organic semiconductor device. Specifically, when the organic semiconductor device is an organic EL element used in a display device, the formation region of the ink receiving layer 4A can be a display region.

[0099] The ink receiving layer 4A has an ink permeable region 41 and an ink permeation preventing region 42. The ink permeable region 41 and the ink permeation preventing region 42 exist in a layered state in the entire formation region of the ink receiving layer 4A. The ink permeable region 41 and the ink permeation preventing region 42 may be formed separately as individual layers, and may be two distinct regions by continuously changing the composition within the layer when the ink receiving layer 4A is formed. In any case, the shape of the interface between the ink permeable region 41 and the ink permeation preventing region 42 is not limited, and may be a flat shape or a concave-convex shape.

[0100] exist Figure 1 In the embodiment, the ink penetration preventing region 42 is provided on the side of the ink receiving layer 4A closest to the electrode 3. In the present invention, the ink penetration preventing region 42 may be provided at a position close to the electrode 3 of the ink receiving layer 4A, and another region may be further provided on the electrode side of the ink penetration preventing region 42. The ink penetration preventing region 42 is preferably provided on the side of the ink receiving layer 4A closest to the electrode 3 from the viewpoint of ease of manufacturing.

[0101] As for the differences in the specific structures of the ink permeation area 41 and the ink permeation prevention area 42, specifically, the following can be listed: compared with the constituent materials of the ink permeation area 41, the constituent materials of the ink permeation prevention area 42 have low affinity for ink or are difficult to dissolve; compared with the constituent materials of the ink permeation area 41, the constituent materials of the ink permeation prevention area 42 have a dense structure; compared with the constituent materials of the ink permeation area 41, the constituent materials of the ink permeation prevention area 42 have high thermal properties represented by the glass transition temperature (Tg) and the like.

[0102] In the ink receiving layer 4A, the ink permeable region 41 and the ink permeation preventing region 42 are preferably layers made of different materials. The layer corresponding to the ink permeable region 41 is referred to as an ink permeable layer, and the layer corresponding to the ink permeation preventing region 42 is referred to as an ink permeation preventing layer. The ink permeation preventing layer is preferably an ink insoluble layer that is insoluble in ink. In the following, the ink permeable region 41 and the ink permeation preventing region 42 are referred to as an ink permeable layer and an ink insoluble layer, respectively, and are described by being labeled with the same reference numerals as the ink permeable region 41 and the ink permeation preventing region 42, respectively.

[0103] The ink permeable layer 41 is a layer including the surface S of the ink receiving layer 4A. The layer thickness t1 of the ink permeable layer 41 is preferably a thickness that can sufficiently ensure the thickness of the region containing the organic semiconductor material formed by the ink In dropped on the surface S of the ink permeable layer 41 by the inkjet method. Specifically, the layer thickness t1 of the ink permeable layer 41 is preferably 2 nm to 4.9 μm, and more preferably 10 to 100 nm.

[0104] On the other hand, the thickness t2 of the ink-resistant layer 42 is a layer that prevents penetration so that the ink that penetrates the ink-permeable layer 41 does not reach the electrode 3. It also depends on the type of ink and the composition of the ink-resistant layer 42, but in order to exert the function of preventing the penetration of ink, the thickness t2 of the ink-resistant layer 42 is preferably 1 to 100 nm, more preferably 2 to 100 nm, and further preferably 5 to 100 nm. In the ink-receiving layer 4A, the distance from one end of the electrode 3 side of the obtained region containing the organic semiconductor material to the electrode 3 is preferably 1 nm or more from the viewpoint of fully suppressing the generation of leakage current, and is preferably 100 nm or less from the viewpoint of suppressing the increase in the driving voltage. From such a viewpoint, the thickness t2 of the ink-resistant layer 42 is preferably in the above range.

[0105] The thickness T of the ink receiving layer 4A is the sum of the thickness t1 of the ink permeable layer 41 and the thickness t2 of the ink insoluble layer 42 , and is preferably 3 nm to 5 μm, and more preferably 30 to 150 nm.

[0106] The constituent material of the ink receiving layer 4A, that is, the constituent material of the ink permeable layer 41 and the ink insoluble layer 42, is preferably a resin, and the resin is preferably insulating. The term "insulating" means a resistivity of 1×10 6 Ω·m or more, preferably 1×10 8 Ω·m or more, more preferably 1×10 10 Ω·m or more. The resistivity of the resin is 1×10 6 If the value is Ω·m or more, it is considered that the leakage current flowing in the organic semiconductor layer 6 of the obtained organic semiconductor device can be suppressed.

[0107] The ink permeable layer 41 is a resin having ink permeability (hereinafter referred to as "resin A"), preferably composed mainly of an insulating resin. As such a resin, a resin having higher stability and a main chain composed of carbon atoms is preferred. As for the ink permeable layer 41, it is preferred that the ink permeable layer 41 does not contain a cross-linked resin from the viewpoint of ink permeability.

[0108] In addition, when the ink permeable layer 41 is formed as a layer mainly composed of resin A, for example, the resin A is preferably soluble in an appropriate solvent so that it can be formed by a coating method, and preferably exhibits solubility in an aprotic polar solvent. Specifically, the solubility of the resin A in 1 g of N,N-dimethylformamide at 25° C. is preferably 0.5 mg or more, more preferably 1.0 mg or more, and further preferably 2.0 mg or more.

[0109] There is no particular limitation on the type of resin A as long as it has ink permeability. From the viewpoint of ink permeability, the resin A is preferably a resin having no crosslinking point or having a low crosslinking density.

[0110] Examples of the resin A include nonionic resins such as polystyrene resins, acrylic resins such as polymethyl methacrylate, polycarbonate resins, polyvinyl alcohol resins, polyacrylamide resins, polyvinyl pyrrolidone resins, polyvinyl polypyrrolidone resins, polyethylene glycol resins, polymethyl vinyl ether resins, and polyisopropyl acrylamide resins; cationic resins such as sodium polyacrylate resins, sodium polystyrene sulfonate resins, sodium polyisopropylene sulfonate resins, polynaphthalenesulfonic acid condensate salts, and polyethyleneimine xanthate salts; anionic resins such as dimethylaminomethyl (meth)acrylate quaternary salt resins, dimethyldiallylammonium chloride resins, polyamidine resins, polyvinyl imidazoline resins, dicyandiamide condensate resins, epichlorohydrin dimethylamine condensates, and polyethyleneimine resins; and amphoteric resins such as dimethylaminoethyl (meth)acrylate quaternary salt acrylic acid copolymers and Hofmann decomposition products of polyacrylamide.

[0111] As resin A, there can be used polyalkylene resins such as polyethylene, polypropylene, polyvinylidene fluoride, and polyacrylonitrile, polyethylene terephthalate, polyethylene naphthalate, polyphenylene ether, polyvinyl ether ketone, polyphenylene sulfide, polyphenylene sulfone, polysulfone, polyether sulfone, polyarylate, polystyrene, polyvinyl phenol, and derivatives of these polymers, polymers containing aromatic rings, and curing resins such as phenolic resins and epoxy resins.

[0112] Among these, polystyrene resin, acrylic resin such as polymethyl methacrylate, or polycarbonate resin is preferred as resin A. In addition, it is preferred from the viewpoint of the bite or entanglement of the polymer containing an aromatic ring with the electrode lattice and the interaction with the adjacent layer. In particular, a resin (polymer) containing a benzene ring such as polystyrene resin is preferred.

[0113] From the viewpoint of carrier blocking, the polymer containing a benzene ring is preferably a non-conjugated polymer. In addition, from the viewpoint of the effect of dispersing the organic semiconductor material described later, the non-conjugated polymer preferably contains a benzene ring as a side chain.

[0114] From the viewpoint of inhibiting interfacial rebonding, it is particularly preferred that the non-conjugated polymer is a polystyrene resin. In the case of a polymer containing a benzene ring, especially a polymer containing a benzene ring in a side chain such as a polystyrene resin, it interacts with a large amount of organic semiconductor materials containing π conjugation, and is easy to enclose the organic semiconductor material when dried to form a phase separation structure, and it is easy to obtain a capture inhibition effect and a carrier blocking effect. In addition, from the viewpoint of controlling the local amount of the polymer interface and being able to adjust the carrier balance, it is preferred that the non-conjugated polymer is a mixture of components with different stereoregularities.

[0115] In this specification, the so-called polystyrene resin refers to a resin mainly containing polymerized units based on styrene monomers. The so-called mainly containing means that the ratio of polymerized units based on styrene monomers to all polymerized units is 50 mol% or more. For other resins, it has the same meaning.

[0116] Styrene monomers include styrene represented by the structural formula of CH2=CH-C6H5 and monomers having a known side chain or functional group in the styrene structure. Examples of the functional group include a hydroxyl group, an ester group, and an amide group.

[0117] Specific examples of styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, etc. These styrene monomers can be used alone or in combination of two or more.

[0118] The polystyrene resin may be composed of polymerized units based on styrene monomers alone, or may contain polymerized units based on vinyl monomers other than styrene monomers. Examples of such vinyl monomers include (meth)acrylic acid (a general term for acrylic acid and methacrylic acid) or (meth)acrylic acid monomers as derivatives thereof, and olefin monomers such as alicyclic or aliphatic olefins.

[0119] As the polystyrene resin, preferably, the polymerized units are all polystyrene based on styrene (CH2=CH-C6H5). In addition, as the polystyrene resin, polyvinylphenol is preferably used from the viewpoint of suppressing the re-bonding of the interface between the two electrode sides. By including a benzene ring with an additional polar group in the side chain as polyvinylphenol, hydrogen bonds are formed between polymers, and the formation of a phase separation structure is promoted by heating during drying.

[0120] As the above-mentioned polymer containing an aromatic ring, a polymer containing an aromatic ring having a structure represented by the following general formula (I) or general formula (II) is preferred. A polymer containing a benzene ring is particularly preferred. In addition, it is preferred that the polymer containing a benzene ring is a non-conjugated polymer. Furthermore, it is also preferred that the non-conjugated polymer is a polymer containing a benzene ring as a side chain, such as polystyrene and a polystyrene derivative.

[0121] Hereinafter, the aromatic ring-containing polymer having a structure represented by the following general formula (I) or (II) will be described in detail.

[0122]

Chemistry 1

[0123] General formula (Ⅰ)

[0124]

[0125]

Chemistry 2

[0126] General formula (Ⅱ)

[0127]

[0128] In the above general formula (I) and general formula (II), A represents an aromatic ring, and the aromatic ring contains an aromatic hydrocarbon ring and an aromatic heterocyclic ring. These may be monocyclic or condensed rings. L represents a divalent linking group. x and y represent integers of 0 or 1 or more. However, x and y are not 0 at the same time. When x is 0, L contains an aromatic ring. n represents a degree of polymerization, which is greater than 10 and less than 100,000. R1 represents a hydrogen atom or a substituent.

[0129] The aromatic ring represented by A includes, as described above, an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Each of these may be a monocyclic ring or a condensed ring. From the viewpoint of electrical conductivity or insulation, the aromatic ring is preferably an aromatic hydrocarbon ring. From the viewpoint of solubility, the number of atoms constituting the aromatic ring after removing the substituent from the above-mentioned general formula (I) and general formula (II) is preferably 20 or less, more preferably 12 or less, and further preferably 6 or less.

[0130] Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a pentacene ring, The acene-based structure is preferably a benzene ring or a naphthalene ring.

[0131] Examples of the aromatic heterocyclic ring include a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, an acridine ring, a thiophene ring, a furan ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring, an indole ring, an imidazole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a triazole ring, an oxadiazole ring, a thiadiazole ring, a dioxazole ring, a dithiazole ring, a tetrazole ring, and a pentazole ring.

[0132] From the viewpoint of making the organic semiconductor material (ink containing the organic semiconductor material) compatible through interaction, the aromatic ring represented by A is preferably a benzene ring, and specifically, the structure of the following general formula (III) can be mentioned.

[0133]

Chemistry 3

[0134] General formula (III)

[0135]

[0136] In the above general formula (III), X and Y represent a hydrogen atom or a bond to the repeating unit L or A in the above general formula (I) or a bond to C (carbon atom) in the above general formula (II).

[0137] R1 to R5 represent a hydrogen atom or a substituent, and each independently represents a hydrogen atom, a heavy hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxycarbonyl group, a haloformyl group, a formyl group, an acyl group, an alkoxy group, a mercapto group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a carbamoyl group, a silyl group, a phosphine oxide group, an imide group, an aromatic imide ring group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a non-aromatic hydrocarbon ring group, or a non-aromatic heterocyclic group, and may further have a substituent.

[0138] In the above general formula (I), general formula (II) and general formula (III), examples of the alkyl group represented by R1 to R5 include methyl, ethyl, propyl, isopropyl, (tert-)butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, benzyl and the like.

[0139] Examples of the alkenyl group represented by R1 to R5 include groups having one or more double bonds in the above-mentioned alkyl groups, and more specifically, vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, and the like.

[0140] Examples of the alkynyl group represented by R1 to R5 include ethynyl, acetylenyl, 1-propynyl, 2-propynyl (propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 1-heptynyl, 2-heptynyl, 5-heptynyl, 1-octynyl, 3-octynyl, and 5-octynyl.

[0141] Examples of the aromatic hydrocarbon ring group (also referred to as an aryl group) represented by R1 to R5 include phenyl, p-chlorophenyl, mesityl, tolyl, xylyl, naphthyl, anthracenyl, azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, and biphenyl.

[0142] Examples of the aromatic heterocyclic group represented by R1 to R5 include pyridyl, pyrimidinyl, furyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrazolyl, pyrazinyl, triazolyl (e.g., 1,2,4-triazol-1-yl, 1,2,3-triazol-1-yl, etc.), oxazolyl, benzoxazolyl, thiazolyl, isoxazolyl, isothiazolyl, furazanyl, thienyl, quinolyl, benzofuranyl, dibenzofuranyl, benzothienyl, dibenzothienyl, indolyl, carbazolyl, carbolyl, diazacarbazolyl (a group in which one of the carbon atoms constituting the carboline ring of the above carbolyl group is replaced by a nitrogen atom), quinoxalinyl, pyridazinyl, triazinyl, quinazolinyl, phthalazinyl, and the like.

[0143] Examples of the non-aromatic hydrocarbon ring group represented by R1 to R5 include cycloalkyl groups (e.g., cyclopentyl, cyclohexyl, etc.), cycloalkyloxy groups (e.g., cyclopentyloxy, cyclohexyloxy, etc.), cycloalkylthio groups (e.g., cyclopentylthio, cyclohexylthio, etc.), and monovalent groups derived from a tetralin ring, a 9,10-dihydroanthracene ring, a biphenylene ring, etc.

[0144] Examples of the non-aromatic hydrocarbon ring group represented by R1 to R5 include an epoxy ring, an aziridine ring, a thiirane ring, an oxetane ring, an azetidine ring, a thietane ring, a tetrahydrofuran ring, a dioxolane ring, a pyrrolidine ring, a pyrazolidine ring, an imidazolidine ring, an oxazolidine ring, a tetrahydrothiophene ring, a sulfolane ring, a thiazolidine ring, an ε-caprolactone ring, an ε-caprolactam ring, a piperidine ring, a hexahydropyridazine ring, and a hexahydropyrimidine ring. , a monovalent group derived from a piperazine ring, a morpholine ring, a tetrahydropyran ring, a 1,3-dioxane ring, a 1,4-dioxane ring, a trioxane ring, a tetrahydrothiopyran ring, a thiomorpholine ring, a thiomorpholine-1,1-dioxide ring, a pyranose ring, a diazabicyclo[2,2,2]-octane ring, a phenoxazine ring, a phenothiazine ring, a dibenzo-p-dioxin ring, a thioxanthene ring, a phenoxathiin ring, and the like.

[0145] Examples of the alkoxy group represented by R1 to R5 include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, and octadecyloxy.

[0146] Examples of the acyl group represented by R1 to R5 include acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl and pyridylcarbonyl.

[0147] Examples of the amino group represented by R1 to R5 include amino, ethylamino, dimethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, and 2-pyridylamino.

[0148] Examples of the silyl group represented by R1 to R5 include a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, and a phenyldiethylsilyl group.

[0149] Examples of the phosphine oxide group represented by R1 to R5 include a diphenylphosphine oxide group, a xylylphosphine oxide group, a dimethylphosphine oxide group, a dinaphthylphosphine oxide group, and a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group.

[0150] As the substituents which the groups represented by R1 to R5 may further have, for example, each independently represents an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, (tert)butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, benzyl, etc.), a cycloalkyl group (e.g., cyclopentyl, cyclohexyl, etc.), an alkenyl group (e.g., vinyl, allyl, etc.), an alkynyl group (e.g., propargyl, etc.), an aromatic hydrocarbon group (also referred to as an aryl group, e.g., phenyl, p-chlorophenyl, mesityl, tolyl, xylyl, naphthyl, anthracenyl, azulenyl, acenaphthenyl, fluorenyl, phenanthrenyl, indenyl, pyrenyl, biphenyl, etc.), a heterocyclic group (e.g., an epoxy ring, an aziridine ring, a thiirane ring, an oxetane ring, an azetidine ring, a thiol ... an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, an alkyl ring, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, furazanyl, thienyl, quinolyl, benzofuranyl, dibenzofuranyl, benzothienyl, dibenzothienyl, indolyl, carbazolyl, carbolyl, diazacarbazolyl (a group in which one of the carbon atoms constituting the carbolyl ring of the above carbolyl group is replaced by a nitrogen atom), quinoxalinyl, pyridazinyl, triazinyl, quinazolinyl, phthalazinyl, etc.), a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a dodecyloxy group, etc.), a cycloalkyloxy group (for example, a cyclopentyloxy group, a cyclohexyloxy group, etc.), an aryloxy group (for example, a phenoxy group, a naphthyloxy group, etc.), an alkylthio group (for example, a methylthio group, an ethylthio group, a propylthio group, a pentylthio group thio groups (e.g., cyclopentylthio, cyclohexylthio, etc.), arylthio groups (e.g., phenylthio, naphthylthio, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl, naphthyloxycarbonyl, etc.), sulfamoyl groups (e.g., aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfonyl, etc.), urea groups (e.g., methylurea, ethylurea, pentylurea, cyclohexylurea, octylurea,ylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy (e.g. acetyloxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, dodecylcarbonyloxy, phenylcarbonyloxy, etc.), acylamino (e.g. methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonyl, etc.), amino, etc.), carbamoyl (e.g., aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl, etc.), sulfinyl (e.g., methylsulfinyl, ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyridylsulfinyl, etc.), alkylsulfonyl or arylsulfonyl (e.g., methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2- 1-Hydroxy-1-methyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, 1-dimethyl-2-nitro-2-ol, any group selected from the group consisting of alkyl phosphino, aryl phosphino, dimethyl phosphino, diethyl phosphino, dicyclohexyl phosphino, methyl phenyl phosphino, diphenyl phosphino, dinaphthyl phosphino, di(2-pyridyl)phosphino, alkyl phosphoryl, aryl phosphoryl, dimethyl phosphoryl, diethyl phosphoryl, dicyclohexyl phosphoryl, methyl phenyl phosphoryl, diphenyl phosphoryl, dinaphthyl phosphoryl, di(2-pyridyl)phosphino, alkyl thiophosphoryl, aryl thiophosphoryl, dimethyl thiophosphoryl, diethyl thiophosphoryl, dicyclohexyl thiophosphoryl, methyl phenyl thiophosphoryl, diphenyl thiophosphoryl, dinaphthyl thiophosphoryl, di(2-pyridyl)phosphino.

[0151] In addition, these substituents may be further substituted by the above-mentioned substituents, and they may be fused with each other to further form a ring.

[0152] L in the above-mentioned general formula (I) and general formula (II) represents a divalent linking group, which represents an alkylene group, an alkenylene group, a carbonyl group, an ether group, an imino group, an imido group, an acylamino group, an o-phenylene group, an m-phenylene group, a p-phenylene group, a sulfonyl group, a thioether group, a thioester group, a silyl group, a phosphine oxide group, or a divalent aromatic heterocyclic group, and may further have a substituent.

[0153] In the above general formula (I) and general formula (II), examples of the alkylene group represented by L include a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, a butane-1,2-diyl group, and a hexylene group.

[0154] In addition, examples of the alkenylene group represented by L include vinylene, propenylene, butenylene, pentenylene, 1-methylvinylene, 1-methylpropenylene, 2-methylpropenylene, 1-methylpentenylene, 3-methylpentenylene, 1-ethylvinylene, 1-ethylpropenylene, 1-ethylbutenylene, and 3-ethylbutenylene.

[0155] Examples of the acylamino group represented by L include methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, and naphthylcarbonylamino.

[0156] Examples of the divalent aromatic heterocyclic group represented by L include divalent groups derived from the groups listed as the aromatic heterocyclic groups represented by R1 to R5 in the above general formula (I), general formula (II) and general formula (III).

[0157] In the above general formula (I) and general formula (II), x and y each represent an integer of 0 or 1 or more.

[0158] n represents the degree of polymerization, and is 10 or more and 100,000 or less.

[0159] These repeating structures may be formed by sequential polymerization like the repetition of ALAL, or by block polymerization like AALL and ALL.

[0160] When both or either one of x and y is 2 or more, two or more A, L, and R1 to R5 may be the same as or different from each other.

[0161] Specific examples of the resin A include polymers having the following structures: In the following structural formula, n, x and y are integers, the degree of polymerization n is in the range of 10 to 100, and the copolymerization ratio is preferably in the range of x:y=1:99 to 99:1.

[0162]

Chemistry 4

[0163]

[0164] Structural formula (9)

[0165]

[0166] Structural formula (10)

[0167]

[0168] Structural formula (11)

[0169]

[0170]

[0171]

[0172] Structural formula (20)

[0173]

[0174] Structural formula (21)

[0175]

[0176] Structural formula (22)

[0177]

[0178]

Chemistry 6

[0179]

[0180] Structural formula (30)

[0181]

[0182] The weight average molecular weight of resin A is appropriately adjusted according to the types of resin A and ink and the thickness t1 of the ink permeable layer 41. The weight average molecular weight of resin A is preferably smaller than that of resin B mainly constituting the ink insoluble layer 42 described below.

[0183] The weight average molecular weight of the resin A is preferably 1×10 3 ~1000×10 3 The range is more preferably 50×10 3 ~400×10 3 The range is more preferably 50×103 ~350×10 3 It is considered that when the weight average molecular weight is within this range, the penetration and diffusion of the ink in the ink permeable layer 41 can be appropriately controlled.

[0184] It should be noted that the weight average molecular weight refers to the weight average molecular weight measured by gel permeation chromatography (GPC) using dimethylformamide as a solvent and converted to polystyrene. When dimethylformamide cannot be used for measurement, tetrahydrofuran is used. When it still cannot be measured, hexafluoroisopropanol is used. When hexafluoroisopropanol cannot be used for measurement, 2-chloronaphthalene is used for measurement.

[0185] The ink permeable layer 41 may be composed of only resin A or may contain any component. Resin A may be used alone or in combination of two or more. As the arbitrary component, resins other than resin A, charge transporting compounds (main compounds for organic semiconductor materials), surfactants, other additives, etc. may be listed. However, from the viewpoint of ink permeability, it is preferred that the ink permeable layer 41 does not contain any resin other than resin A.

[0186] Examples of other additives include halogen elements such as bromine, iodine, and chlorine, halogenated compounds, and compounds, complexes, and salts of alkali metals, alkaline earth metals, and transition metals such as Pd, Ca, and Na. The content of other additives can be arbitrarily determined, but is preferably 1000 ppm by mass or less relative to the total amount of the ink permeable layer.

[0187] The charge transporting compound may be used alone or in combination of two or more. By using two or more charge transporting compounds, the movement of charges can be adjusted, and the efficiency of the organic semiconductor device can be improved.

[0188] As for the charge transport compound, from the viewpoint of driving stability, it is preferred that it can stably exist in the state of all active species in the cationic radical state, the anionic radical state, and the excited state, without causing chemical changes such as decomposition and addition reaction. Furthermore, it is preferred that the charge transport compound molecules in the layer move at the angstrom level over time without being energized.

[0189] From the perspective of luminous efficiency, the electron mobility [cm 2 / (V·s)] and hole mobility [cm 2 / (V·s)], that is, the ratio of electron mobility to hole mobility, is in the range of 0.5 to 2.0.

[0190] Electron mobility [cm 2 / (V·s)] and hole mobility [cm 2 / (V·s)] can be obtained by separately preparing a single-electron device (composition example: ITO anode / calcium layer / charge transport compound layer / potassium fluoride layer / aluminum cathode) and a single-hole device (composition example: ITO anode / charge transport compound layer / α-NPD layer / aluminum cathode), measuring the current density-voltage characteristics of these devices, making two logarithmic coordinate graphs, and using the current density obtained therefrom and the applied voltage and the space charge limited current formula.

[0191] The space charge limited current formula is J = (9 / 8)ε r ε0μ(V 2 / L 3 ). In the formula, J represents the current density, ε r represents the dielectric constant of the charge transport compound layer, ε0 represents the dielectric constant of vacuum, and μ represents the electron mobility [cm 2 / (V·s)] or hole mobility [cm 2 / (V·s)], L represents the thickness of the charge transport compound layer, and V represents the applied voltage.

[0192] As the charge transporting compound, known charge transporting compounds in organic semiconductor devices can be used, and specifically, compounds described in the following documents can be mentioned, but the present invention is not limited to these.

[0193] Japanese Patent Application Laid-Open No. 2001-257076, Japanese Patent Application Laid-Open No. 2002-308855, Japanese Patent Application Laid-Open No. 2001-313179, Japanese Patent Application Laid-Open No. 2002-319491, Japanese Patent Application Laid-Open No. 2001-357977, Japanese Patent Application Laid-Open No. 2002-334786, Japanese Patent Application Laid-Open No. 2002-8860, Japanese Patent Application Laid-Open No. 2002-334787, Japanese Patent Application Laid-Open No. 2002-15871, Japanese Patent Application Laid-Open No. 2002-334788, Japanese Patent Application Laid-Open No. 2002-43056, Japanese Patent Application Laid-Open No. 2002-334789, Japanese Patent Application Laid-Open No. 2002-75645, Japanese Patent Application Laid-Open No. 2002 002-338579, Japanese Patent Application Laid-Open No. 2002-105445, Japanese Patent Application Laid-Open No. 2002-343568, Japanese Patent Application Laid-Open No. 2002-141173, Japanese Patent Application Laid-Open No. 2002-352957, Japanese Patent Application Laid-Open No. 2002-203683, Japanese Patent Application Laid-Open No. 2002-363227, Japanese Patent Application Laid-Open No. 2002-231453, Japanese Patent Application Laid-Open No. 2003-3165, Japanese Patent Application Laid-Open No. 2002-234888, Japanese Patent Application Laid-Open No. 2003-27048, Japanese Patent Application Laid-Open No. 2002-255934, Japanese Patent Application Laid-Open No. 2002-260861, Japanese Patent Application Laid-Open No. 2002- 280183, Japanese Patent Application Publication No. 2002-299060, Japanese Patent Application Publication No. 2002-302516, Japanese Patent Application Publication No. 2002-305083, Japanese Patent Application Publication No. 2002-305084, Japanese Patent Application Publication No. 2002-308837, Japanese Patent Application Publication No. 2016-178274, U.S. Patent Application Publication No. 2003 / 0175553, U.S. Patent Application Publication No. 2006 / 0280965, U.S. Patent Application Publication No. 2005 / 0112407, U.S. Patent Application Publication No. 2009 / 0017330, U.S. Patent Application Publication No. 2009 / 0030202, U.S. Patent Application Publication No. 2005 / 0238919, International Publication No. 2001 / 039234, International Publication No. 2009 / 021126, International Publication No. 2008 / 056746, International Publication No. 2004 / 093207, International Publication No. 2005 / 089025, International Publication No. 2007 / 063796, International Publication No. 2007 / 063754, International Publication No. 2004 / 107822, International Publication No. 2005 / 030900, International Publication No. 2006 / 114966, International Publication No. 2009 / 086028, International Publication No. 2009 / 003898, International Publication No. 2012 / 023947,Japanese Patent Application Publication No. 2008-074939, Japanese Patent Application Publication No. 2007-254297, European Patent Application No. 2034538, International Publication No. 2011 / 055933, International Publication No. 2012 / 035853, Japanese Patent Application Publication No. 2015-38941, and U.S. Patent Application Publication No. 2017 / 056814.

[0194] The charge transporting compound is preferably a compound having a structure represented by the following general formula (1).

[0195]

Chemistry 7

[0196] General formula (1)

[0197]

[0198] [In the general formula (1), X represents O, S or NR9. R9 represents a hydrogen atom, a deuterium atom, an alkyl group, an alkenyl group, an alkynyl group, an arylalkyl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a non-aromatic hydrocarbon ring group, a non-aromatic heterocyclic group, or a substituent represented by the following general formula (2). R1 ​​to R8 each represent a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an acyl group, an amino group, a silyl group, a phosphine oxide group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a non-aromatic hydrocarbon ring group, a non-aromatic heterocyclic group, or a substituent represented by the following general formula (2). At least one of R1 to R9 represents a substituent represented by the following general formula (2). R1 ​​to R9 may be the same as or different from each other and may further have a substituent.]

[0199]

Chemistry 8

[0200] General formula (2)

[0201]

[0202] [In the general formula (2), L each represents an alkylene group, an alkenylene group, an o-phenylene group, an m-phenylene group, a p-phenylene group, an acylamino group or a divalent aromatic heterocyclic group, and may further have a substituent. n represents an integer of 1 to 8. When n represents an integer of 2 or more, the two or more Ls may be the same or different from each other. R represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon ring group, an aromatic heterocyclic group or a non-aromatic hydrocarbon ring group, and may further have a substituent. m represents an integer of 1 to 3. At least one of L and R represents an alkylene group or an alkyl group. When there are multiple substituents represented by the general formula (2), L and R may be the same or different from each other and will not be connected to each other to form a ring.]

[0203] The substituents represented by R1 to R9 in the above general formula (1) have the same meanings as R1 to R6 in the above general formulas (I) to (III). In addition, the linking group represented by L in the above general formula (2) has the same meaning as L in the above general formulas (I) and (II).

[0204] In the above general formula (2), examples of the alkyl group having 1 to 20 carbon atoms represented by R include groups having 1 to 20 carbon atoms among the groups exemplified as the alkyl group represented by R1 to R9 in the above general formula (1).

[0205] Examples of the fluorinated alkyl group having 1 to 20 carbon atoms represented by R include groups in which a hydrogen atom of the above-mentioned alkyl group having 1 to 20 carbon atoms is substituted with a fluorine atom.

[0206] Examples of the alkoxy group having 1 to 20 carbon atoms represented by R include groups having 1 to 20 carbon atoms among the groups exemplified as the alkoxy group represented by R1 to R9 in the general formula (1).

[0207] Examples of the aromatic hydrocarbon ring group, aromatic heterocyclic group or non-aromatic hydrocarbon ring group represented by R include the same groups as those represented by R1 to R9 in the above general formula (1).

[0208] In the above general formula (2), examples of substituents that L and R may further have include the same substituents as those that R1 to R9 may have in the above general formula (1).

[0209] As the compound having a structure represented by the above-mentioned general formula (1), it is preferred that at least one L in the substituent represented by the general formula (2) is an alkylene group having 1 to 6 carbon atoms, and further, it is preferred that at least one R in the substituent represented by the general formula (2) is an alkyl group having 1 to 6 carbon atoms.

[0210] Specific examples of the compound having a structure represented by the general formula (1) according to the present invention are shown below, but the compound is not limited to these.

[0211]

Chemistry 9

[0212]

[0213]

Chemistry 10

[0214]

[0215]

Chemistry 11

[0216]

[0217]

Chemistry 12

[0218]

[0219]

Chemistry 13

[0220]

[0221] The ink permeable layer 41 preferably has high affinity with the ink used from the viewpoint of ink permeability. For example, when the SP value in the constituent material of the ink permeable layer 41 is represented by SP(M1) and the SP value of the ink used for manufacturing the organic semiconductor device is represented by SP(I), the absolute value of the difference between the two represented by |SP(M1)-SP(I)| is preferably 3.0 (J / cm 3 ) 1 / 2 the following.

[0222] The so-called SP value is called the solubility parameter. The SP values ​​of various compounds in the present invention can be obtained from literature such as the Plastic Raw Materials Dictionary (https: / / www.plastics-material.com / Plasticizers, Solvents Solubility Parameters (sp Values) / ). Alternatively, the SP value can be obtained by molecular dynamics (MD) or the like. For example, it can be obtained by a method of obtaining the molecular gravitational constant, that is, by the molecular gravitational constant (G) and molar volume (V) of each functional group or atomic group constituting the molecule of the compound, according to the method of obtaining the SP value = ΣG / V (DA Small, J. Appl. Chem., 3, 71, (1953), KL Hoy, J. Paint Technol., 42, 76 (1970)).

[0223] The ink permeable layer and the ink are usually composed of a plurality of compounds. The SP value of the constituent material in this case can be obtained by weighted average of the SP value and the composition of each component contained in the constituent material. In this specification, the SP value is rounded off to the first decimal place.

[0224] If |SP(M1)-SP(I)| is 3.0(J / cm 3 ) 1 / 2 Below, the ink permeable layer 41 can fully permeate the ink. |SP(M1)-SP(I)| More preferably 2.3 (J / cm 3 ) 1 / 2 the following.

[0225] It should be noted that the SP values ​​of the solvent and the solute in the ink are close to each other. In many cases, the solvent accounts for the majority of the composition of the ink, for example, 98% by mass or more. Therefore, in such a case, the SP value of the solvent can be set as SP(S), which replaces the SP value (I) of the ink, and the absolute value of the difference from SP(M1) can be used as an index. That is, due to Therefore, |SP(M1)-SP(S)| is preferably 3.0(J / cm 3 ) 1 / 2 Below, more preferably 2.3 (J / cm 3 ) 1 / 2 the following.

[0226] The ink-insoluble layer 42 is insoluble in ink, and thus has the function of preventing the ink from penetrating from the ink-permeable layer 41 to the electrode 3 side. As for the ink, as described later, it contains an organic semiconductor material and a solvent as essential components. In order to have the above-mentioned function, the ink-insoluble layer 42 preferably contains a resin (hereinafter referred to as "resin B") having sufficiently lower ink permeability than resin A, and preferably a resin having no ink permeability as a main component. "The ink permeability of resin B is sufficiently lower than that of resin A" means that the ink permeability is so low at the layer thickness t2 of the ink-insoluble layer 42 that the ink does not penetrate into the electrode 3.

[0227] As for resin B, similarly to resin A, it is preferably an insulating resin, and preferably a resin whose main chain is composed of carbon atoms, which has higher stability. Resin B is preferably poorly soluble in ink. The so-called poorly soluble in ink specifically means that it can satisfy the index according to the SP value described later.

[0228] It should be noted that when the ink-insoluble layer 42 is formed as a layer containing resin B as a main component, for example, it is preferably formed by a coating method, and the resin B is soluble in a suitable solvent different from the ink, such as an aprotic polar solvent. Specifically, the solubility of the resin B in 1 g of N,N-dimethylformamide at 25° C. is preferably 0.5 mg or more, more preferably 1.0 mg or more, and further preferably 2.0 mg or more.

[0229] As resin B, it is preferred that the atomic density in the polymerization unit is high, the molecular chain is long, the molecule has a cross-linked structure, the molecular chain is entangled, and the resin is easy to form a dense structure. As resin B, for example, it is a resin of the same type as resin A, and a resin with a higher weight average molecular weight than resin A can be cited.

[0230] For example, when a polystyrene resin is used as the resin B, the weight average molecular weight is preferably 100×10 3 ~3000×10 3 The range is preferably 360×103 ~1500×10 3 , and more preferably 400×10 3 ~1000×10 3 range.

[0231] As the resin B, a cross-linked resin is preferred, and a resin having a high cross-linking density is preferred. Examples of such resin B include melamine cross-linked resins, epoxy cross-linked resins, and phenolic resins.

[0232] As resin B, a resin containing a structure in which heterogeneous polymers are entangled with each other, i.e., an interpenetrating polymer network (IPN) structure (hereinafter also referred to as "resin B1") is preferred. It should be noted that the so-called interpenetrating polymer network structure is characterized by the following state: two or more polymer chains are entangled with each other to form a network structure independent of chemical bond formation. It is different from simple polymer blends and copolymers. The interpenetrating polymer network structure swells in a solvent, but the constituent components do not dissolve. In addition, in the case of heterogeneous polymers, phase separation generally occurs, but it is characterized by the difficulty in phase separation (reference: Life Engineering Research Vol. 8, No. 1, pp. 144-147, 2006).

[0233] Resin B1 can be prepared, for example, by mixing a polymer compound with a monomer (radical polymerizable compound) of a type different from the monomer involved in the polymerization unit of the polymer compound, and polymerizing the monomer under appropriate conditions. Depending on the type of monomer used, a polymerization initiator or the like may be added. In the case of using a monomer that reacts with moisture in the air to cure, such as cyanoacrylate, a polymerization initiator is not necessary.

[0234] Examples of the polymer compound include polystyrene resins, epoxy resins, polyester resins, and the like. Examples of the monomer include (meth)acrylic acid or its derivatives, i.e., (meth)acrylic acid monomers. The mixing ratio (mass %) of the monomer relative to 100 mass % of the polymer compound is, for example, preferably 0.1 to 50 mass %, and more preferably 0.1 to 20 mass %.

[0235] The resin B1 is preferably a resin produced by using a polystyrene resin as a polymer compound and a cyanoacrylate as a monomer mixed therewith. The cyanoacrylate includes methyl-2-cyanoacrylate, ethyl-2-cyanoacrylate, n-butyl cyanoacrylate, 2-octyl cyanoacrylate, and the like.

[0236] As resin B, a resin having a high atomic density in the polymerized unit is preferred. As such a resin, a resin containing tetraphenylbenzidine or a derivative thereof as a main polymerized unit (hereinafter also referred to as "resin B2") can be exemplified. As derivatives of tetraphenylbenzidine, compounds in which the hydrogen atoms bonded to four benzene rings are substituted with hydrocarbon groups or functional groups can be cited. As the hydrocarbon group, an alkyl group having 1 to 8 carbon atoms can be cited, preferably an n-butyl group. As the functional group, a hydroxyl group, an ester group, an acylamino group, etc. can be cited.

[0237] As the resin B2, for example, a resin (PTPD) having a polymerized unit based on N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)-benzidine (TPD) as a repeating unit is preferred.

[0238] The ink-insoluble layer 42 may be composed of only the resin B, or may contain any component. One type of the resin B may be used alone, or two or more types may be used in combination. As the optional component, resins other than the resin B, charge transporting compounds, surfactants, other additives, etc. may be listed. However, from the viewpoint of maintaining low permeability to the ink, it is preferred that the ink-insoluble layer 42 does not contain any resin other than the resin B. As other additives, the same additives as those described in the ink permeable layer 41 may be used in the same content.

[0239] As the charge transport compound, the same charge transport compound as described in the ink permeable layer 41 can be used. The content of the charge transport compound in the ink poorly soluble layer 42 can be the same as that in the ink permeable layer 41 .

[0240] The ink-resistant layer 42 preferably has a property of low ink permeability, that is, low affinity with ink. For example, when the SP value in the constituent material of the ink-resistant layer 42 is represented by SP(M2) and the SP value of the ink used for manufacturing the organic semiconductor device is represented by SP(I), the absolute value of the difference between the two represented by |SP(M2)-SP(I)| is preferably 3.1 (J / cm 3 ) 1 / 2 above.

[0241] If |SP(M2)-SP(I)| is 3.1(J / cm 3 ) 1 / 2 Above, the ink permeability of the ink-insoluble layer 42 is sufficiently low, and the ink is unlikely to reach the electrode 3. |SP(M2)-SP(I)| More preferably, 3.5 (J / cm 3 ) 1 / 2 above.

[0242] It should be noted that the SP values ​​of the solvent and the solute in the ink are close to each other. In many cases, the solvent accounts for a large part of the composition of the ink, for example, 98% by mass or more. Therefore, in such a case, the SP value of the solvent can be set as SP(S), which replaces the SP value (I) of the ink, and the absolute value of the difference with SP(M2) is used as an index. That is, since Therefore, |SP(M2)-SP(S)| is preferably 3.1(J / cm 3 ) 1 / 2 More preferably, 3.5 (J / cm 3 ) 1 / 2 above.

[0243] <Release film>

[0244] The inkjet recording medium of the present invention preferably further comprises a release film on the ink receiving layer. The release film is used to improve the storage stability of the inkjet recording medium and is released from the inkjet recording medium during use.

[0245] As the release film, known resin films such as polyester resin films, silicone resin films, polyolefin resin films, etc. can be used. The thickness of the release film is preferably 0.1 to 1000 μm, more preferably 1 to 50 μm, from the viewpoint of storage stability and handling properties.

[0246] It should be noted that by using a peeling film, it is speculated that not only the general function of a protective film, i.e., blocking physical influences from the outside (such as protection from damage such as scratches, protection from oxygen and water) is achieved, but also the effect of promoting phase separation caused by inhibiting the formation of an interface between gas (air or nitrogen, etc.) and an organic thin film (solid) is achieved.

[0247] (Manufacture of inkjet recording medium)

[0248] The ink jet recording medium of the present invention can be produced, for example, by a method including the following steps.

[0249] (i) Step of forming the electrode 3 on the substrate 2 to obtain the substrate 2 with the electrode 3

[0250] (ii) Step of forming the ink receiving layer 4A on the electrode of the substrate 2 with the electrode 3

[0251] When the inkjet recording medium further includes a release film on the ink receiving layer, after the step (ii), there is further included a step (iii) of laminating the release film on the ink receiving layer 4A.

[0252] (i) Preparation of substrate with electrodes

[0253] The method of forming the electrode 3 on the substrate 2 is as described above.

[0254] (ii) Formation of ink receiving layer

[0255] The process of forming the ink receiving layer 4A will be described below by taking as an example the case of an ink receiving layer including the ink insoluble layer 42 and the ink permeable layer 41 in this order from the electrode 3 side.

[0256] The ink-insoluble layer 42 is preferably formed by a wet method. In addition, as a wet method, there are spin coating, casting, inkjet printing, screen printing, slit die coating, doctor blade coating, roller coating, spray coating, curtain coating, LB method (Langmuir-Blodgett method), etc. From the viewpoint of easy acquisition of a uniform thin film and particularly high productivity, spin coating, screen printing, and slit die coating are preferred, which are excellent in mass production.

[0257] When the ink-resistant layer 42 is formed by a wet method, a coating liquid is used in which the constituent materials of the ink-resistant layer 42 are dissolved or dispersed in a solvent. The solvent is not particularly limited as long as it can dissolve or disperse any components such as the resin B and the charge transporting compound.

[0258] Specifically, the type of liquid medium is not particularly limited as to the solvent, and examples thereof include halogen solvents such as chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, dichlorobenzene, and dichlorohexanone; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, n-propyl methyl ketone, and cyclohexanone; aromatic solvents such as benzene, toluene, xylene, mesitylene, and cyclohexylbenzene; aliphatic solvents such as cyclohexane, decalin, and dodecane; ester solvents such as ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, and diethyl carbonate; ether solvents such as tetrahydrofuran and dioxane; amide solvents such as dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, 1-butanol, and ethylene glycol; nitrile solvents such as acetonitrile and propionitrile; dimethyl sulfoxide; water or a mixed liquid medium thereof; and the like.

[0259] The boiling point of these solvents is preferably lower than the temperature of the drying treatment from the viewpoint of rapidly drying the solvent, and specifically, is preferably in the range of 60 to 200°C, more preferably in the range of 80 to 180°C.

[0260] The coating liquid may contain a surfactant for the purpose of controlling the coating range or suppressing the flow of liquid associated with the surface tension gradient after coating (for example, the flow of liquid causing the phenomenon called coffee ring).

[0261] As for the surfactant, from the viewpoints of the influence of the water contained in the solvent, leveling, wettability to the substrate, for example, anionic or nonionic surfactants can be listed. Specifically, the surfactants listed in International Publication No. 08 / 146681, Japanese Patent Laid-Open No. 2-41308 Gazette, etc. can be used.

[0262] The coating liquid used in the wet method may be a solution in which the constituent material of the ink-insoluble layer 42 is uniformly dissolved in a solvent, or a dispersion in which the constituent material is dispersed as a solid component in a solvent. Dispersion methods such as ultrasonic dispersion, high shear dispersion, and medium dispersion can be used.

[0263] The concentration of the coating liquid can be appropriately selected according to the solubility or dispersibility of the constituent material of the ink-insoluble layer 42 , and for example, the solid content concentration can be selected within the range of 0.1 to 50% by mass.

[0264] The viscosity of the coating liquid can be appropriately selected according to the solubility or dispersibility of the material forming the ink-insoluble layer 42 , and can be selected within a range of 0.3 to 100 mPa·s, for example.

[0265] The thickness of the coating film is preferably set to a thickness that will provide the ink-insoluble layer 42 with the thickness described above after drying.

[0266] After the coating film is formed by a wet method, a drying process for removing the above-mentioned solvent can be provided. There is no particular restriction on the temperature of the drying process, and it is preferred to perform the drying process at a temperature at which the ink insoluble layer 42, the electrode 3, and the substrate 2 are not damaged. Specifically, since it varies depending on the composition of the coating liquid, etc., it cannot be generalized. For example, the temperature can be set to be above 80°C, and the upper limit is considered to be in the range of about 300°C. The time is preferably about 10 seconds or more and about 10 minutes or less. By setting such conditions, drying can be performed quickly.

[0267] The ink permeable layer 41 is formed on the ink insoluble layer 42. The ink permeable layer 41 is preferably formed by a wet method similar to the ink insoluble layer 42. The coating liquid used for forming the ink permeable layer 41 can be the same as the coating liquid used for forming the ink insoluble layer 42 except that the resin A is used instead of the resin B.

[0268] The coating liquid can be applied by the same method as in the case of the ink insoluble layer 42. The coating film preferably has a thickness that will provide the ink permeable layer 41 after drying.

[0269] After forming the coating film for the ink permeable layer 41, drying can be performed in the same manner as in the case of the ink insoluble layer 42. However, drying can be performed simultaneously during the formation of the ink insoluble layer 42 and the ink permeable layer 41. That is, after forming the coating film of the ink insoluble layer 42, the coating film for the ink permeable layer 41 can be formed without drying, and then drying can be performed to obtain the ink receiving layer 4A.

[0270] (iii) Lamination of release films

[0271] The release film is laminated in a form that covers the entire surface S of the ink receiving layer 4A. As a lamination method, for example, a method of subjecting a laminated body in which the release film is laminated on the ink receiving layer 4A of the inkjet recording medium to a pressing treatment, a heat treatment, or a combination of these treatments can be cited. The pressing can be a pressing using a decompression device. As a method of laminating the release film, for example, a method of placing the above-mentioned laminated body in a device and maintaining it at a temperature of 0 to 150° C. and a pressure condition of atmospheric pressure to 10 MPa for 0.1 to 60 minutes can be cited.

[0272] [Members for organic semiconductor devices]

[0273] The organic semiconductor device member of the present invention is a member for organic semiconductor devices in which a substrate, an electrode, and an organic semiconductor layer are sequentially stacked. The organic semiconductor device member of the present invention is characterized in that the organic semiconductor layer has: an ink receiving layer continuously present over the entire region of the organic semiconductor layer formation region on the electrode; and a region containing an organic semiconductor material having an exposed portion in a pattern shape on a surface of the organic semiconductor layer away from the electrode and having no interface with the electrode as a discontinuous region surrounded by the ink receiving layer.

[0274] In the organic semiconductor device member of the present invention, the region containing the organic semiconductor material is, for example, a region formed using ink containing the organic semiconductor material, preferably a region formed by applying the ink containing the organic semiconductor material by an inkjet method. Hereinafter, the case where the region containing the organic semiconductor material is formed by the inkjet method is described as an example, but the invention is not limited thereto.

[0275] For the organic semiconductor device member of the present invention, refer to Figure 2 , Figure 3 and Figure 4 Provide explanation. Figure 2 and Figure 3 The organic semiconductor device member 10A shown in FIG. Figure 1 An example of an organic semiconductor device member obtained by using the inkjet recording medium 1 of the present invention shown in FIG. Figure 4A cross-sectional view of an organic semiconductor device member 10B as another example of the organic semiconductor device member 10A is shown. The organic semiconductor device member 10B can be produced using, for example, an inkjet recording medium other than the inkjet recording medium of the present invention.

[0276] Therefore, as long as the organic semiconductor device member of the present invention has the above-mentioned structural features, it may be an organic semiconductor device member obtained using the inkjet recording medium for an organic semiconductor device of the present invention, or it may be an organic semiconductor device member obtained using other inkjet recording media.

[0277] Preferred organic semiconductor layers include, for example, a light emitting layer when the organic semiconductor device is an organic EL, a photoelectric conversion layer when a photoelectric conversion element is used, and a charge transport layer when an organic TFT is used.

[0278] Figure 2 and Figure 3 The organic semiconductor device member 10A shown in FIG. Figure 1 The member for an organic semiconductor device of the present invention obtained by forming the inkjet recording medium 1 shown in the figure is formed by laminating a substrate 2, an electrode 3, and an organic semiconductor layer 6 in this order. The organic semiconductor layer 6 includes an ink receiving layer 4A which exists continuously over the entire region of the formation region of the organic semiconductor layer 6 on the electrode 3, and a region 5 containing an organic semiconductor material which is a discontinuous region surrounded by the ink receiving layer 4A. The ink receiving layer 4A includes an ink penetration prevention region 42 and an ink penetration region 41 in this order from the electrode 3 side. The region 5 containing an organic semiconductor material has an exposed portion D in a pattern shape on the surface S of the organic semiconductor layer 6 away from the electrode 3, and does not have an interface with the electrode 3.

[0279] Figure 2 1 is a plan view of the organic semiconductor device member 10A, and is a view that allows confirmation of the pattern shape of the exposed portion D of the region 5 containing the organic semiconductor material in the surface S. The organic semiconductor device member 10A has 6 vertical rows and 8 horizontal columns, a total of 48 dot-shaped regions 5 containing organic semiconductor materials, in the plan view. However, Figure 2 The dot pattern of the organic semiconductor device member 10A shown in FIG. 1 is merely an example, and the present invention is not limited thereto. Figure 3 The organic semiconductor device member 10A is used Figure 2 The region 5 containing the organic semiconductor material has a thickness in the thickness direction that is equivalent to the thickness of the ink permeation region 41 and is separated from the electrode 3 by a thickness portion of the ink permeation prevention region 42 .

[0280] It should be noted that in Figure 2 and Figure 3 In the organic semiconductor device member 10A shown in , the organic semiconductor layer 6 is formed so as to cover the entire surface of the electrode 3, but the formation region of the organic semiconductor layer 6 is not limited thereto. The formation region is appropriately selected according to the type and application of the semiconductor device. For example, when the organic semiconductor device is an organic EL element used in a display device, the formation region of the organic semiconductor layer 6 may be a display region.

[0281] The pattern shape on the surface S of the region 5 containing the organic semiconductor material is not limited to Figure 2 The shape and number of patterns are appropriately selected according to the type and application of the semiconductor device. As for the shape of each exposed portion D of the region 5 containing the organic semiconductor material, a circular dot shape is preferred. It should be noted that the term "circular" in this specification does not refer to a true circle, but is used as a concept including circular shapes such as ellipses.

[0282] When the exposed portion D is a circular dot shape, the maximum diameter d of the exposed portion D can be appropriately adjusted by, for example, changing the specifications of the head used for the inkjet method, and specifically, can be set to a range of 30 to 300 μm. It should be noted that the maximum diameter d of the exposed portion D can be measured based on an optical microscope photograph taken from the surface S side.

[0283] The formation of the region 5 containing the organic semiconductor material can be carried out, for example, by: Figure 5 As shown in the figure, ink In is dropped from the head 12 of the inkjet device 11 corresponding to the inkjet method onto the surface S of the ink receiving layer 4A of the inkjet recording medium 1. The dropped ink In bounces onto the exposed area D of the surface S of the ink receiving layer 4A (ink permeation area 41), and permeates into the ink permeation area 41 from the surface S of the ink receiving layer 4A toward the electrode 3 within the range of the exposed area D. Moreover, the permeation of the ink In toward the electrode 3 is stopped due to the presence of the ink permeation prevention area 42. It should be noted that, as for the permeation of the ink, it is sufficient to stop in the ink permeation prevention area 42 until it reaches the bottom of the ink permeation prevention area 42, and it is not necessarily necessary to stop on the top of the ink permeation prevention area 42.

[0284] exist Figure 5 , the situation where the penetration of ink stops at the position above the ink penetration prevention area 42 is shown. The ink used in the inkjet method contains a solvent and an organic semiconductor material. The details of the composition of the ink will be described later. Ink penetration is specifically a phenomenon in which the ink passes through the gaps of the material constituting the ink penetration area 41. For example, in the case where the ink penetration area 41 is mainly composed of a resin, the ink penetrates between the molecules of the resin. In addition, the penetration of the ink is sometimes accompanied by the dissolution of the material constituting the ink penetration area 41.

[0285] In the ink receiving layer 4A, as described above, the solvent is removed from the region permeated with the ink In, and the region 5 containing the organic semiconductor material is formed in which the organic semiconductor material is dispersed in the constituent material of the ink permeating region 41. The region permeated with the ink In in the ink receiving layer 4A and the obtained region 5 containing the organic semiconductor material have substantially the same shape and the same size.

[0286] The content of the organic semiconductor material in the region 5 containing the organic semiconductor material also depends on the design of the organic semiconductor device, but can be about 1 to 100% by mass, preferably about 80 to 99% by mass, based on the total amount of the region 5 containing the organic semiconductor material.

[0287] The thickness Th of the region 5 containing the organic semiconductor material, that is, the depth from the exposed region D in the surface S to one end on the electrode 3 side, depends on the design of the organic semiconductor device. In the ink receiving layer 4A, it is preferable to design the thickness of the ink permeable region 41 so as to ensure that the thickness Th of the region 5 containing the organic semiconductor material is as designed.

[0288] In addition, the distance from one end of the region 5 containing the organic semiconductor material to the electrode 3 is preferably 1 nm or more, more preferably 2 nm or more, and further preferably 5 nm or more from the viewpoint of sufficiently suppressing the generation of leakage current. In addition, the above distance is preferably 100 nm or less from the viewpoint of suppressing the increase of the driving voltage. In the ink receiving layer 4A, the thickness of the ink penetration preventing region 42 is preferably designed in such a way that the distance between the region 5 containing the organic semiconductor material and the electrode 3 can be maintained within the above range.

[0289] At once Figure 4 The organic semiconductor device member 10B shown in FIG. 1 has the same structure except that the organic semiconductor device member 10A and the ink receiving layer have different structures. The ink receiving layer 4A of the organic semiconductor device member 10A has an ink permeation region 41 and an ink permeation prevention region 42, and the ink receiving layer 4B of the organic semiconductor device member 10B is composed of a substantially uniform region.

[0290] It should be noted that in the embodiment of the organic semiconductor device member, whether in the case of the organic semiconductor device member 10A or the organic semiconductor device member 10B, the maximum thickness of the ink receiving layer is preferably in the range of 3 nm to 5 μm. That is, regardless of whether the ink receiving layer is a single layer or a multilayer, the maximum thickness of the ink receiving layer is preferably in the above range.

[0291] Among them, the maximum thickness of the ink receiving layer is the layer thickness from the surface of the ink receiving layer away from the electrode to the top of the electrode. The organic semiconductor layer in the member for organic semiconductor devices is obtained by dripping ink containing organic semiconductor materials in a pattern shape on the surface of the ink receiving layer as described later, and allowing the ink to penetrate in the depth direction of the ink receiving layer in the dripping part to form an area containing organic semiconductor materials. The organic semiconductor layer obtained in this way has a structure having an ink receiving layer and an area containing organic semiconductor materials. Therefore, the maximum thickness of the ink receiving layer in the member for organic semiconductor devices is the same as the thickness of the ink receiving layer before the ink is dripped. In addition, the minimum thickness of the ink receiving layer is the distance from one end of the electrode side of the area containing organic semiconductor materials to the electrode.

[0292] As for the maximum thickness of the ink receiving layer, it is preferred that the thickness of the region containing the organic semiconductor material formed by the penetration of the ink dropped onto the surface of the ink receiving layer by the inkjet method be sufficiently ensured. In addition, as for the maximum thickness of the ink receiving layer, it is preferred that the thickness be capable of designing the distance between the region containing the organic semiconductor material and the electrode to be above 1 nm. From such a point of view, the maximum thickness of the ink receiving layer is preferably within the above range. It should be noted that in the case where the ink receiving layer is composed of a single layer, in order to sufficiently ensure the distance between the region containing the organic semiconductor material and the electrode, the lower limit of the maximum thickness of the ink receiving layer is preferably above 5 nm. In addition, it is known that the thicker the film thickness, the lower the mobility due to the restriction of the low carrier mobility peculiar to the organic semiconductor material. If it exceeds 5 μm, the loss will greatly affect the function as a device, so the upper limit is preferably within 5 μm.

[0293] In the embodiment of the member for an organic semiconductor device, it is preferred that the constituent material of the ink receiving layer mainly contains 3 ~1000×10 3 Specifically, from the viewpoint of ink permeability, it is preferable to have a configuration mainly composed of the resin A in the ink permeable layer 41 described in the organic semiconductor device member 10A. For example, in the organic semiconductor device member 10A, the ink receiving layer 4A is preferably configured mainly with the ink permeable layer 41.

[0294] If the weight average molecular weight of the main constituent material of the ink receiving layer is within 1×10 3 ~1000×10 3 In other words, by keeping the weight average molecular weight within the range of 1×10 3As described above, excessive penetration of the ink into the ink receiving layer can be prevented. For example, even when the ink receiving layer is composed of a single layer, by adjusting the thickness (maximum thickness) of the ink receiving layer, it is easy to prevent the region containing the organic semiconductor material from reaching the electrode. 3 Thereafter, the ink can easily penetrate to an appropriate depth in the ink receiving layer.

[0295] Also, from the viewpoint of ink permeability, the absolute value of the difference between the SP value of the constituent material of the ink receiving layer and the SP value of the ink used for forming the region containing the organic semiconductor material is preferably 3.0 (J / cm 3 ) 1 / 2 It is to be noted that, when the ink receiving layer is composed of multiple layers as in the organic semiconductor device member 10A, in the ink permeable layer 41 as described above, the absolute value of the difference in the SP value is preferably 3.0 (J / cm 3 ) 1 / 2 the following.

[0296] If the absolute value of the difference between the SP value of the constituent material of the ink receiving layer and the SP value of the ink used in forming the region containing the organic semiconductor material is 3.0 (J / cm 3 ) 1 / 2 Below, the affinity between the ink and the ink receiving layer is high, and the permeability of the ink into the ink receiving layer can be sufficiently ensured.

[0297] As the composition of the ink receiving layer 4B, for example, a layer composed of a constituent material equivalent to the constituent material of the above-mentioned ink permeable layer, for example, a constituent material mainly composed of resin A, and having a layer thickness greater than that of the ink permeable layer can be cited. The layer thickness in this case can be cited in the range of 3nm to 5μm, preferably 5 to 200nm, and more preferably 60 to 100nm. It should be noted that the layer thickness refers to the layer thickness (maximum thickness) from the surface S to the upper surface of the electrode 3 in the ink receiving layer 4B.

[0298] In the case of using the ink receiving layer 4B of the constituent material, it also depends on the type of ink, but for example, the distance from one end of the region 5 containing the organic semiconductor material to the electrode 3 can be designed to be 1 nm or more, preferably 2 nm or more, and more preferably 5 nm or more. In addition, for example, when the layer thickness of the ink receiving layer 4B is 60 to 100 nm, the ink can be designed to penetrate from the surface S to a depth of 50 to 95 nm, but the ink cannot penetrate deeper than that and does not reach the electrode 3.

[0299] In the ink receiving layer 4B, the constituent material and thickness are preferably designed so that the thickness Th of the region 5 containing the organic semiconductor material can be ensured as the designed thickness and the distance between the region 5 containing the organic semiconductor material and the electrode 3 can be maintained within the above range.

[0300] The ink receiving layer 4B may be designed as follows, for example, to be mainly composed of a resin AL that is likely to have a dense structure even in the resin A and is likely to have a sparse structure compared to the resin B. The resin AL may be a resin having a high weight average molecular weight even in the resin A. For example, when a polystyrene resin is used as the resin AL, the weight average molecular weight is preferably 10×10 3 ~1000×10 3 The range is more preferably 100×10 3 ~400×10 3 range.

[0301] As described above, the ink receiving layer 4B preferably has appropriate ink permeability to the extent that the ink does not reach the electrode 3. From this point of view, for example, when the SP value in the constituent material of the ink receiving layer 4B is represented by SP(M3) and the SP value of the ink used for manufacturing the organic semiconductor device is represented by SP(I), the ink receiving layer 4B can be formed so that the absolute value of the difference between the two represented by |SP(M3)-SP(I)| is 3.0 (J / cm 3 ) 1 / 2 The following is a structure that has the above-mentioned moderate ink permeability.

[0302] It should be noted that the SP values ​​of the solvent and the solute in the ink are close to each other. In many cases, the solvent accounts for the majority of the composition of the ink, for example, 98% by mass or more. Therefore, in such a case, the SP value of the solvent is set to SP(S), which replaces the SP value (I) of the ink, and the absolute value of the difference from SP(M3) can be used as an index. That is, since Therefore, it is preferred that |SP(M3)-SP(S)| is between 0 and 3.0 (J / cm 3 ) 1 / 2 range.

[0303] <Ink>

[0304] The ink of the present invention is an inkjet ink applicable to an ink coating method using an inkjet method, and contains a solvent and an organic semiconductor material. In the ink, the organic semiconductor material is dissolved or dispersed in the solvent.

[0305] The viscosity of the ink can be appropriately selected so that it can be discharged from the nozzle of the inkjet head (hereinafter also referred to as the "head") used for the inkjet method. The viscosity of the ink can be selected within the range of, for example, 0.3 to 100 mPa·s. It should be noted that the viscosity of the ink can be measured at 25°C using an E-type viscometer. The number of revolutions can be set according to the viscosity, for example, 10 rpm or 20 rpm. Unless otherwise specified, the viscosity in this specification is the viscosity at 25°C measured using the above method.

[0306] Regarding the SP value of the ink, when the ink receiving layer is composed of two layers of different regions, such as the ink permeable layer 41 and the ink insoluble layer 42, as in the ink receiving layer 4A, it is preferable that the above relationship is satisfied in the relationship between the SP value in the constituent material of the ink permeable layer 41 and the SP value in the constituent material of the ink insoluble layer 42. In addition, when the ink receiving layer is composed of one substantially uniform region, as in the ink receiving layer 4B, it is preferable that the above relationship is satisfied in the relationship with the SP value in the constituent material of the ink receiving layer 4B.

[0307] In addition, with respect to the concentration of the organic semiconductor material in the ink, it is preferred that the viscosity of the ink be set to a concentration within the above range. The concentration of the organic semiconductor material in the ink depends on the types of the organic semiconductor material and the solvent, and can be set, for example, to about 0.1 to 80% by mass, preferably 0.1 to 10% by mass.

[0308] The ink may contain various functional additives. For example, various known additives such as viscosity modifiers, surface tension modifiers, resistivity modifiers, film forming agents, dispersants, surfactants, ultraviolet absorbers, antioxidants, anti-fading agents, mildew inhibitors, rust inhibitors, etc. may be appropriately selected according to the purpose of improving discharge stability, print head suitability, storage stability, image preservation, and other performances. In addition, the ink may contain the same charge transporting compound as the charge transporting compound that can be arbitrarily matched in the ink receiving layer.

[0309] (Organic semiconductor materials)

[0310] The organic semiconductor material contained in the ink is appropriately selected according to the type of organic semiconductor device to be manufactured. For example, when the organic semiconductor device is an organic EL element, the organic semiconductor material is a luminescent compound, and the organic semiconductor layer is preferably a luminescent layer. When the organic semiconductor device is an organic photoelectric conversion element, the organic semiconductor material is preferably an n-type organic semiconductor compound and a p-type organic semiconductor compound, and the organic semiconductor layer is a photoelectric conversion layer. When the organic semiconductor device is an organic TFT, various organic semiconductor materials can be widely used.

[0311] [Luminescent Compounds]

[0312] Luminescent compounds are classified into, for example, fluorescent compounds, delayed fluorescent compounds, and phosphorescent compounds. Luminescent compounds can be used in combination in the form of, for example, different phosphorescent compounds or a phosphorescent compound and a fluorescent compound. This can produce any luminescent color.

[0313] The luminescent layer of the present invention also preferably contains a plurality of luminescent compounds of different luminescent colors to emit white light. There is no particular limitation on the combination of luminescent compounds that emit white light, and examples thereof include combinations of cyan and orange, cyan, green, and red. The so-called white in the present invention is preferably 1000 cd / m2 when the front brightness at a 2-degree viewing angle is measured by the following method. 2 The chromaticity in the CIE1931 color system is within the range of x=0.39±0.09 and y=0.38±0.08.

[0314] It should be noted that the color of the light emitted by the organic EL element of the present invention and the compound used in the present invention is as shown on page 108 of the New Handbook of Color Science (edited by the Japan Color Society, published by the University of Tokyo, 1985). Figure 3 .16 The color is determined by substituting the measurement results using the spectroradiometer CS-1000 (manufactured by Konica Minolta Co., Ltd.) into the CIE chromaticity coordinates.

[0315] <Fluorescent compounds>

[0316] In the present invention, the so-called "fluorescent compound" refers to a compound that emits fluorescence other than delayed fluorescence. The so-called "fluorescence" refers to the light emitted when returning from the singlet excited state to the ground state, and the so-called "fluorescence other than delayed fluorescence" refers to fluorescence other than "delayed fluorescence" such as "thermally activated delayed fluorescence (TADF)" and "triplet-triplet annihilation (TTA) delayed fluorescence". That is, in the present invention, the so-called "fluorescent compound" does not include "delayed fluorescence compounds" such as "thermally activated delayed fluorescence compounds" and "triplet-triplet annihilation delayed fluorescence compounds", and refers to a fluorescent compound that does not undergo up-conversion caused by anti-intersystem crossing from the lowest excited triplet energy level to the lowest excited singlet energy level.

[0317] Fluorescent compounds, in particular, are not necessarily heavy metal complexes such as phosphorescent compounds. So-called organic compounds composed of a combination of common elements such as carbon, oxygen, nitrogen and hydrogen can be used. Furthermore, other non-metallic elements such as phosphorus, sulfur and silicon can also be used. In addition, complexes of typical metals such as aluminum and zinc can also be effectively utilized, and the diversity can be said to be almost unlimited.

[0318] The fluorescent compound can be appropriately selected from known fluorescent compounds used in the light-emitting layer of an organic EL device and can be used.

[0319] Examples of known fluorescent compounds that can be used in the present invention include anthracene derivatives, pyrene derivatives, Derivatives, fluoranthene derivatives, perylene derivatives, fluorene derivatives, arylacetylene derivatives, styryl arylene derivatives, styrylamine derivatives, arylamine derivatives, boron complexes, coumarin derivatives, pyran derivatives, cyanine derivatives, croconium derivatives, squalium derivatives, oxobenzanthracene derivatives, fluorescein derivatives, rhodamine derivatives, pyrylium derivatives, perylene derivatives, polythiophene derivatives, or rare earth complex compounds, etc.

[0320] <Phosphorescent compounds>

[0321] In the present invention, the so-called "phosphorescent compound" refers to a compound that emits phosphorescence, specifically, a compound that emits phosphorescence at room temperature (25°C), and is defined as a compound having a phosphorescence quantum yield of 0.01 or more at 25°C. The preferred phosphorescence quantum yield is 0.1 or more. The so-called "phosphorescence" refers to the light emitted when returning from the triplet excited state to the ground state.

[0322] The above-mentioned phosphorescence quantum yield can be measured by the method described in Spectroscopy II of the 4th edition of Experimental Chemistry Lecture 7, page 398 (1992 edition, Maruzen). The phosphorescence quantum yield in a solution can be measured using various solvents, but the phosphorescent compound used in the present invention can achieve the above-mentioned phosphorescence quantum yield (0.01 or more) in any solvent.

[0323] When an organic EL element is excited by an electric field, triplet excitons are generated with a probability of 75% and singlet excitons are generated with a probability of 25%. Therefore, phosphorescence can improve luminous efficiency compared to fluorescence, and is an excellent method for achieving low power consumption.

[0324] Phosphorescence is theoretically three times more efficient than fluorescence in terms of luminescence efficiency. However, the energy deactivation from the triplet excited state to the singlet ground state (=phosphorescence) is a forbidden transition, and similarly, the intersystem crossing from the singlet excited state to the triplet excited state is also a forbidden transition, so its rate constant is usually small. That is, since the transition is difficult to occur, the phosphorescence lifetime is extended to milliseconds to seconds, and it is difficult to obtain the desired luminescence.

[0325] However, when using luminescence from complexes of heavy metals such as iridium (Ir) and platinum (Pt), the rate constant of the above-mentioned bandgap transition increases by more than three digits due to the heavy atom effect of the central metal, and a 100% phosphorescence quantum yield can be obtained by selecting the ligand.

[0326] The phosphorescent compound can be appropriately selected from known phosphorescent compounds used in the light-emitting layer of an organic EL device. Specific examples of known phosphorescent compounds that can be used in the present invention include compounds described in the following documents.

[0327] Nature 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17, 1059 (2005), International Publication No. 2009 / 100991, International Publication No. 2008 / 101842, International Publication No. 2003 / 040257, U.S. Patent Application Publication No. 2006 / 835469, U.S. Patent Application Publication No. 2006 / 0202194, U.S. Patent Application Publication No. 2007 / 0087321 Specification, U.S. Patent Application Publication No. 2005 / 0244673, Inorg. Chem. 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. Int. Ed. 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. 34, 592 (2005), Chem. Commun. 2906 (2005), Inorg. Chem. 42, 1248 (2003), International Publication No. 2 009 / 050290, International Publication No. 2002 / 015645, International Publication No. 2009 / 000673, U.S. Patent Application Publication No. 2002 / 0034656, U.S. Patent No. 7332232, U.S. Patent Application Publication No. 2009 / 0108737, U.S. Patent Application Publication No. 2009 / 0039776, U.S. Patent No. 6921915, U.S. Patent No. 6687266, U.S. Patent Application Publication No. 2007 / 0190359, U.S. Patent Application Publication No. 2006 / 0008670, U.S. Patent Application Publication No. 2009 / 0165846 Specification, U.S. Patent Application Publication No. 2008 / 0015355, U.S. Patent No. 7250226, U.S. Patent No. 7396598, U.S. Patent Application Publication No. 2006 / 0263635, U.S. Patent Application Publication No. 2003 / 0138657, U.S. Patent Application Publication No. 2003 / 0152802, U.S. Patent No. 7090928, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. 18, 5119 (2006), Inorg. Chem. 46, 4308 (2007), Organometallics 23, 3745 (2004), Appl.Phys. Lett. 74, 1361 (1999), International Publication No. 2002 / 002714, International Publication No. 2006 / 009024, International Publication No. 2006 / 056418, International Publication No. 2005 / 019373, International Publication No. 2005 / 123873, International Publication No. 2005 / 123873, International Publication No. 2007 / 004380, International Publication No. 2006 / 082742, U.S. Patent Application Publication No. 2006 / 0251923, U.S. Patent Application Please disclose the specification of U.S. Patent No. 2005 / 0260441, U.S. Patent No. 7393599, U.S. Patent No. 7534505, U.S. Patent No. 7445855, U.S. Patent Application Publication No. 2007 / 0190359, U.S. Patent Application Publication No. 2008 / 0297033, U.S. Patent No. 7338722, U.S. Patent Application Publication No. 2002 / 0134984, U.S. Patent No. 7279704, U.S. Patent Application Publication No. 2006 / 098120, U.S. Patent No. Please disclose the specification No. 2006 / 103874, International Publication No. 2005 / 076380, International Publication No. 2010 / 032663, International Publication No. 2008140115, International Publication No. 2007 / 052431, International Publication No. 2011 / 134013, International Publication No. 2011 / 157339, International Publication No. 2010 / 086089, International Publication No. 2009 / 113646, International Publication No. 2012 / 020327, International Publication No. 2011 / 051404, International Publication No. 2011 / 004639, International Publication No. 2011 / 073149, U.S. Patent Application Publication No. 2012 / 228583, U.S. Patent Application Publication No. 2012 / 212126, Japanese Patent Application Publication No. 2012-069737, Japanese Patent Application Publication No. 2011-181303, Japanese Patent Application Publication No. 2009-114086, Japanese Patent Application Publication No. 2003-81988, Japanese Patent Application Publication No. 2002-302671, Japanese Patent Application Publication No. 2002-363552, etc.

[0328] Among them, preferred phosphorescent compounds include organic metal complexes having Ir as the central metal, and more preferably, complexes having at least one coordination pattern of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond.

[0329] As the phosphorescent compound, a complex having a coordination pattern including a metal-nitrogen bond and having a structure represented by the following general formula (N) is preferred.

[0330]

Chemistry 14

[0331] General formula (N)

[0332]

[0333] In the formula, Ring A and Ring B represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring, and the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring may be further fused to form a fused polycyclic aromatic hydrocarbon ring or fused polycyclic aromatic heterocyclic ring. Ra and Rb each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group, an aryl group, a heteroaryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent. a Indicates 1 or 2, n b represents an integer of 1 to 4. When a plurality of Ra and Rb exist, they may be bonded to each other to form a ring.

[0334] L' is one or more of the monoanionic bidentate ligands coordinated to M, M represents an atomic number of 40 or more and a transition metal atom of Groups 8 to 10 in the periodic table, preferably Ir, Pt, Rh, Ru, Ag, Cu or Os, particularly preferably Ir. m' represents an integer of 0 to 2, n' represents an integer of 1 to 3, and m'+n' is 2 or 3.

[0335] Among the phosphorescent compounds represented by the above general formula (N), preferred are phosphorescent compounds represented by the following general formula (N1) in which ring A is a pyridine ring and phosphorescent compounds represented by the following general formula (N2) in which ring A is an imidazole ring.

[0336]

Chemistry 15

[0337] General formula (N1)

[0338]

[0339] In the formula, ring B represents a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring, and the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring may be further condensed to form a condensed polycyclic aromatic hydrocarbon ring or condensed polycyclic aromatic heterocyclic ring. Ra and Rb each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group, an aryl group, a heteroaryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent. a Indicates 1 or 2, n b represents an integer of 1 to 4. When a plurality of Ra and Rb exist, they may be bonded to each other to form a ring.

[0340] L' is one or more of the monoanionic bidentate ligands coordinated to M, M represents an atomic number of 40 or more and a transition metal atom of Groups 8 to 10 in the periodic table, preferably Ir, Pt, Rh, Ru, Ag, Cu or Os, particularly preferably Ir. m' represents an integer of 0 to 2, n' represents an integer of 1 to 3, and m'+n' is 2 or 3.

[0341]

Chemistry 16

[0342] General formula (N2)

[0343]

[0344] In the formula, Ring B and Ring C represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring, and the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring may be further fused to form a fused polycyclic aromatic hydrocarbon ring or a fused polycyclic aromatic heterocyclic ring. Ar represents an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group. R1 and R2 each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group, an aryl group, a heteroaryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent, and at least one of R1 and R2 is an alkyl group or a cycloalkyl group having 2 or more carbon atoms. Ra, Rb and Rc each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group, an aryl group, a heteroaryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent. a and n c Indicates 1 or 2, n b Indicates an integer from 1 to 4.

[0345] L' is one or more of the monoanionic bidentate ligands coordinated to M, M represents an atomic number of 40 or more and a transition metal atom of Groups 8 to 10 in the periodic table, preferably Ir, Pt, Rh, Ru, Ag, Cu or Os, particularly preferably Ir. m' represents an integer of 0 to 2, n' represents an integer of 1 to 3, and m'+n' is 2 or 3.

[0346] Among the phosphorescent compounds represented by the above general formula (N2), preferred are phosphorescent compounds represented by the following general formula (N21) in which ring B and ring C are benzene rings.

[0347]

Chemistry 17

[0348] General formula (N21)

[0349]

[0350] In the formula, Ar represents an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group. R1 and R2 each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group, an aryl group, a heteroaryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent, and at least one of R1 and R2 is an alkyl group or a cycloalkyl group having 2 or more carbon atoms. Ra, Rb and Rc each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group, an aryl group, a heteroaryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent. n a and n c Indicates 1 or 2, n b Indicates an integer from 1 to 4.

[0351] L' is one or more of the monoanionic bidentate ligands coordinated to M, M represents an atomic number of 40 or more and a transition metal atom of Groups 8 to 10 in the periodic table, preferably Ir, Pt, Rh, Ru, Ag, Cu or Os, particularly preferably Ir. m' represents an integer of 0 to 2, n' is at least 1, and m'+n' is 2 or 3.

[0352] Among the phosphorescent compounds represented by the general formula (N1), as the compound in which M is Ir, specifically, compounds GD-1 to GD-4 and RD-1 to RD-3 having the structures shown below can be cited.

[0353]

Chemistry 18

[0354]

[0355]

Chemistry 19

[0356]

[0357] Among the phosphorescent compounds represented by the general formula (N21), as the compound in which M is Ir, specifically, compounds BD-1 to BD-5 having the structures shown below can be cited.

[0358]

Chemistry 20

[0359]

[0360] <Delayed fluorescence compounds>

[0361] In the present invention, the term "delayed fluorescence compound" refers to a compound that emits delayed fluorescence. The term "delayed fluorescence" refers to light emitted when an upconversion occurs from the lowest excited triplet energy level to the lowest excited singlet energy level, and as a result, the singlet excited state returns to the ground state.

[0362] For the upconversion caused by antisystem crossing from the lowest excited triplet energy level to the lowest excited singlet energy level, the energy difference ΔE between the lowest excited triplet energy level and the lowest excited singlet energy level is ST Occurs in very rare cases.

[0363] “Delayed fluorescence” includes “thermally activated delayed fluorescence” and “triplet-triplet annihilation delayed fluorescence”, that is, “delayed fluorescence compound” includes “thermally activated delayed fluorescence compound” and “triplet-triplet annihilation delayed fluorescence compound”.

[0364] (Thermal activated delayed fluorescence compound)

[0365] The so-called "thermally activated delayed fluorescence compound" refers to a compound that emits thermally activated delayed fluorescence (TADF). The so-called "thermally activated delayed fluorescence (TADF)" refers to the light emitted when returning from the singlet excited state to the ground state as a result of upconversion caused by anti-intersystem crossing from the lowest excited triplet energy level to the lowest excited singlet energy level due to the absorption of ambient heat energy.

[0366] In the case of thermally activated delayed fluorescence compounds, the rate constant of deactivation (= fluorescence emission) from the singlet excited state to the ground state is extremely large, so for triplet excitons, it is more favorable in terms of rate theory to return to the ground state while emitting light via the singlet excited state than to thermally deactivate (radiative deactivation) in the ground state. Therefore, in terms of thermally activated delayed fluorescence (TADF), 100% emission is theoretically possible.

[0367] Examples of thermally activated delayed fluorescence compounds include compounds described in International Publication No. 2011 / 156793, Japanese Patent Application Publication No. 2011-213643, Japanese Patent Application Publication No. 2010-93181, Japanese Patent No. 5366106, International Publication No. 2013 / 161437, and International Publication No. 2016 / 158540, but the present invention is not limited thereto.

[0368] (Triplet-triplet annihilation delayed fluorescence compound)

[0369] The so-called "triplet-triplet annihilation delayed fluorescence compound" refers to a compound that emits triplet-triplet annihilation delayed fluorescence (TTA delayed fluorescence). The so-called "triplet-triplet annihilation delayed fluorescence (TTA delayed fluorescence)" refers to light emitted when the singlet excited state changes to the ground state as a result of up-conversion caused by anti-intersystem crossing from the lowest excited triplet energy level to the lowest excited singlet energy level due to collision between excited triplets.

[0370] The generation of singlet excitons due to the collision between excited triplet states can be described by the following general formula.

[0371] General formula: T ＊ +T ＊ →S ＊ +S

[0372] (Where T ＊ represents triplet exciton, S ＊ represents a singlet exciton, and S represents a ground state molecule. )

[0373] As the triplet-triplet annihilation delayed fluorescence compound, a known compound can be used.

[0374] [n-type organic semiconductor compound and p-type organic semiconductor compound]

[0375] Examples of organic semiconductor materials used when the organic semiconductor device is a photoelectric conversion element include n-type organic semiconductor compounds and p-type organic semiconductor compounds.

[0376] Examples of the p-type organic semiconductor compound include the following condensed polycyclic aromatic low molecular weight compounds, conjugated polymers, and conjugated oligomers.

[0377] Examples of the condensed polycyclic aromatic low molecular weight compound include anthracene, tetracene, pentacene, hexacene, heptacene, , fulminene, pyrene, anthracene, perylene, terylene, quaterylene, coronene, ovalene, circumanthracene, bisanthene, zeslene, heptazeslene, pyranthene, biolanten, isobiolanten, circobiphenyl, anthracenedithiophene and other compounds, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF)-tetracyanoquinodimethane (TCNQ) complex, bis(ethylene dithiotetrathiafulvalene) (BEDTTTF)-perchloric acid complex, and their derivatives and precursors.

[0378] In addition, as examples of the above-mentioned derivatives having fused polycyclic rings, there can be listed pentacene derivatives having substituents described in International Publication No. 03 / 16599, International Publication No. 03 / 28125, U.S. Patent No. 6,690,029, Japanese Patent Publication No. 2004-107216, etc., pentacene precursors described in U.S. Patent Application Publication No. 2003 / 136964, etc., and trialkylsilylethynyl-substituted acene compounds described in J. Amer. Chem. Soc., vol. 127. No. 14. 4986, J. Amer. Chem. Soc., vol. 123, p9482, J. Amer. Chem. Soc., vol. 130 (2008), No. 9, 2706, etc.

[0379] Examples of the conjugated polymer include polythiophene such as poly-3-hexylthiophene (P3HT) and its oligomers, or polythiophene having a polymerizable group as described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, p1225, polythiophene-thienothiophene copolymers as described in Nature Material, (2006) vol.5, p328, polythiophene-diketopyrrolopyrrole copolymers as described in International Publication No. 2008 / 000664, polythiophene-thiazolothiazole copolymers as described in Adv Mater, 2007 p4160, Nature Polymer materials such as polythiophene copolymers such as PCPDTBT described in Mat.vol.6(2007), p497, polypyrrole and its oligomers, polyaniline, polyphenylene and its oligomers, polyphenylene vinylene and its oligomers, polythiophenylene vinylene and its oligomers, polyacetylene, polydiacetylene, polysilane, polygermane and other σ-conjugated polymers.

[0380] In addition, as an oligomer material that is not a polymer material, oligomers such as α-sexithiophene, α,ω-dihexyl-α-sexithiophene, α,ω-dihexyl-α-sexithiophene, and α,ω-bis(3-butoxypropyl)-α-sexithiophene, which are thiophene hexamers, can be preferably used.

[0381] The n-type organic semiconductor compound is not particularly limited as long as it is an organic compound that has acceptor properties (electron accepting properties) for the p-type organic semiconductor compound, and any material that can be used in the art can be appropriately adopted.

[0382] As such a compound, any compound having a LUMO energy level deeper than 0.2 to 0.5 eV relative to that of a p-type organic semiconductor compound may be used, and examples thereof include fullerenes, carbon nanotubes, octaazaporphyrins, etc., perfluorinated bodies in which hydrogen atoms of the above-mentioned p-type organic semiconductor compounds are replaced with fluorine atoms (e.g., perfluoropentacene, perfluorophthalocyanine, etc.), polymer compounds containing aromatic carboxylic acid anhydrides such as naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic diimide, perylenetetracarboxylic anhydride, perylenetetracarboxylic diimide, and their imide products as skeletons, etc.

[0383] Among them, from the viewpoint of being able to carry out charge separation with p-type organic semiconductor compounds at high speed (~50fs) and high efficiency, fullerenes or carbon nanotubes or their derivatives are preferably used. More specifically, fullerene C60, fullerene C70, fullerene C76, fullerene C78, ​​fullerene C84, fullerene C240, fullerene C540, mixed fullerenes, fullerene nanotubes, multilayer carbon nanotubes, single-layer carbon nanotubes, carbon nanoprotrusions (conical type), etc., and fullerene derivatives substituted or unsubstituted with hydrogen atoms, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms) or with alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, silyl, ether group, thioether group, amino group, etc. can be listed.

[0384] In particular, it is preferable to use fullerene derivatives whose solubility is improved by substituents, such as [6,6]-phenyl C61-butyric acid methyl ester (abbreviated as PCBM), [6,6]-phenyl C61-butyric acid n-butyl ester (PCBnB), [6,6]-phenyl C61-butyric acid isobutyl ester (PCBiB), [6,6]-phenyl C61-butyric acid n-hexyl ester (PCBH), [6,6]-phenyl C71-butyric acid methyl ester (abbreviated as PC71BM), bis-PCBM described in Adv. Mater., vol. 20 (2008), p2116, amino fullerene described in Japanese Patent Application Publication No. 2006-199674, metallocene fullerene described in Japanese Patent Application Publication No. 2008-130889, and fullerene having a cyclic ether group described in U.S. Patent No. 7,329,709.

[0385] In addition, the p-type organic semiconductor compound and the n-type organic semiconductor compound may be used alone or in combination of two or more.

[0386] The bonding method of the p-type organic semiconductor compound and the n-type organic semiconductor compound in the photoelectric conversion layer is preferably a bulk heterojunction. In a bulk heterojunction, an ink containing a mixture of a p-type organic semiconductor compound and an n-type organic semiconductor compound is applied to form the bulk heterojunction, and in the obtained single region containing an organic semiconductor material, the domains of the p-type organic semiconductor compound and the domains of the n-type organic semiconductor compound present a microscopic phase separation structure.

[0387] The mixing ratio of the p-type organic semiconductor and the n-type organic semiconductor contained in the ink is preferably in the range of 2:8 to 8:2, and more preferably in the range of 3.3:6.7 to 5:5, expressed as a mass ratio.

[0388] [Organic semiconductor materials for organic TFTs]

[0389] As the organic semiconductor material used when the organic semiconductor device is an organic TFT, various condensed polycyclic aromatic compounds and conjugated compounds can be applied.

[0390] The organic semiconductor material preferably has an alkyl group from the viewpoint of solubility and affinity with the ink receiving layer. The alkyl group has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms.

[0391] Examples of the condensed polycyclic aromatic compound include anthracene, tetracene, pentacene, hexacene, heptacene, , fulminene, pyrene, anthracene, perylene, terylene, quaterylene, coronene, ovalbumen, circumanthracene, bisanthene, zeslene, heptazeslene, pyranthracene, biolanten, isobiolanten, circobiphenyl, phthalocyanine, porphyrin and other compounds and their derivatives.

[0392] Examples of the conjugated compound include polythiophene and oligomers thereof, polypyrrole and oligomers thereof, polyaniline, polyphenylene and oligomers thereof, polyphenylene vinylene and oligomers thereof, polythienylene vinylene and oligomers thereof, polyacetylene, polydiacetylene, tetrathiafulvalene compounds, quinone compounds, cyano compounds such as tetracyanoquinodimethane, fullerene and derivatives or mixtures thereof.

[0393] In particular, among polythiophenes and oligomers thereof, oligomers such as α-sexithiophene, α,ω-dihexyl-α-sexithiophene, α,ω-dihexyl-α-sexithiophene, and α,ω-bis(3-butoxypropyl)-α-sexithiophene, which are thiophene hexamers, can be preferably used.

[0394] Further, metal phthalocyanines such as copper phthalocyanine and fluorine-substituted copper phthalocyanine described in Japanese Patent Application Laid-Open No. 11-251601, naphthalene 1,4,5,8-tetracarboxylic acid diimide, N,N′-bis(4-trifluoromethylbenzyl)naphthalene 1,4,5,8-tetracarboxylic acid diimide, and N,N′-bis(1H,1H-perfluorooctyl), N,N′-bis(1H,1H-perfluorobutyl) and N,N′-dioctylnaphthalene 1,4,5,8-tetracarboxylic acid diimide derivatives, naphthalene tetracarboxylic acid diimides such as naphthalene 2,3,6,7-tetracarboxylic acid diimide, and anthracene tetracarboxylic acid diimides such as anthracene 2,3,6,7-tetracarboxylic acid diimide, and condensed ring tetracarboxylic acid diimides such as C 60 , C 70 , C 76 , C 78 , C 84 Fullerenes such as ethylenediamine, carbon nanotubes such as SWNT, pigments such as merocyanine pigments and hemicyanine pigments, etc.

[0395] Among these π-conjugated materials, at least one selected from condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, and metal phthalocyanines is preferred.

[0396] In addition, as other organic semiconductor materials, organic molecular complexes such as tetrathiafulvalene (TTF)-tetracyanoquinodimethane (TCNQ) complex, bis(ethylenetetrathiafulvalene) (BEDTTTF)-perchloric acid complex, BEDTTTF-iodine complex, TCNQ-iodine complex, etc. can also be used. Furthermore, σ-conjugated polymers such as polysilane and polygermane, and organic-inorganic hybrid materials described in Japanese Patent Application Laid-Open No. 2000-260999 can also be used.

[0397] (Solvent)

[0398] The solvent is not particularly limited as long as it can dissolve or disperse a desired amount of the organic semiconductor material and can discharge droplets from the nozzle of the head, and is preferably appropriately selected depending on the type of the organic semiconductor material and the like.

[0399] Specifically, there can be exemplified alcohols such as water, methanol, ethanol, propanol, isopropanol, butanol, hexanol, heptanol, octanol, decanol, cyclohexanol, and terpineol; hydrocarbon compounds such as n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, cymene, durene, indene, dipentene, tetralin, decalin, and cyclohexylbenzene; and ether compounds such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, and p-dioxane. compounds, glycol ether ester compounds such as ethylene glycol monomethyl ether acetate, glycol oligomer ether esters such as diethylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate, aliphatic or aromatic esters such as ethyl acetate, n-propyl acetate and propyl benzoate, dicarboxylic acid diesters such as diethyl carbonate, alkoxycarboxylates such as methyl 3-methoxypropionate and ethyl 3-ethoxypropionate, ketocarboxylates such as ethyl acetoacetate, and further polar compounds such as propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide and cyclohexanone.

[0400] The solvent is appropriately selected according to the types of the organic semiconductor material and the constituent material of the ink receiving layer, etc., taking into consideration the solubility or dispersibility in the organic semiconductor material and the above-mentioned SP value.

[0401] The state in which the region 5 containing the organic semiconductor material is formed by dropping the ink In onto the ink receiving layers 4A and 4B, that is, the state of the organic semiconductor layer, can be observed by the following method.

[0402] (Observation of ink retention status)

[0403] The state observation of the ink receiving layer can be carried out by using general analysis and analytical means used for observing organic thin films at the nanoscale.

[0404] (1) By performing elemental surface scanning using SEM (scanning electron microscope) or TEM (transmission electron microscope) on the cross section of the component for the organic semiconductor device, it is possible to visually observe how the region 5 containing the organic semiconductor material in the ink receiving layer is maintained, and in particular, whether the lower electrode, which is important in the present invention, is in contact with the organic semiconductor material in the ink.

[0405] (2) By performing time-of-flight secondary ion mass spectrometry (TOF-SIMS) in the thickness direction from a point position (the exposed portion D of the region 5 containing the organic semiconductor material), it is possible to visually observe how the ink in the region 5 containing the organic semiconductor material in the ink receiving layer is maintained, and in particular, whether the lower layer electrode, which is important in the present invention, is in contact with the organic semiconductor material in the ink.

[0406] (3) The conductive diamond-coated cantilever of the AFM is pressed against a point (exposed portion D of the region 5 containing the organic semiconductor material) and the presence or absence of electrode exposure can be confirmed by utilizing the flow of current when the current reaches the electrode of the lower layer.

[0407] [Method for manufacturing organic semiconductor device]

[0408] The method for producing an organic semiconductor device of the present invention is a method for producing an organic semiconductor device using the inkjet recording medium for an organic semiconductor device of the present invention, and is characterized by comprising the following steps.

[0409] (I) Step of dropping ink onto ink receiving layer

[0410] (II) After the step (I), a step of forming a film of the electrode 7 which forms a pair with the electrode 3 on the ink receiving layer

[0411] (I) Ink Dropping Process

[0412] The ink dropping step is a step of dropping ink containing an organic semiconductor material onto the ink receiving layer to make a part of the ink receiving layer a region containing the organic semiconductor material. Thus, for example, an organic semiconductor device member having the structure of the present invention is obtained.

[0413] In the ink dropping process, the method of dropping ink onto the ink receiving layer is an inkjet method. Figure 5 This is a cross-sectional view for explaining an ink dropping step in one example of the method for manufacturing an organic semiconductor device of the present invention. Figure 5 , a process of dropping ink In from the head 12 of the inkjet device 11 corresponding to the inkjet method onto the surface S of the ink receiving layer 4A of the inkjet recording medium 1 is shown.

[0414] In the inkjet method, small droplets of ink In can be formed, thereby forming a fine pattern, which is advantageous compared to other coating methods. In addition, the inkjet method is a non-contact printing method that causes little damage to the ink receiving layer, which is also advantageous in this regard.

[0415] In the ink dropping step of the manufacturing method of the present invention, the volume of the ink droplets during dropping also depends on the fineness of the dot pattern in accordance with the specifications of the organic semiconductor device, and is, for example, preferably 10 μL or less, and more preferably 100 pL or less.

[0416] In the manufacturing method of the present invention, a known inkjet device can be appropriately used as the inkjet device 11. For example, IJCS-1 manufactured by Konica Minolta Inc. can be used.

[0417] The head scanning speed is preferably a value that can set the dot pitch in the scanning direction to an appropriate value (50 to 500 μm), preferably 10 to 200 mm / sec, and more preferably 80 to 100 mm / sec.

[0418] There is no particular limitation on the head 12 that can be applied to the method for manufacturing an organic semiconductor device according to the present invention. For example, it can be a shear mode type (piezoelectric type) head having a vibration plate with a piezoelectric element in an ink pressure chamber, and ink is discharged due to pressure changes in the ink pressure chamber generated by the vibration plate; or a thermal type head having a heating element, and utilizing thermal energy from the heating element to discharge ink from a nozzle due to a rapid volume change caused by film boiling of the ink.

[0419] The head 12 is preferably of a specification capable of forming droplets of a picoliter level, and for example, KM512 and KM1024 manufactured by Konica Minolta Inc. can be used.

[0420] After the ink is dripped, before the counter electrode (II) is prepared, the solvent contained in the ink is removed as needed. The method for removing the solvent is, for example, heating treatment or decompression treatment. In the manufacturing method of the present invention, the treatment temperature is preferably maintained at room temperature (25°C) to 150°C and below atmospheric pressure for about 0.1 to 60 minutes to remove the solvent.

[0421] (II) Fabrication of Counter Electrode

[0422] The method for forming the counter electrode 7 on the ink receiving layer (organic semiconductor layer) of the organic semiconductor device member after the above step (I) is as described above.

[0423] (Structure of Organic Semiconductor Device)

[0424] Figure 6 A cross-sectional view showing an example of an organic semiconductor device obtained by the production method of the present invention. Figure 6 It specifically indicates the use of Figure 1 The inkjet recording medium 1 shown in FIG. Figure 2 and Figure 3 , and finally obtain an organic semiconductor device 100. The organic semiconductor device 100 is an organic semiconductor device manufactured with high precision in a simple process by the manufacturing method of the present invention described above.

[0425] In the organic semiconductor device 100 , even if the organic semiconductor device 10B is replaced with the organic semiconductor device member 10A, the organic semiconductor device can be manufactured with high precision by a simple process.

[0426] Figure 6The organic semiconductor device 100 shown in the figure is a structure in which a substrate 2, an electrode 3, an organic semiconductor layer 6 and a counter electrode 7 are stacked in this order. The organic semiconductor device according to the present invention may have other organic functional layers other than the organic semiconductor layer 6, such as an electron transport layer and a hole transport layer. In addition, for example, when the counter electrode 7 is a cathode, a hole blocking layer (also called a hole shielding layer) and an electron injection layer (also called a cathode buffer layer) may be provided between the organic semiconductor layer 6 and the counter electrode 7. Furthermore, when the counter electrode 7 is an anode, an electron blocking layer (also called an electron shielding layer) and a hole injection layer (also called an anode buffer layer) may be provided between the organic semiconductor layer 6 and the counter electrode 7.

[0427] The "electron transport layer" of the present invention is a layer having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. In addition, the electron transport layer may be composed of multiple layers.

[0428] The "hole transport layer" of the present invention is a layer having a function of transporting holes, and in a broad sense, the hole injection layer and the electron blocking layer are also included in the hole transport layer.

[0429] Examples of organic semiconductor devices to which the production method of the present invention is applied include organic EL elements, organic TFTs, and organic photoelectric conversion elements.

[0430] [Organic EL element]

[0431] In the organic EL element of the present invention, specifically, the organic semiconductor layer 6 is a light-emitting layer. The light-emitting layer in the organic EL element is a layer that provides a field for the electrons and holes injected from the electrode or the adjacent layer to recombine and emit light via excitons, and the light-emitting part may be within the light-emitting layer or at the boundary surface between the light-emitting layer and the adjacent layer.

[0432] There is no particular restriction on the thickness of the light-emitting layer. From the perspective of the homogeneity of the formed layer, preventing unnecessary high voltage from being applied during light emission, and improving the stability of the light-emitting color with respect to the driving current, it is preferably adjusted to a range of 3 nm to 5 μm, more preferably adjusted to a range of 2 to 500 nm, and further preferably adjusted to a range of 5 to 200 nm.

[0433] In the organic EL device, the light-emitting layer contains the light-emitting compound in an amount within a range of 1 to 80% by mass, and particularly preferably within a range of 5 to 40% by mass.

[0434] Next, other organic functional layers and the like in the organic EL layer will be described.

[0435] <Electron transport layer>

[0436] The electron transport layer is a layer composed of a material having a function of transporting electrons and having a function of transferring electrons injected from the cathode to the light-emitting layer.

[0437] The thickness of the electron transport layer is not particularly limited, but is usually in the range of 2 nm to 5 μm, more preferably in the range of 2 to 500 nm, and further preferably in the range of 5 to 200 nm.

[0438] The material used for the electron transport layer (hereinafter also referred to as “electron transport material”) may be any compound as long as it has either electron injecting or transporting properties or hole shielding properties, and any compound can be selected from conventionally known compounds.

[0439] Examples of conventionally known compounds include nitrogen-containing aromatic heterocyclic derivatives (carbazole derivatives, azacarbazole derivatives (products in which one or more carbon atoms constituting a carbazole ring are replaced by nitrogen atoms), pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyridazine derivatives, triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, azabenzo[9,10]phenanthrene derivatives, oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, etc.), dibenzofuran derivatives, dibenzothiophene derivatives, silole derivatives, aromatic hydrocarbon ring derivatives (naphthalene derivatives, anthracene derivatives, benzo[9,10]phenanthrene, etc.), and the like.

[0440] In addition, metal complexes having a quinolinol skeleton or a dibenzoquinolinol skeleton in the ligand, such as tris(8-hydroxyquinoline)aluminum (Alq3), tris(5,7-dichloro-8-hydroxyquinoline)aluminum, tris(5,7-dibromo-8-hydroxyquinoline)aluminum, tris(2-methyl-8-hydroxyquinoline)aluminum, tris(5-methyl-8-hydroxyquinoline)aluminum, bis(8-hydroxyquinoline)zinc (Znq), etc., and metal complexes in which the central metal of these metal complexes is replaced by In, Mg, Cu, Ca, Sn, Ga or Pb can also be used as electron transport materials.

[0441] In addition, products containing no metal or metal phthalocyanine, or whose ends are substituted by alkyl, sulfonic acid, etc., can also be preferably used as electron transport materials. In addition, distyryl pyrazine derivatives can also be used as electron transport materials, and inorganic semiconductors such as n-type-Si, n-type-SiC can also be used as electron transport materials, similarly to hole injection layers and hole transport layers.

[0442] In addition, it is also possible to use a polymer material in which these materials are introduced into a polymer chain or in which these materials are used as a main chain of a polymer.

[0443] In the electron transport layer to which the present invention relates, the doping material can be doped as a guest material in the electron transport layer to form an electron transport layer with high n-property (electron-rich). As doping materials, n-type dopants such as metal compounds such as metal complexes and metal halides can be listed. As a specific example of an electron transport layer of such a structure, for example, examples described in Japanese Patent Laid-Open No. 4-297076, Japanese Patent Laid-Open No. 10-270172, Japanese Patent Laid-Open No. 2000-196140, Japanese Patent Laid-Open No. 2001-102175, J.Appl.Phys., 95, 5773 (2004) and other documents can be listed.

[0444] Specific examples of known and preferred electron transport materials used in the organic EL device according to the present invention include compounds described in the following documents, but the present invention is not limited thereto.

[0445] U.S. Patent No. 6528187, U.S. Patent No. 7230107, U.S. Patent Publication No. 2005 / 0025993, U.S. Patent Publication No. 2004 / 0036077, U.S. Patent Publication No. 2009 / 0115316, U.S. Patent Publication No. 2009 / 0101870, U.S. Patent Publication No. 2009 / 0179554, International Publication No. 2003 / 060956, International Publication No. 2008 / 132085, Appl. Phys. Lett. 75, 4 (1999), Appl. Phys. Lett. 79, 449 (2001), Appl. Phys. Lett. 81, 162 (2002), Appl. Phys. Lett. 81, 162 (2002), Appl. Phys. Lett. 79, 156 (2001), U.S. Patent No. 7964293, U.S. Patent Publication No. 2009 / 030202, International Publication No. 2004 / 080975, International Publication No. 2004 / 063159, International Publication No. 2005 / 085387, International Publication No. 2006 / 067931, International Publication No. 2007 / 086552, International Publication No. 2008 / 114690, International Publication No. 2009 / 069442, International Publication No. 2009 / 066779, International Publication No. 2009 / 054253, International Publication No. 2011 / 086935, International Publication No. 2010 / 150593, International Publication No. 2010 / 047707, EP2311826 No. 2010-251675, No. 2009-209133, No. 2009-124114, No. 2008-277810, No. 2006-156445, No. 2005-340122, No. 2003-45662, No. 2003-31367, No. 2003-282270, International Publication No. 2012 / 115034, etc.

[0446] More preferred electron transport materials include pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives, and benzimidazole derivatives.

[0447] The electron transport material may be used alone or in combination of two or more.

[0448] <Hole blocking layer>

[0449] The so-called hole blocking layer, in a broad sense, is a layer having the function of an electron transport layer. It is preferably composed of a material that has the function of transporting electrons but has a low ability to transport holes. It is a layer that can increase the probability of recombination between electrons and holes by blocking holes while transporting electrons.

[0450] Furthermore, the above-mentioned structure of the electron transport layer can be used as a hole blocking layer as needed.

[0451] The hole blocking layer is preferably provided adjacent to the cathode side of the light emitting layer. The thickness of the hole blocking layer is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.

[0452] Among the materials used for the hole blocking layer, the materials used for the above-mentioned electron transporting layer are preferably used.

[0453] <Electron injection layer>

[0454] The so-called electron injection layer (also called "cathode buffer layer") refers to a layer provided between the cathode and the light-emitting layer in order to reduce the driving voltage and increase the luminous brightness. It is described in detail in Volume 2, Chapter 2 "Electrode Materials" (pages 123 to 166) of "Organic EL Elements and Their Industrialization Frontiers (published by Electrode Essence on November 30, 1998)".

[0455] The electron injection layer is provided as required, and may be present between the cathode and the light-emitting layer, or between the cathode and the electron transport layer as described above. The electron injection layer is preferably an extremely thin layer, and its thickness is preferably within the range of 0.1 to 5 nm, depending on the material. In addition, it may be an uneven layer in which the constituent material exists intermittently.

[0456] The electron injection layer is also described in detail in Japanese Patent Laid-Open No. 6-325871, Japanese Patent Laid-Open No. 9-17574, Japanese Patent Laid-Open No. 10-74586, etc., and as a specific example of the material preferably used for the electron injection layer, metals represented by strontium, aluminum, etc., alkali metal compounds represented by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkaline earth metal compounds represented by magnesium fluoride, calcium fluoride, etc., metal oxides represented by aluminum oxide, metal complexes represented by 8-hydroxyquinoline lithium (Liq), etc. can be listed. In addition, the above-mentioned electron transport material can also be used.

[0457] The above-mentioned materials used in the electron injection layer may be used alone or in combination of two or more.

[0458] <Hole transport layer>

[0459] The hole transport layer is a layer composed of a material having a function of transporting holes, and has a function of transporting holes injected from the anode to the light-emitting layer.

[0460] The thickness of the hole transport layer is not particularly limited, but is usually in the range of 5 nm to 5 μm, more preferably in the range of 2 to 500 nm, and further preferably in the range of 5 to 200 nm.

[0461] The material used for the hole transport layer (hereinafter referred to as "hole transport material") may be any compound as long as it has any one of hole injection or transport properties and electron shielding properties, and any compound may be selected from conventionally known compounds and used.

[0462] For example, porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyaryl alkane derivatives, triarylamine derivatives, carbazole derivatives, indolocarbazole derivatives, isoindole derivatives, anthracene, naphthalene and other benzoic derivatives, fluorene derivatives, fluorenone derivatives, and polyvinylcarbazole, polymer materials or oligomers having aromatic amines introduced into the main chain or side chain, polysilanes, conductive polymers or oligomers (such as PEDOT:PSS, aniline copolymers, polyaniline, polythiophene, etc.), etc. can be listed.

[0463] Examples of the triarylamine derivatives include benzidine-type derivatives represented by α-NPD, starburst-type derivatives represented by MTDATA, and compounds having fluorene or anthracene in a triarylamine linking core.

[0464] In addition, hexaazabenzo[9,10]phenanthrene derivatives described in JP-A-2003-519432 and JP-A-2006-135145 can also be used as hole transport materials in the same manner.

[0465] Furthermore, a hole transport layer with high p-type doped with impurities can also be used. Examples thereof include hole transport layers described in Japanese Patent Application Publication No. 4-297076, Japanese Patent Application Publication No. 2000-196140, Japanese Patent Application Publication No. 2001-102175, and J. Appl. Phys., 95, 5773 (2004).

[0466] In addition, inorganic compounds such as so-called p-type hole transport materials, p-type-Si, p-type-SiC, etc. described in Japanese Patent Publication No. 11-251067 and J. Huang et al. (Applied Physics Letters 80 (2002), page 139) can also be used. Furthermore, ortho-metallated organic metal complexes having Ir or Pt as the central metal, represented by Ir(ppy)3, are also preferably used.

[0467] As the hole transport material, the above-mentioned hole transport materials can be used, preferably triarylamine derivatives, carbazole derivatives, indolocarbazole derivatives, azabenzo[9,10]phenanthrene derivatives, organic metal complexes, polymer materials or oligomers having aromatic amines introduced into the main chain or side chain, etc.

[0468] Specific examples of known and preferred hole transport materials used in the organic EL device according to the present invention include compounds described in the following documents in addition to the documents listed above, but the present invention is not limited thereto.

[0469] For example, Appl.Phys.Lett.69,2160(1996), J.Lumin.72-74,985(1997), Appl.Phys.Lett.78,673(2001), Appl.Phys.Lett.90,183503(2007), Appl.Phy s.Lett.90,183503(2007), Appl.Phys.Lett.51,913(1987), Synth.Met.87,171(1997), Synth.Met.91,209(1997), Synth.Met.111,421(2000), SID Symposium Digest, 37, 923 (2006), J. Mater. Chem. 3, 319 (1993), Adv. Mater. 6, 677 (1994), Chem. Mater. 15, 3148 (2003), U.S. Patent Publication No. 2003 / 0162053, U.S. Patent Publication No. 2002 / 0158242, U.S. Patent Publication No. 2006 / 0240279, U.S. Patent Publication No. 2008 / 0220265, U.S. Patent No. 5061569, International Publication No. 2 007 / 002683, International Publication No. 2009 / 018009, EP650955, U.S. Patent Publication No. 2008 / 0124572, U.S. Patent Publication No. 2007 / 0278938, U.S. Patent Publication No. 2008 / 0106190, U.S. Patent Publication No. 2008 / 0018221, International Publication No. 2012 / 115034, Japanese Unexamined Patent Application Publication No. 2003-519432, Japanese Unexamined Patent Application Publication No. 2006-135145, U.S. Patent Application No. 13 / 585981, etc.

[0470] The hole transport material may be used alone or in combination of two or more.

[0471] <Electron blocking layer>

[0472] The so-called electron blocking layer, in a broad sense, is a layer having the function of a hole transport layer, and is preferably composed of a material having the function of transporting holes but a low ability to transport electrons, and is a layer that can increase the probability of recombination between electrons and holes by blocking electrons while transporting holes.

[0473] Furthermore, the above-mentioned structure of the hole transport layer can be used as an electron blocking layer as necessary.

[0474] The electron blocking layer is preferably provided adjacent to the anode side of the light emitting layer. The thickness of the electron blocking layer is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.

[0475] Among the materials used for the electron blocking layer, the materials used for the hole transporting layer described above are preferably used.

[0476] <Hole injection layer>

[0477] The so-called hole injection layer (also called "anode buffer layer") refers to a layer provided between the anode and the light-emitting layer in order to reduce the driving voltage and improve the luminous brightness. For example, it is described in detail in the second volume, chapter 2 "Electrode Materials" (pages 123 to 166) of "Organic EL Elements and Their Industrialization Frontiers (published by エヌ·ティー·エス Corporation on November 30, 1998)".

[0478] The hole injection layer is provided as required, and may exist between the anode and the light-emitting layer or between the anode and the hole transport layer as described above.

[0479] The hole injection layer is described in detail in Japanese Patent Application Laid-Open Nos. 9-45479, 9-260062, and 8-288069. Examples of materials used for the hole injection layer include the materials used for the hole transport layer described above.

[0480] Among them, preferred are phthalocyanine derivatives represented by copper phthalocyanine, hexaazabenzo[9,10]phenanthrene derivatives described in JP-A-2003-519432 and JP-A-2006-135145, metal oxides represented by vanadium oxide, amorphous carbon, polyaniline (emeraldine), conductive polymers such as polythiophene, ortho-metallated complexes represented by tris(2-phenylpyridine)iridium complexes, triarylamine derivatives, and the like.

[0481] The above-mentioned materials used for the hole injection layer may be used alone or in combination of two or more.

[0482] <Other additives>

[0483] The organic functional layer of the present invention may further contain other additives, such as halogen elements such as bromine, iodine and chlorine, halogenated compounds, alkali metals such as Pd, Ca, Na, alkaline earth metals, transition metal compounds, complexes, salts, etc.

[0484] The content of the additive can be determined arbitrarily, but is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 50 ppm or less, based on the total mass % of the layer contained.

[0485] However, the content may not be within this range for the purpose of improving the transportability of electrons and holes or facilitating the energy transfer of excitons.

[0486] There is no particular limitation on the method for forming the organic functional layer (e.g., hole injection layer, hole transport layer, hole blocking layer, electron transport layer, electron injection layer, etc.) other than the organic semiconductor layer, and a conventionally known method can be used. For example, the organic functional layer can be formed by a vacuum evaporation method, a wet method, or the like. For the wet method, the same method as the method for forming the ink receiving layer can be used.

[0487] When the organic functional layer is formed by a vapor deposition method, the vapor deposition conditions vary depending on the type of compound used, etc. Generally, it is preferred to heat the boat at a temperature of 50 to 450° C. and a vacuum degree of 10 -6 ~10 -2 Pa, a vapor deposition rate of 0.01 to 50 nm / sec, a substrate temperature of -50 to 300°C, and a thickness of 0.1 nm to 5 μm, preferably 5 to 200 nm are appropriately selected.

[0488] It should be noted that different formation methods may be applied to each organic functional layer.

[0489] When the organic EL element is applied to various purposes, it is sealed and used as described below. As a sealing means used in the sealing of the organic EL element, for example, a method of bonding a sealing member to a member on the outermost surface of the organic EL element, such as an electrode, a substrate, etc., with an adhesive can be cited. As a sealing member, it can be arranged in a manner to cover the display area of ​​the organic EL element, and can be a concave plate or a flat plate. In addition, there is no particular limitation on transparency and electrical insulation.

[0490] Specifically, glass plates, polymer plates, polymer films, metal plates, metal films, etc. can be cited. As the constituent glass of the glass plate, in particular, soda-lime glass, glass containing barium and strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, etc. can be cited. In addition, as the constituent resin of the polymer plate and the polymer film, polycarbonate resin, acrylic resin, polyester resin such as PET and PEN, polyether sulfide resin, polysulfone resin, etc. can be cited. As the metal plate and the metal film, a metal plate and a metal film composed of one or more metals or alloys selected from stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium and tantalum can be cited.

[0491] In the present invention, a polymer film or a metal film can be preferably used because the organic EL element can be made thinner. In addition, the polymer film preferably has an oxygen permeability of 1×10 -3 mL / m 2 / 24h or less, the water vapor permeability measured by the method according to JIS K7129-1992 (25±0.5℃, relative humidity (90±2)%) is 1×10 -3 g / (m 2 / 24h) or less polymer film.

[0492] When processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

[0493] As adhesives, specifically, light-curing and heat-curing adhesives having reactive vinyl groups such as (meth) acrylic oligomers, and moisture-curing adhesives such as 2-cyanoacrylates can be cited. In addition, heat- and chemical-curing (two-liquid mixing) adhesives such as epoxy adhesives can be cited. In addition, hot-melt polyamide adhesives, polyester adhesives, and polyolefin adhesives can be cited. In addition, cationic curing ultraviolet curing epoxy resin adhesives can be cited.

[0494] It should be noted that the organic EL element may be degraded by heat treatment, so an adhesive that can be bonded and cured from room temperature to 80° C. is preferred. In addition, a desiccant may be dispersed in the above adhesive. The adhesive may be applied to the sealing portion using a commercially available dispenser or by printing such as screen printing.

[0495] In addition, it is also preferred to sandwich an organic functional layer, coat the electrode and the organic functional layer on the outside of the electrode on the side opposite to the substrate, and form an inorganic and organic layer in contact with the substrate to form a sealing film. In this case, the material for forming the film can be any material that has the function of inhibiting the infiltration of substances such as moisture and oxygen that cause degradation of the element, for example, silicon oxide, silicon dioxide, silicon nitride, etc. can be used.

[0496] Furthermore, in order to improve the fragility of the film, it is preferred to have a laminated structure of these inorganic layers and layers composed of organic materials. There is no particular limitation on the method for forming these films, and for example, vacuum evaporation, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam method, ion plating method, plasma polymerization, atmospheric pressure plasma polymerization, plasma CVD method, laser CVD method, thermal CVD method, coating method, etc. can be used.

[0497] In the gap between the sealing member and the display area of ​​the organic EL element, if it is a gas phase and a liquid phase, it is preferred to inject an inert gas such as nitrogen, argon, a fluorinated hydrocarbon, an inert liquid such as silicone oil. In addition, it can also be made into a vacuum. In addition, a hygroscopic compound can also be enclosed inside.

[0498] Examples of hygroscopic compounds include metal oxides (e.g., sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide, etc.), sulfates (e.g., sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.), metal halides (e.g., calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.), perchloric acids (e.g., barium perchlorate, magnesium perchlorate, etc.), and the like. Among sulfates, metal halides and perchloric acids, anhydrous salts are preferably used.

[0499] As for the organic EL element, when it is applied to various purposes, it can be sealed as described above, and then, on the outside of the sealing film or sealing film on the side opposite to the substrate with the organic functional layer clamped, a protective film or protective plate for improving the mechanical strength of the element can be provided and used. In particular, when the sealing is performed by the above-mentioned sealing film, its mechanical strength may not be high, so it is preferred to provide such a protective film or protective plate. As a material that can be used here, a glass plate, a polymer plate, a polymer film, a metal plate, a metal film, etc., which are the same as the material used for the above-mentioned sealing, can be used. Considering light weight and thin filmization, it is preferred to use a polymer film.

[0500] <Light extraction enhancement technology>

[0501] In the case of organic EL elements, light is emitted from inside a layer having a higher refractive index than air (within the range of about 1.6 to 2.1 refractive index), and generally only about 15 to 20% of the light generated in the light-emitting layer is extracted. This is because light that enters the interface (the interface between the transparent substrate and the air) at an angle θ above the critical angle is totally reflected and cannot be extracted to the outside of the element; light is totally reflected between the transparent electrode or the light-emitting layer and the transparent substrate, and the light is waveguided in the transparent electrode or the light-emitting layer, and as a result, the light escapes in the side direction of the element.

[0502] As a method for improving the light extraction efficiency, for example, there can be listed a method of forming projections and depressions on the surface of a transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (for example, U.S. Patent No. 4,774,435); a method of improving efficiency by making the substrate have light-collecting properties (for example, Japanese Patent Publication No. 63-314795); a method of forming a reflective surface on the side surface of an element (for example, Japanese Patent Publication No. 1-220394); a method of introducing a flat layer with an intermediate refractive index between the substrate and the light-emitting body to form an anti-reflection film (for example, Japanese Patent Publication No. 62-172691); a method of introducing a flat layer with a refractive index lower than that of the substrate between the substrate and the light-emitting body (for example, Japanese Patent Publication No. 2001-202827); a method of forming a diffraction grating between any of the substrate, the transparent electrode layer, and the light-emitting layer (including between the substrate and the outside world) (Japanese Patent Publication No. 11-283751), etc.

[0503] The method of introducing a diffraction grating at an interface causing total reflection or in any medium has the characteristic of having a high effect of improving the light extraction efficiency. This method uses the property of the diffraction grating to change the direction of light to a specific direction different from refraction, such as the so-called Bragg diffraction of the first-order diffraction and the second-order diffraction. Among the light generated by the light-emitting layer, the light that cannot be taken out by total reflection between layers, etc., is diffracted by introducing a diffraction grating between any layers or in the medium (inside the transparent substrate, in the transparent electrode), and the light is extracted to the outside.

[0504] The introduced diffraction grating preferably has a two-dimensional periodic refractive index. This is because the light emitted from the light-emitting layer is randomly generated in all directions. Therefore, for a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only the light advancing in a specific direction is diffracted, and the light extraction efficiency is not increased that much. However, by making the refractive index distribution a two-dimensional distribution, the light advancing in all directions is diffracted, and the light extraction efficiency is improved.

[0505] The position where the diffraction grating is introduced can be between any layers or in the medium (inside the transparent substrate, in the transparent electrode), but it is preferably near the organic light-emitting layer where the light is generated. In this case, the period of the diffraction grating is preferably within the range of about 1 / 2 to 3 times the wavelength of the light in the medium. The arrangement of the diffraction grating is preferably repeated in two dimensions in a square lattice, a triangular lattice, a honeycomb lattice, or the like.

[0506] <Light collecting sheet>

[0507] With regard to the organic EL element involved in the present invention, by processing the light extraction side of the substrate so as to provide a structure such as a microlens array, or by combining it with a so-called light collecting sheet, light can be collected in a specific direction, such as the front direction relative to the light emitting surface of the element, thereby improving the brightness in the specific direction.

[0508] As an example of a microlens array, a quadrangular pyramid with a side of 30 μm and a vertex angle of 90 degrees is arranged two-dimensionally on the light extraction side of the substrate. One side is preferably within the range of 10 to 100 μm. If it is smaller than this, diffraction effect is generated and coloring occurs. If it is too large, the thickness becomes thick and is not preferred.

[0509] As the light collecting sheet, for example, a light collecting sheet that has been put into practical use in the LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo Thread Co., Ltd. can be used. As the shape of the prism sheet, for example, it can be a shape of a △-shaped strip with a vertex angle of 90 degrees and a pitch of 50 μm formed on a substrate, or a shape with rounded vertex angles, a shape with randomly changing pitches, or other shapes.

[0510] In order to control the light radiation angle from the organic EL element, a light diffusion plate or film may be used together with a light collecting sheet. For example, a diffusion film (LIGHT UP) manufactured by Kimoto Co., Ltd. may be used.

[0511] (use)

[0512] The organic semiconductor device of the present invention, for example, an organic EL element, can be preferably used in a display device that displays high-quality color images. In addition, the organic EL element of the present invention can also be preferably used in lighting devices such as home lighting and in-car lighting.

[0513] As for the organic EL element involved in the present invention, in addition to the above, it can also be used as other light sources, for example, it can be used in clocks, liquid crystal backlights, signboards, traffic lights, light sources for optical storage media, light sources for electronic photographic copiers, light sources for optical communication processors, light sources for optical sensors, etc.

[0514] The organic semiconductor device of the present invention, for example, an organic photoelectric conversion element, can be preferably used for an organic thin-film solar cell. In addition, the organic photoelectric conversion element can be used as a photosensor array in which the organic photoelectric conversion elements are arranged in an array. That is, the organic photoelectric conversion element of this embodiment can also be used as a photosensor array that converts an image projected on the photosensor array into an electrical signal by utilizing its photoelectric conversion function.

[0515] Example

[0516] The present invention is specifically described below with reference to the following examples, but the present invention is not limited to these examples. It should be noted that the expression "parts" or "%" used in the examples represents "parts by mass" or "mass %" unless otherwise specified.

[0517] [Inkjet recording medium for organic semiconductor devices]

[0518] An inkjet recording medium for an organic semiconductor device of each example was produced using a polyethylene film substrate having an ITO film of 100 nm as an electrode (anode) which was ultrasonically cleaned with isopropyl alcohol, dried in dry nitrogen, and cleaned with UV ozone (hereinafter referred to as "ITO-attached substrate 1").

[0519] (Inkjet recording medium for organic semiconductor device 1-1)

[0520] On the ITO of the ITO-attached substrate 1, a 1.0% n-propyl acetate solution of polystyrene (manufactured by ACROS ORGANICS, with a weight average molecular weight of 260,000, represented by "PS1" in Table I. The same applies hereinafter) is formed into a film by spin coating at 500 rpm for 30 seconds, and then dried at 120°C for 30 minutes to produce an inkjet recording medium 1-1 for an organic semiconductor device having a polystyrene ink receiving layer with a thickness of 50 nm.

[0521] (Inkjet recording medium for organic semiconductor device 2-1)

[0522] An ink receiving layer composed of the following two layers (an ink-insoluble layer and an ink-permeable layer) was formed on the ITO of the ITO-attached substrate 1 to prepare an inkjet recording medium 2-1 for an organic semiconductor device.

[0523] A 1.0% chlorobenzene solution of POLY-TPD [N, N'-bis(4-butylphenyl)-N, N'-bis(phenyl)-benzidine] (manufactured by Fuji Film Co., Ltd. Wako Pure Chemical Industries, Ltd.; LT-N149, weight average molecular weight 45,000, indicated as "PTPD" in Table I) was formed into a coating film by spin coating at 500 rpm for 30 seconds. The coating film was formed by forming the coating film for the ink permeable layer below, and then dried together with the coating film for the ink permeable layer under the following conditions to form a POLY-TPD layer (ink insoluble layer) with a layer thickness of 50 nm.

[0524] A 1.0% n-propyl acetate solution of polystyrene (manufactured by Acros Organics, weight average molecular weight 260,000) was spin-coated at 500 rpm for 30 seconds and then dried at 120°C for 30 minutes to form a polystyrene layer (ink permeable layer) with a thickness of 50 nm.

[0525] (Inkjet recording medium for organic semiconductor device 2-2)

[0526] An ink receiving layer composed of the following two layers (an ink-insoluble layer and an ink-permeable layer) was formed on the ITO of the ITO-attached substrate 1 to prepare an inkjet recording medium 2-2 for an organic semiconductor device.

[0527] A 0.5% chlorobenzene solution of high molecular weight polystyrene (manufactured by Aldrich, weight average molecular weight 400,000, indicated as "PS2" in Table 1, the same below) was spin-coated at 100 rpm for 30 seconds to form a coating film. The coating film was formed by drying the coating film for the ink permeable layer together with the coating film for the ink permeable layer under the following conditions to form a high molecular weight polystyrene layer with a thickness of 30 nm.

[0528] A 1.0% n-propyl acetate solution of polystyrene (manufactured by Acros Organics, weight average molecular weight 260,000) was spin-coated at 500 rpm for 30 seconds and then dried at 120°C for 30 minutes to form a polystyrene layer (ink permeable layer) with a thickness of 50 nm.

[0529] (Inkjet recording medium for organic semiconductor device 2-3)

[0530] An ink receiving layer composed of the following two layers (an ink-insoluble layer and an ink-permeable layer) was formed on the ITO of the ITO-attached substrate 1 to produce an inkjet recording medium 2-3 for an organic semiconductor device.

[0531] In a 1.0% n-propyl acetate solution of polystyrene (manufactured by Acros Organics, weight average molecular weight 260000), 50 μL of ethyl 2-cyanoacrylate (manufactured by Aldrich) was added to 1000 μL of the n-propyl acetate solution, and then a coating film was formed by spin coating at 1000 rpm for 30 seconds. The coating film was formed by drying the coating film for the ink permeable layer together with the coating film for the ink permeable layer under the following conditions to form a polystyrene (represented by "IPN-PS" in Table 1) layer having an IPN (interpenetrating polymer network) structure with a thickness of 30 nm.

[0532] A 1.0% n-propyl acetate solution of polystyrene (manufactured by Acros Organics, weight average molecular weight 260,000) was spin-coated at 500 rpm for 30 seconds and then dried at 120° C. for 30 minutes to form a polystyrene layer with a thickness of 50 nm.

[0533] (Inkjet recording medium for organic semiconductor device 2-4)

[0534] An ink receiving layer composed of the following two layers (an ink-insoluble layer and an ink-permeable layer) was formed on the ITO of the ITO-attached substrate 1 to produce an inkjet recording medium 2-4 for an organic semiconductor device.

[0535] A 0.5% chlorobenzene solution of high molecular weight polystyrene (manufactured by Aldrich, weight average molecular weight 400000) was spin coated at 100 rpm for 30 seconds to form a coating film. The coating film was formed by forming the following coating film for the ink permeable layer and then drying it together with the coating film for the ink permeable layer under the following conditions to form a high molecular weight polystyrene layer with a thickness of 30 nm.

[0536] A 0.7% n-propyl acetate solution of poly(bisphenol A carbonate) (manufactured by Aldrich, weight average molecular weight 45,000, represented by "PC" in Table I) was formed into a film by spin coating at 500 rpm for 30 seconds, and then dried at 120°C for 30 minutes to form a poly(bisphenol A carbonate) layer with a thickness of 50 nm.

[0537] <Observation of the state of ink receiving layer>

[0538] The SEM observation of the thin film cross section of the inkjet recording medium 1-1 for an organic semiconductor device of the present invention was performed, and as a result, a single layer (thickness 50 nm) of organic thin film was observed as designed. Similarly, the measurement was also performed on the inkjet recording media 2-1 to 2-4 for organic semiconductor devices, and as a result, it was confirmed that each of them had an organic layer composed of two layers (ink insoluble layer and ink permeable layer) as designed. The composition of the ink receiving layer of the obtained inkjet recording medium for an organic semiconductor device is shown in Table I.

[0539]

[0540] [Members for organic semiconductor devices]

[0541] An organic semiconductor device member was prepared using the inkjet recording medium for an organic semiconductor device obtained above and the inkjet recording medium 1-2 for an organic semiconductor device produced as described below.

[0542] (Manufacture of Inkjet Recording Medium 1-2 for Organic Semiconductor Device)

[0543] On the ITO of the ITO-attached substrate 1, a 1.5% n-propyl acetate solution of polystyrene (manufactured by ACROS ORGANICS, with a weight-average molecular weight of 260,000) was formed into a film by spin coating at 500 rpm for 30 seconds, and then dried at 120°C for 30 minutes to produce an inkjet recording medium 1-2 for an organic semiconductor device having a polystyrene ink receiving layer with a thickness of 80 nm.

[0544] (Manufacturing of organic semiconductor device member)

[0545] On the ink receiving layer of the inkjet recording medium 1-1 for an organic semiconductor device manufactured as described above, the ink 1 manufactured as described below was dropped by the following inkjet method to prepare an inkjet recording medium for an organic semiconductor device. Figure 2 The organic semiconductor device member 1-1 having dot regions was formed in the pattern shown in FIG. Ink dropping was performed without leaving any time after the production of the inkjet recording medium 1-1 for an organic semiconductor device.

[0546] Organic semiconductor device members 1-2, 2-1 to 2-4 were produced by using the organic semiconductor device inkjet recording media 1-2 and 2-1 to 2-4 instead of the organic semiconductor device inkjet recording medium 1-1.

[0547] (Manufacturing of Ink 1)

[0548] Using n-propyl acetate as a solvent, tris[2-(p-tolyl)pyridine]iridium(III) (Ir(mppy)3; emitting green light) as a luminescent compound was mixed with the solvent at a concentration of 1 mass %, and ultrasonically heated while being maintained at 90°C for 30 minutes, and then filtered with a 0.2 μm filter to remove the agglomerated components to prepare ink 1. The viscosity of ink 1 was 0.6 mPa·s. The SP value of Ir(mppy)3 was 20.3 (J / cm 3 ) 1 / 2 The SP value of n-propyl acetate as a solvent, SP(S) is 18.0 (J / cm 3 ) 1 / 2 Therefore, the SP value of ink 1, SP(I), is 18.0 (J / cm 3 ) 1 / 2 .

[0549] (Conditions of inkjet method)

[0550] Inkjet device: IJCS-1 manufactured by Konica Minolta

[0551] Inkjet head: Konica Minolta KM512

[0552] Number of injections: 2 injections

[0553] Distance between discharge nozzles of the head: 140μm pitch

[0554] Head scanning speed: 90mm / sec

[0555] <Evaluation; Observation of ink holding state of ink receiving layer>

[0556] For each of the organic semiconductor device members obtained above, the ink discharge to the ink receiving layer and the ink retention state were examined.

[0557] The elemental scanning of the cross section of the thin film at the dotted part of the organic semiconductor device member 1-1 using SEM (scanning electron microscope) revealed that the Ir element contained in the luminescent compound was in contact with the In element, which was a component from the electrode. In addition, in the conductivity measurement using the (2) TOF-SIMS method and (3) AFM conductive diamond coated cantilever described in (Observation of the ink retention state), the results showing that the ink component was in contact with the lower electrode were also obtained.

[0558] For the organic semiconductor device members 1-2, 2-1 to 2-4, elemental scanning using SEM was performed, and it was observed that the Ir element contained in the luminescent compound was not in contact with the In element, which is a component derived from the electrode. In addition, even when the TOF-SIMS method was used in the same manner, the presence of an organic layer was observed between the ink component and the component derived from the electrode, which supported the results of the elemental scanning.

[0559] The results are shown in Table II together with the composition of the ink receiving layer of the member for an organic semiconductor device. In Table II, |SP(M1)-SP(I)| (expressed as "SP value difference 1" in Table II) and |SP(M2)-SP(I)| (expressed as "SP value difference 2" in Table II) are shown together with the penetration depth of the ink (thickness Th of the region 5 containing the organic semiconductor material).

[0560]

[0561] [Manufacturing of organic semiconductor devices (organic EL elements)]

[0562] Using the organic semiconductor device member 2-2 obtained above, an organic EL element 2-2 was produced as follows.

[0563] After the organic semiconductor device member 2-2 was manufactured, it was immediately installed in a vacuum deposition apparatus and the vacuum chamber was depressurized to 4×10 -4 After Pa, an electron injection layer and an electrode (cathode) were formed under the following conditions. For the electron injection layer, potassium fluoride was added at a film forming rate of The electrode was deposited at a film forming rate of 2.0 nm. The organic EL element 2-2 was produced by the above steps. Similarly, the organic semiconductor device components 1-1, 1-2, 2-1, 2-3 and 2-4 obtained above were used to produce organic EL elements 1-1, 1-2, 2-1, 2-3 and 2-4.

[0564] <Evaluation: Repeated stability of organic EL elements>

[0565] The obtained organic EL elements 1-1, 1-2, and 2-1 to 2-4 were sealed as follows to prepare light-emitting elements for evaluation, and the repeated stability of light emission of the organic EL elements was evaluated as follows.

[0566] (Fabrication of Light Emitting Element for Evaluation)

[0567] As a sealing member for the entire organic EL element, a gas barrier film was prepared as follows. That is, a SiO2 film was formed on the entire surface of a polyethylene naphthalate film (produced by Teijin Film Solutions Co., Ltd.) using an atmospheric pressure plasma discharge treatment apparatus having a structure described in Japanese Patent Application Publication No. 2004-68143. x The inorganic gas barrier layer was formed so that the layer thickness was 500 nm. Thus, a film having an oxygen permeability of 0.001 mL / (m 2 ·24h) or less, water vapor permeability 0.001g / (m 2 · A flexible gas barrier film having gas barrier properties for a period of less than 24 hours.

[0568] Secondly, a thermosetting liquid adhesive (epoxy resin) layer with a thickness of 25 μm is formed on one side of the gas barrier film as a sealing resin layer. Then, the gas barrier film provided with the sealing resin layer is overlapped with the organic EL element 2-2. At this time, the sealing resin layer forming surface of the gas barrier film is continuously overlapped with the sealing surface side of the organic EL element 2-2 in such a way that the ends of the take-out parts of the anode and the cathode are facing the outside. Secondly, the sample with the gas barrier film affixed is arranged in a decompression device, and extrusion is applied under a reduced pressure condition of 0.1 MPa at 90°C for 5 minutes. Next, the sample is returned to the atmospheric pressure environment, and then heated at 90°C for 30 minutes to cure the adhesive, thereby obtaining a light-emitting element for evaluation.

[0569] To the produced light-emitting element for evaluation, a current of 2.5 mA / cm was applied at a temperature of 23°C. 2 The constant current was applied for 5 seconds to make it emit light, and then stopped for 10 seconds to make it extinguish. The emission and extinguishing were regarded as one cycle, and the situation of emission after 10 cycles was recorded as "○", and the situation of no emission was recorded as "×". The results are shown in Table III.

[0570]

Table 3

[0571] Table III

[0572]

[0573] The above results show that the organic semiconductor material (luminescent compound) contained in the ink is in contact with the electrode (anode) located in the lower layer, causing disorder (defect) in the contact part, and the leakage current passing therethrough causes poor light emission of the device (organic EL element). Since it has a close influence on the initial poor light emission of about 10 cycles, the organic semiconductor device process and the practical use of the organic semiconductor device described in the present invention, which are accompanied by the ink droplet landing on the ink receiving layer, are effective.

[0574] [Manufacturing of inkjet recording medium for organic semiconductor device with release film]

[0575] A polyethylene naphthalate film (thickness: 25 μm, manufactured by Teijin Flexure Co., Ltd.) was superimposed on the ink receiving layer of the inkjet recording medium 2-1 for an organic semiconductor device produced in the same manner as above. Next, the inkjet recording medium 2-1P for an organic semiconductor device with a release film was produced by placing it in a decompression device and applying pressure under a decompression condition of 0.1 MPa at 50° C. for 5 minutes. The decompression condition was maintained to produce an inkjet recording medium 2-1P for an organic semiconductor device with a release film. Production: Inkjet recording media 1-1P, 1-2P, 2-2P and 2-3P for an organic semiconductor device with a release film were produced in the same manner as the inkjet recording media 1-1, 1-2, 2-2 and 2-3 for an organic semiconductor device.

[0576] [Manufacturing of an organic semiconductor device (organic EL element) using an inkjet recording medium for an organic semiconductor device with a release film]

[0577] The prepared inkjet recording media 1-1P, 1-2P and 2-1P to 2-3P for organic semiconductor devices with release films were stored in an automatic dryer (manufactured by Aswan Co., Ltd., humidity 10%) at 25°C for 14 days, and then organic semiconductor devices were prepared.

[0578] In the manufacture of the device, after the release film on the outermost surface of the inkjet recording medium for the organic semiconductor device with a release film is peeled off, the ink 1 is dropped onto the ink receiving layer by the inkjet method in exactly the same manner as in the manufacture of the organic EL element 2-2, to manufacture the device. Figure 2 The ink holder having the dot region formed in the pattern shown in the figure was mounted on a vacuum deposition device to form an electron injection layer and an electrode (cathode), thereby manufacturing organic EL elements 1-1P, 1-2P, and 2-1P to 2-3P.

[0579] The organic semiconductor device inkjet recording medium 2-1 prepared above was stored in an automatic dryer (manufactured by Aswan Corporation, humidity 10%) at 25°C for 14 days, and then an organic EL element 2-1H prepared in exactly the same manner as above was prepared.

[0580] <Evaluation>

[0581] The organic semiconductor device (organic EL element) using the inkjet recording medium for an organic semiconductor device with a release film, the organic EL element 2-1H, and the organic EL elements 1-1, 1-2, and 2-1 to 2-3 were subjected to a sealing step using a gas barrier film as described above to prepare light-emitting elements for evaluation, and the following evaluation was performed. The results are shown in Table IV.

[0582] (Repeated stability)

[0583] To the organic EL element fabricated, 2.5 mA / cm was applied at 23°C. 2 After applying a constant current of 500 nm for 5 seconds to make it emit light, the application was stopped for 10 seconds to make it extinguish. The emission and extinguishing were regarded as one cycle, and the situation of emitting light after 10 cycles was recorded as "○", and the situation of no longer emitting light was recorded as "×".

[0584] (Luminous intensity)

[0585] The measurement was performed at 23°C with an applied current of 2.5 mA / cm 2 The luminous intensity is shown as a relative value when the intensity of the organic EL element 2-1 is set to 100. The luminous intensity is measured using a spectroradiometer CS-2000 (manufactured by Konica Minolta).

[0586]

Table 4

[0587] Table IV

[0588]

[0589] As for the above results, for organic EL elements 1-1 and 1-1P, the main cause was the effect of contact with the electrode (anode) located in the lower layer, and no improvement was found in the repeated stability by the release film. In addition, the luminous intensity was reduced compared with the organic EL element 2-1 due to the extinction effect on the electrode, and the driving stability of 1-1P with a release film was poor and could not be measured.

[0590] On the other hand, for the organic EL element of the present invention, the extinction effect on the electrode can be suppressed, and the driving stability of the device is improved, and the significant effect is obvious. In particular, the organic EL element 2-1 and the organic EL element 2-1H are compared, and it can be seen that they show substantially the same luminous intensity. This result means that in the organic semiconductor process that has been continuously manufactured from the cleaning of the substrate to the sealing, it can be separated into two processes: the preparation of the inkjet recording medium for organic semiconductor devices and the preparation of organic semiconductor devices, and it is obvious that the inkjet recording medium for organic semiconductor devices can be preserved. It can be seen from this that it is a device and device manufacturing process that is strongly resistant to the external environment. The advantages of the inkjet recording medium for organic semiconductor devices of the present invention and the manufacturing process using it are obvious.

[0591] In addition, when the organic EL element 2-1P provided with a release film is compared with the organic EL element 2-1 or the organic EL element 2-1H, it is found that the luminous intensity is improved. This tendency is also found in the organic EL element 2-2P and the organic EL element 2-3P provided with a release film. Therefore, it is speculated that it not only has the function of a general protective film, that is, blocking external physical influences (for example, protecting from damage such as scratches, protecting from oxygen and water), but also has the effect of inhibiting the promotion of phase separation caused by the formation of an interface between gas (air or nitrogen, etc.) and organic thin film (solid).

[0592] [Manufacturing of organic semiconductor devices (organic photodiodes (photodetectors))]

[0593] In the manufacture of each of the above-mentioned organic EL elements, an organic photodiode 2-1 was produced in the same manner except that the luminescent compound of ink 1 was changed to a 1:1 (mass ratio) mixture of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) using ink 2. In addition, an organic photodiode 2-2 was produced in the same manner except that the inkjet recording medium 2-1 for the organic semiconductor device was changed to 2-2. It should be noted that the viscosity of ink 2 is 0.8 mPa·s. The SP value of the above-mentioned mixture is 16.8 (J / cm 3 ) 1 / 2 The SP value of n-propyl acetate as a solvent, SP(S) is 18.0 (J / cm 3 ) 1 / 2 Therefore, the SP value of ink 2, SP(I), is 18.0 (J / cm 3 ) 1 / 2 .

[0594] The prepared organic photodiodes 2-1 and 2-2 were irradiated with a xenon lamp from the transparent electrode (ITO electrode) side, and the irradiation brightness and the current between the electrodes were measured. As a result, an increase in the current was observed as the irradiation intensity was changed from 100 mW to 1000 mW, confirming that the prepared elements functioned as photodiodes.

[0595] [Manufacturing of organic semiconductor devices (electrochemical sensors)]

[0596] Using the organic semiconductor device member 2-2 obtained above, an electrochemical sensor 1 was produced as follows.

[0597] After the organic semiconductor device member 2-2 was manufactured, it was immediately installed in a vacuum deposition apparatus and the vacuum chamber was depressurized to 4×10 -4 After 1.5 Å, an electron injection layer and an electrode were formed under the following conditions. For the electron injection layer, potassium fluoride was added at a film forming rate of For the electrode, Al was deposited at a film forming rate of 100 nm. The layer was formed by second vapor deposition to a thickness of 50 nm, thereby producing an electrochemical sensor 1 .

[0598] <Evaluation>

[0599] The applied current is 2.5 mA / cm2 at 23°C. 2 The luminous intensity at a constant current of 1.5 0.5 0.6 0.8 0.9 0.1 0.2 0.4 0.6 0.7 0.8 0.9 0.9 0.1 0.3 0.6 0.7 0.8 0.9 0.9 0.1 0.6 0.7 0.8 ...8 0.9 0.1 0.6 0.8 0.9 0.1 0.6 0.8 0.9 0.1 0.6 0.8 0.9 0.1 0.6 0.8 0.9 0.1 0.6 0.8 0.9 0.1 0.6 0.8 0.9 0.1 0.6 0.8 0.9 0.1 0.6 0.8 0.9 0.1 0.6

[0600] [Manufacturing of organic semiconductor devices (electrochemical sensors 2)]

[0601] The organic semiconductor device inkjet recording medium 2-2 was prepared in the same manner as described above. The following ink 3 was dropped onto the ink receiving layer of the organic semiconductor device inkjet recording medium 2-2 using the following inkjet method to form a Figure 2 The pattern shown in forms a dot area.

[0602] (Manufacturing of Ink 3)

[0603] Using n-propyl acetate as a solvent, poly(3-hexylthiophene-2,5-diyl) (manufactured by TCI, weight average molecular weight 45,000, high positional regularity (>99%)) was mixed with the solvent at a concentration of 1 mass %, and ultrasonically heated at 90° C. for 30 minutes, and then filtered with a 0.2 μm filter to remove the agglomerated components to prepare Ink 3. It should be noted that the viscosity of Ink 3 was 0.7 mPas. The SP value of poly(3-hexylthiophene-2,5-diyl) was 16.8 (J / cm 3 ) 1 / 2 The SP value of n-propyl acetate as a solvent, SP(S) is 18.0 (J / cm 3 ) 1 / 2 Therefore, the SP value of ink 3, SP(I), is 18.0 (J / cm 3 )1 / 2

[0604] (Conditions of inkjet method)

[0605] Inkjet device: IJCS-1 manufactured by Konica Minolta

[0606] Inkjet head: Konica Minolta KM512

[0607] Number of injections: 2 injections

[0608] Distance between discharge nozzles of the head: 140μm pitch

[0609] Head scanning speed: 90mm / sec

[0610] Next, install it in a vacuum deposition device and reduce the vacuum tank pressure to 4×10 -4 After 100 Pa, an electron injection layer and an electrode (cathode) were formed under the following conditions. For the electron injection layer, potassium fluoride was added at a film forming rate of For the electrode, A1 was deposited at a film forming rate of The layer was formed by second vapor deposition to a thickness of 50 nm, thereby producing an electrochemical sensor 2 .

[0611] <Evaluation>

[0612] At 23°C, the measurement was performed with 2.5 mA / c m 2. In the measurement, dry air was sprayed at a flow rate of 0.1 L / min on the Al (cathode) surface of the electrochemical sensor 2 using a spectroradiometer CCS-2000 (manufactured by Konica Minolta). As a result, when the initial brightness was set to 100, it decreased with the passage of time of the dry air discharge, and it was observed that the relative brightness decreased to 60 after 30 minutes. The results confirmed that the electrochemical sensor 2 functions as an electrochemical sensor for oxygen.

[0613] [Manufacturing of organic semiconductor devices (white)]

[0614] Ink 1 used in the manufacture of the above-mentioned organic EL elements and Ink 4 (red) and Ink 5 (cyan) were prepared by replacing the luminescent compound (Ir(mppy)3; emitting green light) in Ink 1 with Ir(phq)3 (tris(2-phenylquinoline)iridium(III); emitting red light) and (Ir(mpim)3 (tris(mesitylene-2-phenyl-1H-imidazole)iridium(III); emitting cyan light). The viscosity and SP value of Ink 4 and 5 were the same as those of Ink 1.

[0615] The above-mentioned ink 1 (green), ink 4 (red), and ink (cyan) are mixed in Figure 2 The white organic EL element 2-1W is manufactured in the same manner as the above-mentioned organic EL element 2-1 except that all the dots in the 1st and 4th rows become ink 4 (red), all the dots in the 2nd and 5th rows become ink 1 (green), and all the dots in the 3rd and 6th rows become ink (cyan).

[0616] <Evaluation>

[0617] The white organic EL element 2-1W was sealed in the same manner as above, and a current of 2.5 mA / cm was applied at a temperature of 23°C. 2 1. Apply a constant current and confirm white light emission.

[0618] [Manufacturing of organic semiconductor devices (displays)]

[0619] Ink 1 (green), ink 4 (red), and ink (cyan) are prepared in the same manner as described above. Ink 1 (green), ink 4 (red), and ink (cyan) are dropped onto the ink receiving layer of the inkjet recording medium 2-1 for an organic semiconductor device by an inkjet method in a predetermined pattern (the ratio of the number of dots of green: red: cyan is 1:1:2). Next, wiring and electrodes are formed according to the design of an active matrix full-color display device to obtain an organic EL element 2-1D.

[0620] The organic EL element 2-1D has a wiring section including a plurality of scanning lines and data lines, and a plurality of juxtaposed pixels (pixels (dots) in the red region, pixels (dots) in the green region, and pixels (dots) in the cyan region) on the same substrate. The scanning lines and the plurality of data lines in the wiring section are each made of a conductive material, and the scanning lines and the data lines are orthogonal to each other in a grid shape, and are connected to the pixels (dots) at the positions where they are orthogonal. The organic EL element 2-1D is used to combine other components to produce an active matrix full-color display device.

[0621] Each pixel (dot) on the organic EL element 2-1D is driven in an active matrix manner by a switching transistor and a driving transistor as active elements. If a scanning signal is applied from a scanning line, an image data signal is received from a data line, and light is emitted according to the received image data.

[0622] It was found that by driving an active matrix full-color display device including the organic EL element 2-1D obtained in this way, a bright full-color moving picture display with high brightness and high durability can be obtained.

Claims

1. An inkjet recording medium for an organic semiconductor device, wherein a substrate, an electrode, and an ink receiving layer are sequentially stacked, characterized in that: The ink receiving layer has an ink penetration preventing region on the electrode side, the ink penetration preventing region preventing ink penetrating from a surface away from the electrode toward the electrode from reaching the electrode, The ink receiving layer has an ink permeable layer including a surface away from the electrode, and has an ink insoluble layer on the electrode side as the ink permeation preventing region. The ink-resistant layer contains an interpenetrating polymer network structure, or the ink-permeable layer contains a polystyrene resin and the ink-resistant layer contains a resin containing tetraphenylbenzidine or a derivative thereof as a main polymerization unit.

2. The inkjet recording medium for an organic semiconductor device according to claim 1, wherein The absolute value of the difference between the SP value of the constituent component of the ink permeable layer and the SP value of the ink is 3.0 (J / cm 3 ) 1 / 2 Hereinafter, the absolute value of the difference between the SP value of the constituent component of the ink insoluble layer and the SP value of the ink is 3.1 (J / cm 3 ) 1 / 2 above.

3. The inkjet recording medium for an organic semiconductor device according to claim 1 or 2, characterized in that: A release film is also provided on the ink receiving layer.

4. An organic semiconductor device member, which is a member for an organic semiconductor device formed by laminating a substrate, an electrode, and an organic semiconductor layer in this order, characterized in that: The organic semiconductor layer has: an ink receiving layer continuously present over the entire region of the formation region of the organic semiconductor layer on the electrode; and a region containing an organic semiconductor material having a pattern-shaped exposed portion on a surface of the organic semiconductor layer away from the electrode and having no interface with the electrode as a discontinuous region surrounded by the ink receiving layer, The region containing the organic semiconductor material is a region formed using ink containing the organic semiconductor material, and the ink receiving layer includes an ink permeable layer including a surface away from the electrode and an ink insoluble layer on the electrode side. The ink-resistant layer contains an interpenetrating polymer network structure, or the ink-permeable layer contains a polystyrene resin and the ink-resistant layer contains a resin containing tetraphenylbenzidine or a derivative thereof as a main polymerization unit.

5. The organic semiconductor device member according to claim 4, wherein: The maximum thickness of the ink receiving layer is in the range of 3 nm to 5 μm.

6. The organic semiconductor device member according to claim 4 or 5, characterized in that: The region containing the organic semiconductor material is a region formed using an ink containing the organic semiconductor material, and the absolute value of the difference between the SP value of the constituent material of the ink receiving layer and the SP value of the ink is 3.0 (J / cm 3 ) 1 / 2 the following.

7. A method for producing an organic semiconductor device, the method using the inkjet recording medium for an organic semiconductor device according to any one of claims 1 to 3, characterized in that: have: A step of dropping ink onto the ink receiving layer; and After the ink dropping, a film is formed on the ink receiving layer of an electrode which forms a pair with the electrode.

8. The method for manufacturing an organic semiconductor device according to claim 7, characterized in that: The organic semiconductor device is selected from an organic electroluminescent element, an organic thin film transistor or an organic photoelectric conversion element.

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