Organic metal compound for masks, method for processing organic semiconductor layer, and method for producing organic semiconductor device
Patent Information
- Application Number
- JP2023542024
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2021-08-20
- Filing Date
- 2022-08-09
- Publication Date
- 2025-08-13
- Estimated Expiration
- 2042-08-09
AI Technical Summary
The challenge in organic semiconductor devices is to prevent the increase in voltage and maintain good characteristics while forming an aluminum oxide film on an organic semiconductor layer, as prolonged exposure to treatment conditions can deteriorate the surface and residual aluminum oxide can lead to increased voltage in the device.
An organometallic compound represented by specific general formulas is used as a mask layer between the organic semiconductor layer and the aluminum oxide film, facilitating the removal of the aluminum oxide film using water or a liquid solvent, thereby minimizing damage and preventing voltage increase.
This method effectively suppresses the deterioration of the organic semiconductor device characteristics and prevents voltage increase by easily removing the aluminum oxide film while protecting the organic semiconductor layer, enabling the production of high-definition devices with improved reliability.
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Abstract
Description
Organometallic compound for mask, layer, method for processing organic semiconductor layer, and method for fabricating organic semiconductor device
[0001] One embodiment of the present invention relates to an organic compound, an organic EL device, a display module, a lighting module, a display device, a light-emitting device, an electronic device, a lighting device, and an electronic device. Note that one embodiment of the present invention is not limited to the above technical field. The technical field of one embodiment of the invention disclosed in this specification etc. relates to an object, a method, or a manufacturing method. Alternatively, one embodiment of the present invention relates to a process, a machine, manufacture, or a composition of matter. Therefore, more specific examples of the technical field of one embodiment of the present invention disclosed in this specification include semiconductor devices, display devices, liquid crystal display devices, light-emitting devices, lighting devices, power storage devices, memory devices, imaging devices, driving methods thereof, and manufacturing methods thereof.
[0002] Organic EL devices that utilize electroluminescence (EL) using organic compounds are becoming increasingly common. These devices are basically constructed by sandwiching an organic compound layer (EL layer) containing a light-emitting material between a pair of electrodes. By applying a voltage to the device, carriers are injected, and the recombination energy of the carriers is utilized to emit light from the light-emitting material.
[0003] Since such organic EL devices are self-luminous, when used as display pixels, they have advantages such as higher visibility and no need for backlighting compared to liquid crystals, making them particularly suitable for flat panel displays. Another major advantage of displays using such organic EL devices is that they can be fabricated to be thin and lightweight. Another feature is their extremely fast response speed.
[0004] Furthermore, these organic EL devices can have a continuous light-emitting layer formed two-dimensionally, enabling them to emit light in a planar form. This is a feature that is difficult to obtain with point light sources such as incandescent lamps and LEDs, or linear light sources such as fluorescent lamps, making them highly useful as planar light sources for lighting and other applications.
[0005] Thus, light-emitting devices using organic EL devices are suitable for a variety of electronic devices, but research and development is ongoing to find organic EL devices with even better characteristics.
[0006] In order to obtain a light-emitting device with higher resolution using an organic EL device, research has been conducted into patterning of organic layers by photolithography using photoresist, etc., instead of vapor deposition using a metal mask. By using photolithography, a high-resolution light-emitting device with an EL layer spacing of several micrometers can be obtained (see, for example, Patent Document 1).
[0007] Special table 2018-521459 publication
[0008] When patterning an organic layer by photolithography, an aluminum oxide film may be used as a mask layer for the organic layer. Aluminum oxide films are suitable as mask layers for organic layers because they are less likely to cause significant damage to the organic layer during deposition or removal. However, even though they are less susceptible to significant damage, prolonged exposure of the surface of the organic layer to the processing conditions used to remove the aluminum oxide film can lead to deterioration of the characteristics. On the other hand, if the aluminum oxide film remains on the surface of the organic layer, it may result in a higher voltage for the subsequently fabricated device.
[0009] Therefore, one embodiment of the present invention aims to suppress high voltage in an organic semiconductor device that has a step of forming an aluminum oxide film in contact with an organic semiconductor layer, or to provide an organic semiconductor device with good characteristics that is fabricated through a step of forming an aluminum oxide film in contact with an organic semiconductor layer.
[0010] In view of the above, one embodiment of the present invention provides an organometallic compound for masking an organic semiconductor layer, which is represented by the following general formula (G1) and is used to remove an aluminum oxide film formed on an organic semiconductor layer:
[0011]
[0012] In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, X represents oxygen or sulfur, M represents a metal, n represents an integer of 1 to 5, and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0013] Another embodiment of the present invention is an organometallic compound for a mask of an organic semiconductor layer, in which, in the above structure, the organometallic compound represented by General Formula (G1) is an organometallic compound represented by General Formula (G2):
[0014]
[0015] In General Formula (G2), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, M represents a metal, n represents an integer of 1 to 3, and n is the same as the valence of the metal M. When n is 2 or more, the multiple Ars may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0016] Another embodiment of the present invention is an organometallic compound for masking an organic semiconductor layer in the above structure, wherein the organic semiconductor layer includes a photoelectric conversion layer.
[0017] Another embodiment of the present invention is an organometallic compound for masking an EL layer, in which the organic semiconductor layer in the above structure is an EL layer.
[0018] Another embodiment of the present invention is a layer which is located between an organic semiconductor layer and an aluminum oxide film and contains an organometallic compound represented by General Formula (G1) below.
[0019]
[0020] In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, X represents oxygen or sulfur, M represents a metal, n represents an integer of 1 to 5, and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0021] Another embodiment of the present invention is a layer formed between an organic semiconductor layer and an aluminum oxide film, which contains an organometallic compound represented by the following general formula (G1) and is used to remove the aluminum oxide film:
[0022]
[0023] In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, X represents oxygen or sulfur, M represents a metal, n represents an integer of 1 to 5, and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0024] Another embodiment of the present invention is a layer having the above structure, in which the organometallic compound represented by General Formula (G1) is an organometallic compound represented by General Formula (G2):
[0025]
[0026] In General Formula (G2), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, M represents a metal, n represents an integer of 1 to 3, and n is the same as the valence of the metal M. When n is 2 or more, the multiple Ars may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0027] Alternatively, in another embodiment of the present invention, in the above structure, the organic semiconductor layer includes a photoelectric conversion layer.
[0028] Another embodiment of the present invention is a layer in which the organic semiconductor layer in the above structure is an EL layer.
[0029] Another embodiment of the present invention is a method for processing an organic semiconductor layer, including: forming an organic semiconductor layer over a first electrode; forming a mask layer over the organic semiconductor layer, the mask layer including an organometallic compound represented by General Formula (G1) below; forming an aluminum oxide film over the mask layer; processing a shape of the organic semiconductor layer by using the aluminum oxide film; and removing the mask layer and the aluminum oxide film by using water or a liquid containing water as a solvent.
[0030]
[0031] In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, X represents oxygen or sulfur, M represents a metal, n represents an integer of 1 to 5, and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0032] Another embodiment of the present invention is a method for processing an organic semiconductor layer having the above structure, in which the organometallic compound represented by General Formula (G1) is an organometallic compound represented by General Formula (G2):
[0033]
[0034] In General Formula (G2), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, M represents a metal, n represents an integer of 1 to 3, and n is the same as the valence of the metal M. When n is 2 or more, the multiple Ars may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0035] Another aspect of the present invention is a method for processing an organic semiconductor layer, in which the aluminum oxide film is formed by atomic layer deposition in the above-described configuration.
[0036] Another embodiment of the present invention is a method for processing an organic semiconductor layer having the above structure, wherein the mask layer containing the organometallic compound is formed by a vacuum evaporation method.
[0037] Alternatively, another aspect of the present invention is a method for processing an organic semiconductor layer having the above-described configuration, including the steps of: forming an aluminum oxide film on the mask layer; forming a metal film or a metal compound film on the aluminum oxide film; processing the shape of the organic semiconductor layer using the aluminum oxide film and the metal film or the metal compound film; and removing the mask layer and the aluminum oxide film using water or a liquid containing water as a solvent.
[0038] Alternatively, another aspect of the present invention is a method for processing an organic semiconductor layer having the above-described configuration, including, after the step of processing the shape of the organic semiconductor layer, a step of removing the metal film or the metal compound film, and a step of removing the mask layer and the aluminum oxide film using water or a liquid containing water as a solvent.
[0039] Alternatively, another aspect of the present invention is the method for processing an organic semiconductor layer having the above structure, wherein water is used in the step of removing the mask layer and the aluminum oxide film using water or a liquid containing water as a solvent.
[0040] Alternatively, another aspect of the present invention is a method for processing an organic semiconductor layer having the above-described structure, further comprising the step of removing part or all of the aluminum oxide film using an alkaline solution or an acidic solution before the step of removing the mask layer and the aluminum oxide film using water.
[0041] Another embodiment of the present invention is a method for processing an organic semiconductor layer having the above structure, wherein the organic semiconductor layer includes a photoelectric conversion layer.
[0042] Another embodiment of the present invention is a method for processing an EL layer, in which the organic semiconductor layer is an EL layer in the above-described structure.
[0043] Another embodiment of the present invention is a method for processing an EL layer having the above-described structure, wherein the EL layer has a stacked structure including, in order from the first electrode side, a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer.
[0044] Alternatively, another embodiment of the present invention provides a method for manufacturing a semiconductor device, comprising: forming an organic semiconductor film on a first electrode; forming a mask film on the organic semiconductor film, the mask film including an organometallic compound represented by the following general formula (G1); forming a first aluminum oxide film on the mask film; forming a metal film or a metal compound film on the first aluminum oxide film; forming a photomask on the metal film or the metal compound film; etching the metal film or the metal compound film using the photomask to form a metal layer or a metal compound layer that overlaps the first electrode; removing the photomask; a step of etching the aluminum oxide film, the mask film, and the organic semiconductor film to form a first aluminum oxide layer, a mask layer, and an organic semiconductor layer; a step of removing the metal layer or the metal compound layer; a step of forming an organic resin film to cover the first electrode, the organic semiconductor layer, the mask layer, and the first aluminum oxide layer; a step of forming openings in the organic resin film that overlap the first electrode, the organic semiconductor layer, the mask layer, and the first aluminum oxide layer; and a step of removing the mask layer and the first aluminum oxide layer that overlap the openings using water or a liquid containing water as a solvent.
[0045]
[0046] In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, X represents oxygen or sulfur, M represents a metal, n represents an integer of 1 to 5, and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0047] Another embodiment of the present invention is a method for manufacturing an organic semiconductor device having the above structure, wherein the organometallic compound represented by General Formula (G1) is an organometallic compound represented by General Formula (G2):
[0048]
[0049] In General Formula (G2), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, M represents a metal, n represents an integer of 1 to 3, and n is the same as the valence of the metal M. When n is 2 or more, the multiple Ars may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0050] Another embodiment of the present invention is a method for manufacturing an organic semiconductor device having the above structure, wherein water is used in the step of removing the mask layer and the first aluminum oxide layer that overlap the opening using water or a liquid containing water as a solvent.
[0051] Alternatively, another embodiment of the present invention is a method for manufacturing an organic semiconductor device having the above structure, further comprising the step of removing a part or all of the first aluminum oxide layer using an alkaline solution or an acidic solution before the step of removing the mask layer and the first aluminum oxide layer that overlap the opening using water.
[0052] Alternatively, another embodiment of the present invention provides a method for manufacturing a semiconductor device, comprising the steps of: forming an organic semiconductor film on a first electrode; forming a mask film containing an organometallic compound represented by the following general formula (G1) on the organic semiconductor film; forming a first aluminum oxide film on the mask film; forming a metal film or a metal compound film on the first aluminum oxide film; forming a photomask on the metal film or the metal compound film; etching the metal film or the metal compound film using the photomask to form a metal layer or a metal compound layer that overlaps the first electrode; removing the photomask; and etching the first aluminum oxide film, the mask film, and the organic semiconductor film using the metal layer or the metal compound layer as a mask to form the first aluminum oxide layer, the mask layer, and the organic semiconductor film. forming an organic resin film covering the first electrode, the organic semiconductor layer, the mask layer, the first aluminum oxide layer, and the second aluminum oxide film; forming openings in the organic resin film that overlap the first electrode, the organic semiconductor layer, the mask layer, the first aluminum oxide layer, and the second aluminum oxide film; and removing the mask layer, the first aluminum oxide layer, and the second aluminum oxide film that overlap the openings using water or a liquid containing water as a solvent.
[0053]
[0054] In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, X represents oxygen or sulfur, M represents a metal, n represents an integer of 1 to 5, and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0055] Another embodiment of the present invention is a method for manufacturing an organic semiconductor device having the above structure, wherein the organometallic compound represented by General Formula (G1) is an organometallic compound represented by General Formula (G2):
[0056]
[0057] In General Formula (G2), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, M represents a metal, n represents an integer of 1 to 3, and n is the same as the valence of the metal M. When n is 2 or more, the multiple Ars may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0058] Alternatively, another embodiment of the present invention is a method for manufacturing an organic semiconductor device having the above structure, wherein water is used in the step of removing the mask layer, the first aluminum oxide layer, and the second aluminum oxide film that overlap the opening using water or a liquid containing water as a solvent.
[0059] Alternatively, another embodiment of the present invention is a method for manufacturing an organic semiconductor device having the above structure, further comprising the step of removing the second aluminum oxide film and part or all of the first aluminum oxide layer using an alkaline solution or an acidic solution before the step of removing the mask layer and the first aluminum oxide layer that overlap the opening using water.
[0060] Another aspect of the present invention is a method for manufacturing an organic semiconductor device having the above-described structure, wherein the second aluminum oxide film is formed by atomic layer deposition.
[0061] Another aspect of the present invention is a method for manufacturing an organic semiconductor device having the above-described structure, wherein the first aluminum oxide film is formed by atomic layer deposition.
[0062] Another embodiment of the present invention is a method for manufacturing an organic semiconductor device having the above structure, wherein the mask layer containing the organometallic compound is formed by a vacuum deposition method.
[0063] Another embodiment of the present invention is a method for manufacturing an organic semiconductor device having the above structure, wherein the organic semiconductor layer includes a photoelectric conversion layer.
[0064] Another aspect of the present invention is a method for producing an organic EL device having the above-described structure, wherein the organic semiconductor layer is an EL layer.
[0065] Alternatively, another aspect of the present invention is a method for manufacturing an organic EL device having the above-described configuration, wherein the EL layer has a stacked structure, and the EL layer has, in order from the first electrode side, a hole injection layer, a hole transport layer, an emitting layer, and an electron transport layer.
[0066] In this specification, the term "light-emitting device" includes an image display device using an organic EL device. The term "light-emitting device" may also include a module in which a connector, such as an anisotropic conductive film or a TCP (Tape Carrier Package), is attached to an organic EL device, a module in which a printed wiring board is provided at the end of a TCP, or a module in which an IC (integrated circuit) is directly mounted on an organic EL device using a COG (Chip On Glass) method. Furthermore, lighting fixtures and the like may have a light-emitting device.
[0067] In one embodiment of the present invention, an increase in voltage can be suppressed in an organic semiconductor device having a step of forming an aluminum oxide film in contact with an organic semiconductor layer, or an organic semiconductor device having good characteristics can be provided.
[0068] Note that the description of this effect does not preclude the existence of other effects. Note that one embodiment of the present invention does not necessarily have all of these effects. Note that effects other than these will become apparent from the description in the specification, drawings, claims, etc., and it is possible to extract other effects from the description in the specification, drawings, claims, etc.
[0069] FIGS. 1A and 1B are diagrams illustrating one embodiment of the present invention. FIGS. 2A to 2C are diagrams illustrating a conventional configuration. FIGS. 3A to 3E are diagrams illustrating a film processing method. FIGS. 4A to 4E are diagrams illustrating a film processing method. FIGS. 5A to 5C are diagrams illustrating an organic semiconductor device. FIGS. 6A to 6D are diagrams illustrating a light-emitting device. FIG. 7 is a diagram illustrating a light-emitting device. FIGS. 8A to 8F are diagrams illustrating a method for fabricating an organic EL device and a light-emitting device. FIGS. 9A to 9F are diagrams illustrating a method for fabricating an organic EL device and a light-emitting device. FIG. 10 is a diagram illustrating an organic EL device. FIGS. 11A and 11B are diagrams illustrating an active matrix light-emitting device. FIGS. 12A and 12B are diagrams illustrating an active matrix light-emitting device. FIG. 13 is a diagram illustrating an active matrix light-emitting device. FIGS. 14A, 14B1, 14B2, and 14C are diagrams illustrating electronic devices. Figures 15A, 15B, and 15C are diagrams showing electronic devices. Figure 16 is a diagram showing an in-vehicle display device and a lighting device. Figures 17A and 17B are diagrams showing electronic devices. Figures 18A, 18B, and 18C are diagrams showing electronic devices. Figure 19 is a diagram showing measurement results by high performance liquid chromatography.
[0070] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and it will be readily understood by those skilled in the art that various changes in form and details can be made without departing from the spirit and scope of the present invention. Therefore, the present invention should not be interpreted as being limited to the description of the embodiments shown below.
[0071] In this specification, etc., a device fabricated using a metal mask or an FMM (fine metal mask, high-resolution metal mask) may be referred to as a device with an MM (metal mask) structure. In addition, in this specification, etc., a device fabricated without using a metal mask or an FMM may be referred to as a device with an MML (metal maskless) structure.
[0072] Furthermore, in this specification and the like, a film that has not undergone shape processing after deposition is generally referred to as a "film," and a film that has undergone shape processing is generally referred to as a "layer." However, these terms are used solely for the purpose of making it easier to understand the progress of the process, and there is no significant difference between them, so "film" can be read as a "layer" and "layer" as a "film." In particular, when describing a film that has not undergone a processing step, both terms are considered to have the same meaning.
[0073] (Embodiment 1) Vacuum deposition using a metal mask (mask deposition) is widely used as one method for fabricating an organic semiconductor film into a predetermined shape. However, with the recent trend toward higher density and higher definition, mask deposition is approaching its limit in achieving higher definition due to various reasons, including problems with alignment accuracy and the spacing between the mask and the substrate. On the other hand, by processing the shape of an organic semiconductor film using a photolithography method, it is possible to form a denser pattern. In addition, since photolithography can easily be used to fabricate large-area films, research into processing organic semiconductor films using photolithography is also being conducted.
[0074] However, in order to process the shape of an organic semiconductor film using photolithography, many problems must be overcome, such as the effect of exposure of the organic semiconductor film to the atmosphere, the effect of light irradiation when exposing a photosensitive resin, the effect of the developer to which the exposed photosensitive resin is exposed when developing it, and the effect of forming a metal film when a metal film is formed to reduce the effect of the developer.
[0075] These effects are considered problematic because they can cause situations such as the organic semiconductor film itself disappearing or the surface of the organic semiconductor film being damaged, resulting in a significant deterioration in the characteristics of devices subsequently fabricated.
[0076] One way to solve the above-mentioned problems is to provide an aluminum oxide film 153 as a protective film on the organic semiconductor film 151, as shown in Figure 2A, and then carry out the above-mentioned problematic process. The aluminum oxide film can be formed as a dense film and has a high ability to block liquids and gases, making it possible to suppress the adverse effects of the above-mentioned process. Furthermore, the aluminum oxide film can be formed and removed using a method that causes little damage to the organic semiconductor film, making it extremely suitable as a protective film for the organic semiconductor film 151.
[0077] As a method for forming the aluminum oxide film, atomic layer deposition (ALD) is preferred because it allows the formation of a denser film and causes less damage to the organic semiconductor film.
[0078] As described above, the aluminum oxide film is a film that inflicts relatively little damage on the organic semiconductor film during its formation and removal, and therefore can be suitably used as a protective film when processing the organic semiconductor film by photolithography. However, if the surface of the organic semiconductor film is excessively exposed to the aluminum oxide film removal process, the surface 151s of the organic semiconductor film 151 may be damaged, as shown in Figure 2B, which may lead to a deterioration in the characteristics of the organic semiconductor. Therefore, it is preferable to spend as little time as possible removing the aluminum oxide film.
[0079] To minimize the removal process, the process should be terminated when the aluminum oxide is no longer present on the organic semiconductor film. However, determining this is extremely difficult, and if there is in-plane variation in the film quality of the aluminum oxide film, the etching process for removing the aluminum oxide film will also have in-plane differences in the etching rate. As shown in Figure 2C, even if a portion of the aluminum oxide film is successfully removed, aluminum oxide film 153r may remain in other portions. In particular, when forming an aluminum oxide film on an organic film using the ALD method, the in-plane variation described above is likely to occur because high temperatures cannot be used for film formation, which can result in the partial generation of residual aluminum oxide film 153r. Residual aluminum oxide on the organic semiconductor film may increase the driving voltage of the device to be fabricated later. Furthermore, excessive etching to completely remove the residual aluminum oxide film 153r is highly undesirable because it can result in side etching of the aluminum oxide film that should be left in the process (aluminum oxide film that is not removed) in the direction of adjacent pixels.
[0080] Therefore, in one embodiment of the present invention, as shown in FIG. 1A , a film (mask film) 152 containing an organometallic compound having a specific structure is used between the organic semiconductor film 151 and the aluminum oxide film 153 to facilitate removal of the aluminum oxide film.
[0081] As such an organometallic compound, it is preferable to use an organometallic compound represented by the following general formula (G1).
[0082]
[0083] In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, X represents oxygen or sulfur, M represents a metal, n represents an integer of 1 to 5, and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0084] By providing a layer (mask layer) containing the organometallic compound represented by the general formula (G1) between the organic semiconductor film and the aluminum oxide film, the aluminum oxide film can be easily removed from the organic semiconductor film 151 using water or a liquid containing water as a solvent, as shown in Figure 1B. Removal of the mask layer using water or a liquid containing water as a solvent, particularly water, can reduce damage to the organic semiconductor film 151 more than removal of the aluminum oxide film, and can also significantly reduce damage to the aluminum oxide film in the lateral direction that should be left when patterning the organic semiconductor layer, thereby making it possible to suppress deterioration of the characteristics of the device to be fabricated later.
[0085] In the organometallic compound represented by the general formula (G1), X is preferably an oxygen atom, because X has a strong interaction with water or a liquid containing water as a solvent, which makes it possible to more easily remove the aluminum oxide film, to stably carry out vapor deposition, and to form a highly heat-resistant and stable film. That is, an organometallic compound represented by the following general formula (G2) is preferred.
[0086]
[0087] In General Formula (G2), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, M represents a metal, n represents an integer of 1 to 3, and n is the same as the valence of the metal M. When n is 2 or more, the multiple Ars may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.
[0088] In the above general formula (G1) or (G2), it is preferable that M is aluminum, because it increases the interaction with water or a liquid using water as a solvent, it allows the layer containing the organometallic compound represented by the above general formula (G1) or (G2) (mask layer) to be removed more easily, it enables stable vapor deposition, it allows the formation of a stable film with high heat resistance, and it is expected to have an effect of improving adhesion to an aluminum oxide film.
[0089] Furthermore, the aryl group having 6 to 30 carbon atoms is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, a dibenzofluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, a pyrenyl group, a phenanthrenyl group, a triphenylenyl group, a perylenyl group, a tetracenyl group, or a chrysenyl group. Furthermore, the heteroaryl group having 1 to 30 carbon atoms is preferably a group having a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a quinoline ring, a quinazoline ring, an isoquinoline ring, a pyrrole ring, a naphthyridine ring, a phenanthridine ring, a quinoxaline ring, an imidazole ring, a benzimidazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, or a benzofuran ring, more preferably a pyridyl group or a quinolyl group because they easily form a coordinate bond with the metal M, and even more preferably a 2-pyridyl group or an 8-quinolyl group for forming a stable coordinate bond with the metal M. Note that when the aryl group having 6 to 30 carbon atoms or the heteroaryl group having 1 to 30 carbon atoms has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.
[0090] Specific examples of the organometallic compounds represented by the general formula (G1) and the general formula (G2) include organometallic compounds represented by the following structural formulas (100) to (115).
[0091]
[0092] In particular, (8-quinolinolato)lithium (abbreviation: Liq) and tris(8-quinolinolato)aluminum (abbreviation: Alq 3 ) is a highly preferred material because it is inexpensive, has been used for a long time, and can be easily removed with water.
[0093] Here, Liq, Alq 3 It is generally known that Liq and Alq are hardly soluble in water. However, when Liq and Alq are deposited on an organic semiconductor layer, 3 It has been found that the organic metal compounds represented by the general formula (G1) and the general formula (G2), particularly Liq or Alq, can be easily removed with water and can be very suitably used as a mask layer for an organic semiconductor layer used to remove an aluminum oxide film. This result cannot be derived from the common technical knowledge that the organic metal compounds are insoluble in water. 3 It can be said that the effect of forming a film containing the above compound between an organic semiconductor layer and an aluminum oxide layer and using the film as a mask layer for the organic semiconductor to remove the aluminum oxide film, which can be easily removed with water, is an effect that would not have been anticipated by a person skilled in the art.
[0094] By forming a film containing such an organometallic compound between an organic semiconductor layer and an aluminum oxide film, it becomes possible to easily remove the aluminum oxide film while suppressing damage to the organic semiconductor layer and preventing high voltages, and as a result, it becomes possible to realize an ultra-high-definition device with excellent characteristics that has been processed by photolithography.
[0095] The structure of this embodiment mode can be used in appropriate combination with other structures.
[0096] Embodiment 2 In this embodiment, a method for processing an organic semiconductor layer according to one embodiment of the present invention will be described with reference to FIGS.
[0097] First, an organic semiconductor film 151 is formed on an underlayer 150 (FIG. 3A). The underlayer may be an insulating film or a conductive film depending on the device to be fabricated. The organic semiconductor film 151 may be formed by a dry method such as vapor deposition, or by a wet method such as spin coating.
[0098] Next, a mask layer 152 containing an organometallic compound represented by the general formula (G1) or (G2) is formed on the organic semiconductor film 151 (FIG. 3A). The mask layer 152 is preferably formed by vacuum deposition.
[0099] Subsequently, an aluminum oxide film 153 is formed on the mask layer 152 (FIG. 3A). The aluminum oxide film is preferably formed by a method that causes minimal damage to the organic semiconductor film 151, and is preferably formed by the ALD method.
[0100] It is preferable to form a metal film or metal compound film 154 on the aluminum oxide film 153 ( FIG. 3B ). The presence of the aluminum oxide film 153 can suppress damage to the organic semiconductor film 151, so that a film formation method that causes relatively large damage to the surface on which the film is formed, such as sputtering, can be selected for the formation of the metal film or metal compound film 154. Examples of materials that can be used to form the metal film or metal compound film 154 include silicon, silicon nitride, silicon oxide, tungsten, titanium, molybdenum, tantalum, tantalum nitride, an alloy containing molybdenum and niobium, an alloy containing molybdenum and tungsten, and indium gallium zinc oxide (In—Ga—Zn oxide, also referred to as IGZO). Furthermore, indium oxide, indium zinc oxide (In—Zn oxide), indium tin oxide (In—Sn oxide), indium titanium oxide (In—Ti oxide), indium tin zinc oxide (In—Sn—Zn oxide), indium titanium zinc oxide (In—Ti—Zn oxide), indium gallium tin zinc oxide (In—Ga—Sn—Zn oxide), etc. can also be used. Alternatively, indium tin oxide containing silicon can also be used.
[0101] Thereafter, a photosensitive resin is applied onto the metal film or metal compound film 154 to form a resin film 155 (FIG. 3C). The photosensitive resin may be a positive resist or a negative resist.
[0102] Next, the resin is exposed to light in accordance with its photosensitivity and developed to form a photomask layer 155a (FIG. 3D). The metal or metal compound film 154 is etched using the photomask layer 155a to form a metal or metal compound layer 154a (FIG. 3E). The metal or metal compound film 154 may be etched by wet etching or dry etching. It is preferable to select conditions for the etching that provide a higher selectivity for the metal or metal compound film 154 than the aluminum oxide film 153.
[0103] After the metal or metal compound layer 154a is formed, the photomask layer 155a is removed (FIG. 4A). The presence of the metal or metal compound film 154 and the aluminum oxide film 153 prevents the organic semiconductor film 151 from being adversely affected, such as being lost or damaged, during the processes of forming and removing the photomask layer 155a, and therefore an organic semiconductor device with excellent characteristics can be fabricated.
[0104] Thereafter, the metal film or metal compound film 154a is used as a mask to perform etching to form the organic semiconductor layer 151a, the mask layer 152a, and the aluminum oxide layer 153a (FIG. 4B). These etchings may be performed by wet etching or dry etching, but dry etching is preferred.
[0105] After processing of the organic semiconductor layer 151a is completed, the metal layer or metal compound layer 154a is removed (FIG. 4C). The metal layer or metal compound layer 154a may be removed by etching, which may be wet etching or dry etching, but dry etching is preferred. The etching is preferably performed under conditions that provide a higher selective ratio for the metal layer or metal compound layer 154a than the aluminum oxide layer 153a.
[0106] Finally, the aluminum oxide layer 153a and the mask layer 152a are simultaneously removed by treatment with water or a liquid containing water as a solvent (FIG. 4E). The removal method involves immersing the layer in water or a liquid containing water as a solvent for a certain period of time, followed by rinsing with a shower of pure water. This single process is sufficient to remove the metal layer or metal compound layer 154a and the mask layer 152a. Water is the preferred liquid for removal, as it causes less damage to the organic semiconductor layer 151a.
[0107] After removing the metal or metal compound layer 154a, the aluminum oxide layer 153a may be removed to some extent before treating the mask layer 152a with water or a water-based liquid ( FIG. 4D ). The aluminum oxide layer 153a can be removed by etching, either wet etching or dry etching. However, wet etching using an alkaline or acidic solution is preferred, and wet etching using an alkaline solution is even more preferred. The presence of the mask layer 152a prevents the surface of the organic semiconductor layer 151a from being exposed to the alkaline or acidic solution, thereby preventing deterioration of its characteristics. Furthermore, by performing the treatment so that some of the aluminum oxide film 153r remains on the mask layer 152a, the subsequent process of removing the mask layer 152a can be carried out more smoothly.
[0108] The organic semiconductor layer 151a processed by this process suffers little damage from processing, and therefore can be made into an organic semiconductor device with good characteristics. Furthermore, the aluminum oxide film 153r can be prevented from remaining on the surface of the organic semiconductor layer 151a, which can prevent the organic semiconductor device to be fabricated subsequently from requiring high voltage.
[0109] The organic semiconductor layer 151 a can be used in an organic TFT having an organic semiconductor layer 151 a provided on an insulating layer 160, a gate insulating layer 161, a gate electrode 162, and source and drain electrodes 163 and 164 as shown in FIG. 5A ; a photoelectric conversion device such as a solar cell or a photosensor having a first electrode 165 and a second electrode 166 and a photoelectric conversion layer 167 provided on the insulating layer 160 as shown in FIG. 5B ; and an organic EL device having a first electrode 165, a second electrode 166 and a light-emitting layer 168 provided on the insulating layer 160 as shown in FIG. 5C .
[0110] The structure of this embodiment mode can be used in appropriate combination with other structures.
[0111] (Embodiment 3) [Manufacturing Method Example] In this embodiment, an example of a manufacturing method of an organic semiconductor device according to one embodiment of the present invention will be described with reference to the drawings. Here, a light-emitting device 450 as shown in FIG. 6 will be described as an example. The light-emitting device 450 is a light-emitting device including an organic EL device in which the organic semiconductor layer in Embodiment 1 or 2 is an EL layer. That is, what will be referred to as an EL layer hereinafter corresponds to the above-described organic semiconductor layer. Note that by using an organic semiconductor layer including a photoelectric conversion layer instead of the EL layer, the device can also be used as a photosensor. A photosensor and an organic EL device may be included simultaneously in the light-emitting device.
[0112] 6A shows a schematic top view of a light-emitting device 450. The light-emitting device 450 includes a plurality of blue organic EL devices 110B, a plurality of green organic EL devices 110G, and a plurality of red organic EL devices 110R. In FIG. 6A, the light-emitting regions of the respective organic EL devices are labeled with R, G, and B to easily distinguish between the respective organic EL devices.
[0113] The organic EL devices 110B, 110G, and 110R are arranged in a matrix. Fig. 6A shows a so-called stripe arrangement in which organic EL devices of the same color are arranged in one direction. Note that the arrangement of the organic EL devices is not limited to this, and other arrangements such as a delta arrangement or a zigzag arrangement may also be used, or a pentile arrangement may also be used.
[0114] The organic EL devices 110B, 110G, and 110R are arranged in the X direction. In the Y direction intersecting the X direction, organic EL devices of the same color are arranged.
[0115] The organic EL device 110B, the organic EL device 110G, and the organic EL device 110R are organic EL devices having the above-described configuration.
[0116] 6B is a schematic cross-sectional view corresponding to the dashed dotted line A1-A2 in FIG. 6A, and FIG. 6C is a schematic cross-sectional view corresponding to the dashed dotted line B1-B2.
[0117] 6B shows cross sections of organic EL devices 110B, 110G, and 110R. The organic EL device 110B includes a first electrode (pixel electrode) 101B, a first EL layer 120B, a second EL layer 121, and a second electrode 102. The organic EL device 110G includes a first electrode (pixel electrode) 101G, a first EL layer 120G, a second EL layer (electron injection layer) 121, and a second electrode 102. The organic EL device 110R includes a first electrode (pixel electrode) 101R, a first EL layer 120R, a second EL layer 121, and a second electrode (common electrode) 102. The second EL layer 121 and the second electrode 102 are common to the organic EL devices 110B, 110G, and 110R. The second EL layer 121 can also be called a common layer. Note that in this embodiment mode, a case where the first electrode 101 is an anode and the second electrode 102 is a cathode will be described as an example.
[0118] The first EL layer 120B of the organic EL device 110B contains a light-emitting organic compound that emits light having an intensity in at least the blue wavelength range. The first EL layer 120G of the organic EL device 110G contains a light-emitting organic compound that emits light having an intensity in at least the green wavelength range. The first EL layer 120R of the organic EL device 110R contains a light-emitting organic compound that emits light having an intensity in at least the red wavelength range.
[0119] The first EL layer 120B, the first EL layer 120G, and the first EL layer 120R each have at least a light-emitting layer and may additionally have one or more of a hole-blocking layer, an electron-injecting layer, an electron-transporting layer, a hole-transporting layer, a hole-injecting layer, an electron-blocking layer, an exciton-blocking layer, and the like. The second EL layer 121 does not have a light-emitting layer. The second EL layer 121 is preferably an electron-injecting layer. Note that when the surfaces of the first EL layer 120B, the first EL layer 120G, and the first EL layer 120R on the second electrode side also serve as an electron-injecting layer, the second EL layer 121 does not need to be provided.
[0120] The first electrode (anode) 101B, the first electrode (anode) 101G, and the first electrode (anode) 101R are provided for each organic EL device, respectively. The second electrode 102 and the second EL layer 121 are preferably provided as a continuous layer common to each organic EL device.
[0121] A conductive film that is translucent to visible light is used for either the first electrode 101 or the second electrode 102, and a conductive film that is reflective is used for the other. By making the first electrode 101 translucent and the second electrode 102 reflective, a bottom-emission display device can be obtained. Conversely, by making each first electrode reflective and the second electrode 102 translucent, a top-emission display device can be obtained. Note that by making both the first electrode and the second electrode 102 translucent, a dual-emission display device can also be obtained. The organic EL device of this embodiment is suitable for a top-emission organic EL device.
[0122] The first EL layer 120B, the first EL layer 120G, and the first EL layer 120R are provided to cover the edges of the first electrode 101B, the first electrode 101G, and the first electrode 101R, respectively. An insulating layer 125 is provided to cover the edges of the first EL layer 120B, the first EL layer 120G, and the first EL layer 120R. In other words, the insulating layer 125 has openings that overlap with the first electrode 101B, the first electrode 101G, and the first electrode 101R and the first EL layer 120B, the first EL layer 120G, and the first EL layer 120R. The edges of the openings of the insulating layer 125 are preferably tapered. Note that the ends of the first electrode 101B, the first electrode 101G, and the first electrode 101R do not necessarily have to be covered with the first EL layer 120B, the first EL layer 120G, and the first EL layer 120R, respectively.
[0123] The first EL layer 120B, the first EL layer 120G, and the first EL layer 120R have regions in contact with the top surfaces of the first electrode 101B, the first electrode 101G, and the first electrode 101R, respectively. Ends of the first EL layer 120B, the first EL layer 120G, and the first EL layer 120R are located under the insulating layer 125. The top surfaces of the first EL layer 120B, the first EL layer 120G, and the first EL layer 120R have a region in contact with the insulating layer 125 and a region in contact with the second EL layer 121 (or the second electrode 102 in the case where the second EL layer is not provided).
[0124] FIG. 7 is a modified example of FIG. 6B . In FIG. 7 , the ends of the first electrode 101B, the first electrode 101G, and the first electrode 101R have a tapered shape that widens toward the substrate, improving coverage of the film formed thereon. Furthermore, the ends of the first electrode 101B, the first electrode 101G, and the first electrode 101R are covered by the first EL layer 120B, the first EL layer 120G, and the first EL layer 120R, respectively. A mask layer 107 is formed covering the EL layer. This serves to prevent damage to the EL layer during etching by photolithography. An insulating layer 108 is provided between the organic EL device 110B, the organic EL device 110G, and the organic EL device 110R. The insulating layer 108 has a gently tapered end portion, which can prevent the second EL layer 121 and the second electrode 102 from being broken down.
[0125] As shown in Figures 6B and 7, a gap is provided between the two EL layers of organic EL devices of different colors. In this manner, it is preferable that the first EL layer 120B, the first EL layer 120G, and the first EL layer 120R are arranged so as not to contact each other. This effectively prevents current from flowing through two adjacent EL layers, thereby preventing unintended light emission. This improves contrast and realizes a display device with high display quality. Furthermore, by using photolithography to fabricate the gap between the edges of the opposing EL layers of adjacent organic EL devices (e.g., organic EL device 110B and organic EL device 110G), it is possible to set the gap between 2 μm or more and 5 μm or less. This can also be referred to as the gap between the light-emitting layers included in the EL layer. It is difficult to achieve a gap of less than 10 μm using a metal mask formation method.
[0126] In this way, by fabricating a light-emitting device using a photolithography method, it is possible to significantly reduce the area of a non-light-emitting region that may exist between two organic EL devices, and to significantly increase the aperture ratio. For example, in a display device according to one embodiment of the present invention, the aperture ratio can be 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or even 90% or more, but less than 100%.
[0127] Increasing the aperture ratio of a display device can improve the reliability of the display device. More specifically, when the lifetime of a display device using an organic EL device and having an aperture ratio of 10% is taken as the reference, the lifetime of a display device having an aperture ratio of 20% (i.e., an aperture ratio twice as high as the reference) is approximately 3.25 times longer, and the lifetime of a display device having an aperture ratio of 40% (i.e., an aperture ratio four times as high as the reference) is approximately 10.6 times longer. As such, as the aperture ratio increases, the current density flowing through the organic EL device can be reduced, thereby improving the lifetime of the display device. In the display device described in this embodiment, the aperture ratio can be increased, thereby improving the display quality of the display device. Furthermore, as the aperture ratio of the display device increases, an excellent effect is achieved, such as a significant improvement in the reliability (especially the lifetime) of the display device.
[0128] 6C shows an example in which the EL layer 120R is formed so as to be separated for each organic EL device in the Y direction. While FIG. 6C shows a cross section of the organic EL device 110R as an example, the organic EL device 110G and the organic EL device 110B may also have a similar shape. The EL layer may be continuous in the Y direction, and the EL layer 120R may be formed in a strip shape. By forming the EL layer 120R, etc. in a strip shape, no space is required to separate them, and the area of the non-light-emitting region between the organic EL devices can be reduced, thereby increasing the aperture ratio.
[0129] A barrier layer 131 is provided on the second electrode 102 to cover the organic EL device 110B, the organic EL device 110G, and the organic EL device 110R. The barrier layer 131 has a function of preventing impurities that could adversely affect each organic EL device from diffusing from above.
[0130] The barrier layer 131 may have, for example, a single-layer structure or a multilayer structure including at least an inorganic insulating film. Examples of the inorganic insulating film include oxide films or nitride films such as a silicon oxide film, a silicon oxynitride film, a silicon nitride oxide film, a silicon nitride film, an aluminum oxide film, an aluminum oxynitride film, and a hafnium oxide film. Alternatively, the barrier layer 131 may be made of a semiconductor material such as indium gallium oxide or indium gallium zinc oxide.
[0131] Alternatively, the barrier layer 131 may be a laminated film of an inorganic insulating film and an organic insulating film. For example, a configuration in which an organic insulating film is sandwiched between a pair of inorganic insulating films is preferable. Furthermore, it is preferable that the organic insulating film functions as a planarizing film. This allows the upper surface of the organic insulating film to be flat, thereby improving the coverage of the inorganic insulating film thereon and enhancing the barrier properties. Furthermore, since the upper surface of the barrier layer 131 is flat, when a structure (e.g., a color filter, a touch sensor electrode, a lens array, etc.) is provided above the barrier layer 131, the influence of uneven shapes caused by the structure below can be reduced, which is preferable.
[0132] 6A also shows a connection electrode 101C that is electrically connected to the second electrode 102. The connection electrode 101C is given a potential (e.g., an anode potential or a cathode potential) to be supplied to the second electrode 102. The connection electrode 101C is provided outside the display area where the organic EL devices 110B and the like are arranged. In addition, in FIG. 6A, the second electrode 102 is shown by a dashed line.
[0133] The connection electrode 101C can be provided along the periphery of the display area. For example, it may be provided along one side of the periphery of the display area, or it may be provided over two or more sides of the periphery of the display area. That is, when the top surface shape of the display area is rectangular, the top surface shape of the connection electrode 101C can be strip-shaped, L-shaped, U-shaped (square bracket-shaped), square-shaped, or the like.
[0134] Fig. 6D is a schematic cross-sectional view corresponding to the dashed-dotted line C1-C2 in Fig. 6A. Fig. 6D shows a connection portion 130 where the connection electrode 101C and the second electrode 102 are electrically connected. In the connection portion 130, the second electrode 102 is provided in contact with the connection electrode 101C, and a barrier layer 131 is provided covering the second electrode 102. In addition, an EL layer 121 is provided covering the end of the connection electrode 101C.
[0135] 8A to 9F are schematic cross-sectional views illustrating the steps of the above-described method for fabricating the light-emitting device 450. Also shown on the right side of each of these views are schematic cross-sectional views of the connection portion 130 and its vicinity.
[0136] Thin films (insulating films, semiconductor films, conductive films, etc.) constituting the display device can be formed using a sputtering method, a chemical vapor deposition (CVD) method, a vacuum evaporation method, a pulsed laser deposition (PLD) method, an atomic layer deposition (ALD) method, etc. CVD methods include a plasma enhanced chemical vapor deposition (PECVD) method and a thermal CVD method. One type of thermal CVD method is a metal organic chemical vapor deposition (MOCVD) method.
[0137] Furthermore, thin films (insulating films, semiconductor films, conductive films, etc.) constituting the display device can be formed by methods such as spin coating, dipping, spray coating, inkjet, dispensing, screen printing, offset printing, doctor knife method, slit coating, roll coating, curtain coating, knife coating, etc.
[0138] Furthermore, when processing the thin films that constitute the display device, photolithography or the like can be used.
[0139] There are two typical photolithography methods: one is to form a resist mask on the thin film to be processed, process the thin film by etching or the like, and then remove the resist mask; the other is to form a photosensitive thin film, and then process the thin film into the desired shape by exposure and development.
[0140] In photolithography, the light used for exposure can be, for example, i-line (wavelength 365 nm), g-line (wavelength 436 nm), h-line (wavelength 405 nm), or a mixture of these. Other light sources that can be used include ultraviolet light, KrF laser light, ArF laser light, etc. Exposure can also be performed by immersion exposure technology. Extreme ultraviolet (EUV) light, X-rays, etc. can also be used as light for exposure. An electron beam can also be used instead of light for exposure. Extreme ultraviolet light, X-rays, or an electron beam are preferred because they enable extremely fine processing. When exposure is performed by scanning a beam such as an electron beam, a photomask is not required.
[0141] For etching the thin film, dry etching, wet etching, sandblasting, or the like can be used.
[0142] [Preparation of Substrate 100] A substrate having heat resistance sufficient to withstand at least subsequent heat treatment can be used as the substrate 100. When an insulating substrate is used as the substrate 100, a glass substrate, a quartz substrate, a sapphire substrate, a ceramic substrate, an organic resin substrate, or the like can be used. In addition, a semiconductor substrate such as a single crystal semiconductor substrate made of silicon, silicon carbide, or the like, a polycrystalline semiconductor substrate, a compound semiconductor substrate such as silicon germanium, or an SOI substrate can be used.
[0143] In particular, it is preferable to use a substrate in which a semiconductor circuit including semiconductor elements such as transistors is formed on the semiconductor substrate or insulating substrate as the substrate 100. The semiconductor circuit preferably constitutes, for example, a pixel circuit, a gate line driving circuit (gate driver), a source line driving circuit (source driver), etc. In addition to the above, an arithmetic circuit, a memory circuit, etc. may also be constituted.
[0144] [Formation of First Electrodes 101B, 101G, 101R, and Connection Electrode 101C] Next, the first electrode 101B, the first electrode 101G, the first electrode 101R, and the connection electrode 101C are formed on the substrate 100. First, a conductive film that will become the pixel electrode (first electrode) is formed, a resist mask is formed by photolithography, and unnecessary portions of the conductive film are removed by etching. Then, the resist mask is removed, thereby forming the first electrode 101B, the first electrode 101G, and the first electrode 101R.
[0145] When a conductive film reflective to visible light is used as each pixel electrode, it is preferable to use a material (e.g., silver or aluminum) with as high a reflectivity as possible across the entire wavelength range of visible light. This not only improves the light extraction efficiency of the organic EL device but also enhances color reproducibility. When a conductive film reflective to visible light is used as each pixel electrode, a so-called top-emission light-emitting device can be obtained, in which light is extracted in the direction away from the substrate. When a light-transmitting conductive film is used as each pixel electrode, a so-called bottom-emission light-emitting device can be obtained, in which light is extracted toward the substrate.
[0146] [Formation of EL Film 120Bb] Subsequently, an EL film 120Bb, which will later become the EL layer 120B, is formed on the first electrode 101B, the first electrode 101G, and the first electrode 101R.
[0147] The EL film 120Bb has at least a light-emitting layer containing a light-emitting material. In addition, the EL film 120Bb may have a structure in which one or more of films functioning as an electron injection layer, an electron transport layer, a charge generation layer, a hole transport layer, or a hole injection layer are stacked. The EL film 120Bb can be formed by, for example, a vapor deposition method, a sputtering method, an inkjet method, or the like. However, the method is not limited to these, and any known film formation method can be used as appropriate.
[0148] For example, the EL film 120Bb is preferably a laminated film in which a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order. In this case, a film having an electron injection layer can be used as the EL layer 121 to be formed later.
[0149] It is preferable that the EL film 120Bb is formed so as not to be provided on the connection electrode 101C. For example, when the EL film 120Bb is formed by vapor deposition (or sputtering), it is preferable that the EL film 120Bb is formed using a shielding mask or removed in a subsequent etching step so that the EL film 120Bb is not formed on the connection electrode 101C.
[0150] [Formation of Mask Film 148a] Next, a mask film 148a is formed to cover the EL film 120Bb. The mask film 148a is preferably formed using a shielding mask so as not to be deposited on the connection electrode 101C, or it is preferably removed in a subsequent etching step.
[0151] The mask film 148a is formed using an organometallic compound represented by general formula (G1) or general formula (G2) described in embodiment 1. This organometallic compound is highly suitable as a material for the mask film 148a, which is formed to protect the EL film 120Bb and facilitate the removal of the aluminum oxide film to be formed later. By using this organometallic compound as the material for the mask film 148a, the aluminum oxide film to be formed later or its residue (etching residue) can be easily removed with water or a liquid containing water as a solvent, preventing the organic EL device from increasing in voltage. Furthermore, it is possible to suppress deterioration of the characteristics of the organic EL device.
[0152] [Formation of Aluminum Oxide Film 144a] Subsequently, the aluminum oxide film 144a is formed to cover the mask film 148a. The aluminum oxide film 144a is preferably formed using a shielding mask so as not to be formed on the connection electrode 101C, or is preferably removed in a subsequent etching step.
[0153] The aluminum oxide film 144a can be a film that is highly resistant to the etching process of each EL film, such as the EL film 120Bb, i.e., a film with a large etching selectivity. The aluminum oxide film 144a can also be a film that has a large etching selectivity with respect to a protective film, such as a metal film or metal compound film 146a (described later). Furthermore, the aluminum oxide film 144a can be a film that can be removed by wet etching, which causes little damage to each EL film.
[0154] The aluminum oxide film 144a can be formed by various film formation methods such as sputtering, evaporation, CVD, and ALD. However, it is preferable to use the ALD method because it is possible to obtain a dense film that has a high barrier property against atmospheric components such as oxygen or water and liquids such as water.
[0155] [Formation of Metal Film or Metal Compound Film 146a] Subsequently, a metal film or metal compound film 146a is formed on the aluminum oxide film 144a (FIG. 8B).
[0156] The metal film or metal compound film 146a is a film that is used as a hard mask when etching the aluminum oxide film 144a later. Furthermore, when processing the metal film or metal compound film 146a later, the aluminum oxide film 144a is exposed. Therefore, a combination of films that have a high etching selectivity between the aluminum oxide film 144a and the metal film or metal compound film 146a is selected. Therefore, a film that can be used for the metal film or metal compound film 146a can be selected depending on the etching conditions for the aluminum oxide film 144a and the metal film or metal compound film 146a.
[0157] For example, when dry etching using a gas containing fluorine (also referred to as a fluorine-based gas) is used to etch the metal film or metal compound film 146 a, silicon, silicon nitride, silicon oxide, tungsten, titanium, molybdenum, tantalum, tantalum nitride, an alloy containing molybdenum and niobium, an alloy containing molybdenum and tungsten, or the like can be used for the metal film or metal compound film 146 a. Here, a metal oxide film can be given as a film that can have a large etching selectivity (i.e., can slow down the etching rate) compared to dry etching using the above-mentioned fluorine-based gas.
[0158] Examples of usable metal oxides include indium gallium zinc oxide (In-Ga-Zn oxide, also referred to as IGZO). Other examples include indium oxide, indium zinc oxide (In-Zn oxide), indium tin oxide (In-Sn oxide), indium titanium oxide (In-Ti oxide), indium tin zinc oxide (In-Sn-Zn oxide), indium titanium zinc oxide (In-Ti-Zn oxide), and indium gallium tin zinc oxide (In-Ga-Sn-Zn oxide). Alternatively, indium tin oxide containing silicon can be used.
[0159] It is also possible to use a metal oxide using an element M (wherein M is one or more elements selected from aluminum, silicon, boron, yttrium, copper, vanadium, beryllium, titanium, iron, nickel, germanium, zirconium, molybdenum, lanthanum, cerium, neodymium, hafnium, tantalum, tungsten, and magnesium) instead of the gallium. In particular, it is preferable that M is one or more elements selected from gallium, aluminum, and yttrium.
[0160] However, the metal film or metal compound film 146a is not limited to this, and can be selected from various materials depending on the etching conditions for the aluminum oxide film 144a and the etching conditions for the metal film or metal compound film 146a. For example, it can be selected from films that can be used for the aluminum oxide film 144a.
[0161] The metal film or metal compound film 146a may be, for example, a nitride film, such as silicon nitride, aluminum nitride, hafnium nitride, titanium nitride, tantalum nitride, tungsten nitride, gallium nitride, or germanium nitride.
[0162] Alternatively, an oxide film can be used as the metal film or metal compound film 146 a. Typically, an oxide film or an oxynitride film such as silicon oxide, silicon oxynitride, aluminum oxynitride, hafnium oxide, or hafnium oxynitride can be used.
[0163] Alternatively, an organic film that can be used for the EL film 120B or the like may be used as the metal film or metal compound film 146a. For example, the same organic film as that used for the EL film 120B, the EL film 120G, or the EL film 120R can be used for the metal film or metal compound film 146a. Using such an organic film is preferable because it allows the film formation equipment to be shared with the EL film 120Bb or the like.
[0164] [Formation of Resist Mask 143a] Subsequently, resist masks 143a are formed on the metal film or metal compound film 146a at positions overlapping the first electrode 101B and the connection electrode 101C (FIG. 8C).
[0165] The resist mask 143a can be made of a resist material containing a photosensitive resin, such as a positive resist material or a negative resist material.
[0166] If the resist mask 143a is formed on the aluminum oxide film 144a without the metal film or metal compound film 146a, the EL film 120Bb may be dissolved by the solvent of the resist material if the aluminum oxide film 144a has defects such as pinholes. By using the metal film or metal compound film 146a, such a problem can be prevented.
[0167] When a film that is less likely to cause defects such as pinholes is used as the aluminum oxide film 144a, the resist mask 143a may be formed directly on the aluminum oxide film 144a without using the metal film or metal compound film 146a.
[0168] [Etching of Metal or Metal Compound Film 146a] Subsequently, a portion of the metal or metal compound film 146a that is not covered by the resist mask 143a is removed by etching to form a strip-shaped or island-shaped metal or metal compound layer 147a. At this time, the metal or metal compound layer 147a is also formed on the connection electrode 101C.
[0169] When etching the metal film or metal compound film 146a, it is preferable to use etching conditions with a high selectivity so that the aluminum oxide film 144a is not removed by the etching. The metal film or metal compound film 146a can be etched by wet etching or dry etching, but using dry etching can prevent the pattern of the metal film or metal compound film 146a from shrinking.
[0170] [Removal of Resist Mask 143a] Subsequently, the resist mask 143a is removed (FIG. 8D).
[0171] The resist mask 143a can be removed by wet etching or dry etching. In particular, the resist mask 143a is preferably removed by dry etching (also called plasma ashing) using oxygen gas as an etching gas.
[0172] At this time, the resist mask 143a is removed while the EL film 120Bb is still covered with the aluminum oxide film 144a, so that the effect on the EL film 120Bb is suppressed. In particular, if the EL film 120Bb comes into contact with oxygen, it may have an adverse effect on the electrical characteristics, so this is suitable for etching using oxygen gas, such as plasma ashing.
[0173] [Etching of Aluminum Oxide Film 144a] Next, using the metal layer or metal compound layer 147a as a mask, a portion of the aluminum oxide film 144a that is not covered by the metal layer or metal compound layer 147a is removed by etching to form strip-shaped aluminum oxide layers 145a and mask layers 149a (FIG. 8E). At the same time, the aluminum oxide layer 145a is also formed on the connection electrode 101C.
[0174] The aluminum oxide film 144a can be etched by wet etching or dry etching, but dry etching is preferable because it can prevent the pattern from shrinking.
[0175] [Etching of EL film 120Bb and metal or metal compound layer 147a] Next, while the metal or metal compound layer 147a is being etched, a portion of the EL film 120Bb that is not covered by the aluminum oxide layer 145a is simultaneously etched away to form a strip-shaped EL layer 120B (FIG. 8F). At this time, the metal or metal compound layer 147a on the connection electrode 101C is also removed.
[0176] Etching the EL film 120Bb and the metal layer or metal compound layer 147a by the same process is preferable because it is possible to simplify the process and reduce the manufacturing cost of the display device.
[0177] In particular, it is preferable to use dry etching using an etching gas that does not contain oxygen as a main component for etching the EL film 120Bb. This makes it possible to suppress deterioration of the EL film 120Bb and realize a highly reliable display device. Examples of etching gases that do not contain oxygen as a main component include CF 4 , C 4 F 8 , S.F. 6 , CHF 3 , Cl 2 , H 2 O, BCl 3 , H 2 Alternatively, a noble gas such as He may be used. Also, a mixed gas of the above gas and a dilution gas that does not contain oxygen may be used as the etching gas.
[0178] The etching of the EL film 120Bb and the etching of the metal layer or metal compound layer 147a may be performed separately. In this case, the EL film 120Bb may be etched first, or the metal layer or metal compound layer 147a may be etched first.
[0179] At this point, the EL layer 120B and the connection electrode 101C are covered with the aluminum oxide layer 145a.
[0180] [Formation of EL Layers 120G and 120R] By repeating the same steps, island-shaped EL layers 120G and 120R and island-shaped aluminum oxide layers 145b and 145c can be formed (FIG. 9A).
[0181] [Formation of Insulating Layer 126b] Subsequently, the insulating layer 126b is formed over the aluminum oxide layer 145a, the aluminum oxide layer 145b, and the aluminum oxide layer 145c (FIG. 9B). The insulating layer 126b can be formed in the same manner as the aluminum oxide layer 145a, the aluminum oxide layer 145b, and the aluminum oxide layer 145c.
[0182] [Formation of Insulating Layer 125b] Then, the insulating layer 125b is formed to cover the insulating layer 126b ( FIG. 9C ). The insulating layer 125b may be formed using a photosensitive organic resin. Examples of the organic material include acrylic resin, polyimide resin, epoxy resin, imide resin, polyamide resin, polyimideamide resin, silicone resin, siloxane resin, benzocyclobutene resin, phenolic resin, and precursors of these resins. Alternatively, the insulating layer 125b may be formed using an organic material such as polyvinyl alcohol (PVA), polyvinyl butyral, polyvinylpyrrolidone, polyethylene glycol, polyglycerin, pullulan, water-soluble cellulose, or alcohol-soluble polyamide resin. Alternatively, a photoresist may be used as the photosensitive resin. The photosensitive resin may be a positive-type material or a negative-type material.
[0183] The insulating layer 125b is preferably subjected to heat treatment after application. The heat treatment is performed at a temperature lower than the heat resistance temperature of the EL layer. The substrate temperature during the heat treatment may be 50° C. or higher and 200° C. or lower, preferably 60° C. or higher and 150° C. or lower, and more preferably 70° C. or higher and 120° C. or lower. This allows the solvent contained in the insulating layer 125b to be removed.
[0184] Next, exposure and development are performed to form openings in the regions of the insulating layer 125b that overlap with the first electrode and the first EL layer, thereby forming the insulating layer 125 (FIG. 9D). When a positive acrylic resin is used for the insulating layer 125b, visible light or ultraviolet light may be irradiated using a mask to the regions where the insulating layer 125b is to be removed.
[0185] When visible light is used for exposure, the visible light preferably includes i-line (wavelength 365 nm). Visible light including g-line (wavelength 436 nm) or h-line (wavelength 405 nm) may also be used.
[0186] When an acrylic resin is used for the insulating layer 125b, an alkaline solution is preferably used as a developer, such as an aqueous solution of tetramethylammonium hydroxide (TMAH).
[0187] After that, it is preferable to expose the entire substrate to visible light or ultraviolet light and irradiate the insulating layer 125. The energy density of the exposure is 0 mJ / cm. 2 Larger than 800 mJ / cm 2 or less, 0 mJ / cm 2 Greater than 500 mJ / cm 2 By performing such exposure after development, the transparency of the insulating layer 125 can be improved in some cases. Furthermore, the substrate temperature required for heat treatment to deform the end portions of the insulating layer 125 into a tapered shape in a later step can be reduced in some cases.
[0188] Next, heat treatment can be performed to transform the insulating layer 125b into an insulating layer 125 having tapered side surfaces. The heat treatment is performed at a temperature lower than the heat resistance temperature of the EL layer. The substrate temperature during the heat treatment may be 50° C. or higher and 200° C. or lower, preferably 60° C. or higher and 150° C. or lower, and more preferably 70° C. or higher and 130° C. or lower. The substrate temperature during the heat treatment in this step is preferably higher than that during the heat treatment performed after the application of the insulating layer 125. This can also improve the corrosion resistance of the insulating layer 125.
[0189] Subsequently, the exposed aluminum oxide layers 145a, 145b, and 145c are removed together with the mask layers 149a, 149b, and 149c using water or a liquid containing water as a solvent (FIG. 9E).
[0190] The removal using water or a liquid containing water as a solvent is carried out by immersing the substrate in water or a liquid containing water as a solvent. This may be followed by shower rinsing with pure water. This treatment removes the aluminum oxide layer together with the mask layer.
[0191] Note that, before the treatment with water or a liquid containing water as a solvent, it is preferable to remove the aluminum oxide layer 145 a, the aluminum oxide layer 145 b, and the aluminum oxide layer 145 c to some extent by wet etching or dry etching. At this time, it is not necessary to remove the aluminum oxide layer 145 a, the aluminum oxide layer 145 b, and the aluminum oxide layer 145 c completely, and since a mask layer exists on the EL layer, the removal of the aluminum oxide layer 145 a, the aluminum oxide layer 145 b, and the aluminum oxide layer 145 c hardly damages the EL layer.
[0192] In this case, it is particularly preferable to use a wet etching method, such as wet etching using a tetramethylammonium hydroxide solution (TMAH), diluted hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, nitric acid, or a mixture thereof.
[0193] Alternatively, the aluminum oxide layer 145 a, the aluminum oxide layer 145 b, and the aluminum oxide layer 145 c are preferably removed by dissolving them in a solvent such as water or alcohol. Here, various alcohols such as ethyl alcohol, methyl alcohol, isopropyl alcohol (IPA), or glycerin can be used as the alcohol capable of dissolving the aluminum oxide layer 145 a, the aluminum oxide layer 145 b, and the aluminum oxide layer 145 c.
[0194] After removing the aluminum oxide layer 145a, the aluminum oxide layer 145b, the aluminum oxide layer 145c, the mask layer 149a, the mask layer 149b, and the mask layer 149c, it is preferable to perform a drying treatment to remove water contained inside the EL layer 120B, the EL layer 120G, and the EL layer 120R and water adsorbed on the surface. For example, it is preferable to perform a heat treatment in an inert gas atmosphere or a reduced-pressure atmosphere. The heat treatment can be performed at a substrate temperature of 50°C or higher and 200°C or lower, preferably 60°C or higher and 150°C or lower, and more preferably 70°C or higher and 120°C or lower. A reduced-pressure atmosphere is preferable because it enables drying at a lower temperature.
[0195] In this manner, the EL layer 120B, the EL layer 120G, and the EL layer 120R can be separately produced.
[0196] [Formation of EL Layer 121] Subsequently, the EL layer 121 is formed to cover the EL layer 120B, the EL layer 120G, the EL layer 120R, and the insulating layer 125.
[0197] The EL layer 121 can be formed by the same method as the EL film 120Bb, etc. When the EL layer 121 is formed by evaporation, it is preferable to form the EL layer 121 using a shielding mask so that the EL layer 121 is not formed on the connection electrode 101C.
[0198] [Formation of Second Electrode 102] Subsequently, the second electrode 102 is formed to cover the EL layer 121 and the connection electrode 101C (FIG. 9F).
[0199] The second electrode 102 can be formed by a film formation method such as evaporation or sputtering. Alternatively, a film formed by evaporation and a film formed by sputtering may be stacked. In this case, the second electrode 102 is preferably formed so as to encompass a region where the electron injection layer 115 is formed. That is, the second electrode 102 can have an edge portion overlapping with the second electrode 102. The second electrode 102 is preferably formed using a shielding mask.
[0200] The second electrode 102 is electrically connected to the connection electrode 101C outside the display area.
[0201] [Formation of Barrier Layer] Subsequently, a barrier layer is formed on the second electrode 102. For depositing the inorganic insulating film used as the protective layer, it is preferable to use a sputtering method, a PECVD method, or an ALD method. In particular, the ALD method is preferable because it has excellent step coverage and is less likely to cause defects such as pinholes. Furthermore, for depositing the organic insulating film, it is preferable to use an inkjet method because it can form a uniform film in a desired area.
[0202] In this manner, a light-emitting device can be manufactured.
[0203] Note that although the above description shows the case where the second electrode 102 and the second EL layer 121 are formed to have different top surface shapes, they may be formed in the same region.
[0204] The structure of this embodiment mode can be used in appropriate combination with other structures.
[0205] In this embodiment, the configuration of an organic EL device, which is an organic semiconductor device having an EL layer as an organic semiconductor layer, will be described with reference to Fig. 10. The organic EL device is an organic semiconductor device including a configuration including an EL layer having a light-emitting layer between a first electrode 101 and a second electrode 102.
[0206] One of the first electrode 101 and the second electrode 102 functions as an anode, and the other functions as a cathode. Fig. 10 illustrates an example in which the first electrode 101 is the anode.
[0207] The anode is preferably formed using a metal, alloy, conductive compound, or mixture thereof having a large work function (specifically, 4.0 eV or more). Specific examples include indium oxide-tin oxide (ITO), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, and indium oxide containing tungsten oxide and zinc oxide (IWZO). These conductive metal oxide films are usually formed by sputtering, but may also be prepared by applying a sol-gel method. As an example of a preparation method, indium oxide-zinc oxide can be formed by sputtering using a target in which 1 to 20 wt % of zinc oxide is added to indium oxide. Indium oxide containing tungsten oxide and zinc oxide (IWZO) can also be formed by sputtering using a target containing 0.5 to 5 wt % tungsten oxide and 0.1 to 1 wt % zinc oxide relative to indium oxide. Other materials that can be used for the anode include, for example, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), and nitrides of metal materials (e.g., titanium nitride). Alternatively, graphene can be used for the anode. Note that using a composite material (described below) for the layer in contact with the anode in the EL layer 103 allows the electrode material to be selected regardless of the work function.
[0208] The EL layer 103 preferably has a stacked layer structure, but the stacked layer structure is not particularly limited, and various layer structures such as a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, a carrier blocking layer (hole blocking layer, electron blocking layer), an exciton blocking layer, and a charge generation layer can be applied. Note that any of the layers does not necessarily have to be provided. In this embodiment, a structure including a hole injection layer 111, a hole transport layer 112, a light-emitting layer 113, an electron transport layer 114, and an electron injection layer 115 as shown in FIG. 10 will be specifically described below.
[0209] The hole-injection layer 111 is a layer containing a substance having acceptor properties. As the substance having acceptor properties, either an organic compound or an inorganic compound can be used.
[0210] As the substance having acceptor properties, a compound having an electron-withdrawing group (a halogen group or a cyano group) can be used, and 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F 4 -TCNQ), chloranil, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (abbreviation: HAT-CN), 1,3,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane (abbreviation: F6-TCCNNQ), 2-(7-dicyanomethylene-1,3,4,5,6,8,9,10-octafluoro-7H-pyren-2-ylidene)malononitrile, etc. In particular, compounds in which an electron-withdrawing group is bonded to a fused aromatic ring having a plurality of heteroatoms, such as HAT-CN, are thermally stable and preferred. Furthermore, [3]radialene derivatives having an electron-withdrawing group (especially a halogen group such as a fluoro group or a cyano group) are preferred because of their extremely high electron-accepting properties. Specific examples include α,α',α''-1,2,3-cyclopropanetriylidenetris[4-cyano-2,3,5,6-tetrafluorobenzeneacetonitrile], α,α',α''-1,2,3-cyclopropanetriylidenetris[2,6-dichloro-3,5-difluoro-4-(trifluoromethyl)benzeneacetonitrile], and α,α',α''-1,2,3-cyclopropanetriylidenetris[2,3,4,5,6-pentafluorobenzeneacetonitrile]. In addition to the organic compounds mentioned above, other materials that can be used as acceptors include molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, manganese oxide, and the like. Other examples include phthalocyanine (abbreviated as H 2The hole injection layer 111 can also be formed from a phthalocyanine complex compound such as copper phthalocyanine (CuPc), aromatic amine compounds such as 4,4'-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB) or N,N'-bis{4-[bis(3-methylphenyl)amino]phenyl}-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (abbreviation: DNTPD), or a polymer such as poly(3,4-ethylenedioxythiophene) / poly(styrenesulfonic acid) (PEDOT / PSS). A substance having acceptor properties can extract electrons from an adjacent hole transport layer (or hole transport material) when an electric field is applied.
[0211] Among substances having acceptor properties, organic compounds having acceptor properties are easy to use because they can be easily vapor-deposited and formed into a film.
[0212] Furthermore, a composite material in which the above-described acceptor substance is contained in a material having a hole-transporting property can also be used for the hole-injection layer 111. Note that by using a composite material in which the acceptor substance is contained in a material having a hole-transporting property, a material for forming an electrode can be selected regardless of the work function. In other words, not only a material with a high work function but also a material with a low work function can be used for the anode.
[0213] As the material having a hole transport property used for the composite material, various organic compounds such as aromatic amine compounds, carbazole derivatives, aromatic hydrocarbons, and polymer compounds (oligomers, dendrimers, polymers, etc.) can be used. −6 cm 2 A substance having a hole mobility of 1 / Vs or more is preferred. Specific examples of organic compounds that can be used as a material having a hole transport property in a composite material are listed below.
[0214] Examples of aromatic amine compounds that can be used in the composite material include N,N'-di(p-tolyl)-N,N'-diphenyl-p-phenylenediamine (abbreviation: DTDPPA), 4,4'-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), N,N'-bis{4-[bis(3-methylphenyl)amino]phenyl}-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (abbreviation: DNTPD), and 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene (abbreviation: DPA3B). Specific examples of the carbazole derivative include 3-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA2), 3-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amino]-9-phenylcarbazole, and Carbazolyl (abbreviation: PCzPCN1), 4,4'-di(N-carbazolyl)biphenyl (abbreviation: CBP), 1,3,5-tris[4-(N-carbazolyl)phenyl]benzene (abbreviation: TCPB), 9-[4-(10-phenyl-9-anthracenyl)phenyl]-9H-carbazole (abbreviation: CzPA), 1,4-bis[4-(N-carbazolyl)phenyl]-2,3,5,6-tetraphenylbenzene, etc. can be used.Examples of aromatic hydrocarbons include 2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA), 2-tert-butyl-9,10-di(1-naphthyl)anthracene, 9,10-bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA), 2-tert-butyl-9,10-bis(4-phenylphenyl)anthracene (abbreviation: t-BuDBA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA), 9,10-diphenylanthracene (abbreviation: DPAnth), 2-tert-butylanthracene (abbreviation: t-BuAnth), 9,10-bis(4-methyl-1-naphthyl)anthracene (abbreviation: DMNA), 2-tert- Examples of suitable anthracene include butyl-9,10-bis[2-(1-naphthyl)phenyl]anthracene, 9,10-bis[2-(1-naphthyl)phenyl]anthracene, 2,3,6,7-tetramethyl-9,10-di(1-naphthyl)anthracene, 2,3,6,7-tetramethyl-9,10-di(2-naphthyl)anthracene, 9,9'-bianthryl, 10,10'-diphenyl-9,9'-bianthryl, 10,10'-bis(2-phenylphenyl)-9,9'-bianthryl, 10,10'-bis[(2,3,4,5,6-pentaphenyl)phenyl]-9,9'-bianthryl, anthracene, tetracene, rubrene, perylene, and 2,5,8,11-tetra(tert-butyl)perylene. In addition, pentacene, coronene, and the like can also be used. The aromatic hydrocarbon having a vinyl group may also have a vinyl skeleton. Examples of the aromatic hydrocarbon having a vinyl group include 4,4′-bis(2,2-diphenylvinyl)biphenyl (abbreviation: DPVBi) and 9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene (abbreviation: DPVPA). Note that the organic compound of one embodiment of the present invention can also be used.
[0215] In addition, polymer compounds such as poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA), poly[N-(4-{N'-[4-(4-diphenylamino)phenyl]phenyl-N'-phenylamino}phenyl)methacrylamide] (abbreviation: PTPDMA), and poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine] (abbreviation: Poly-TPD) can also be used.
[0216] The hole-transporting material used in the composite material preferably has a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, or an anthracene skeleton. In particular, the organic compound may be an aromatic amine having a substituent containing a dibenzofuran ring or a dibenzothiophene ring, an aromatic monoamine having a naphthalene ring, or an aromatic monoamine in which a 9-fluorenyl group is bonded to the nitrogen of the amine via an arylene group. It is preferable that the organic compound is a substance having an N,N-bis(4-biphenyl)amino group, since this allows for the production of an organic EL device with a long life. Specific examples of such organic compounds include N-(4-biphenyl)-6,N-diphenylbenzo[b]naphtho[1,2-d]furan-8-amine (abbreviation: BnfABP), N,N-bis(4-biphenyl)-6-phenylbenzo[b]naphtho[1,2-d]furan-8-amine (abbreviation: BBABnf), 4,4′-bis(6-phenylbenzo[b]naphtho[1,2-d]furan-8-amine), and 4,4′-bis(6-phenylbenzo[b]naphtho[1,2-d]furan-8-amine. N,N-bis(4-biphenyl)benzo[b]naphtho[1,2-d]furan-6-amine (abbreviation: BBABnf(6)), N,N-bis(4-biphenyl)benzo[b]naphtho[1,2-d]furan-8-amine (abbreviation: BBABnf(8)), N,N-bis(4-biphenyl)benzo[b]naphtho[2,3-d]furan-6-amine (abbreviation: BBABnf(8)), N,N-bis(4-biphenyl)benzo[b]naphtho[2,3-d]furan-8 ... lan-4-amine (abbreviation: BBABnf(II)(4)), N,N-bis[4-(dibenzofuran-4-yl)phenyl]-4-amino-p-terphenyl (abbreviation: DBfBB1TP), N-[4-(dibenzothiophen-4-yl)phenyl]-N-phenyl-4-biphenylamine (abbreviation: ThBA1BP), 4-(2-naphthyl)-4',4''-diphenyltriphenylamine (abbreviation: : BBAβNB), 4-[4-(2-naphthyl)phenyl]-4',4''-diphenyltriphenylamine (abbreviation: BBAβNBi), 4,4'-diphenyl-4''-(6;1'-binaphthyl-2-yl)triphenylamine (abbreviation: BBAαNβNB), 4,4'-diphenyl-4''-(7;1'-binaphthyl-2-yl)triphenylamine (abbreviation: BBAαNβNB-03), 4,4'-Diphenyl-4''-(7-phenyl)naphthyl-2-yltriphenylamine (abbreviation: BBAPβNB-03), 4,4'-diphenyl-4''-(6;2'-binaphthyl-2-yl)triphenylamine (abbreviation: BBA(βN2)B), 4,4'-diphenyl-4''-(7;2'-binaphthyl-2-yl)triphenylamine (abbreviation: BBA(βN2)B-03), 4,4'-diphenyl-4''-(4;2'-binaphthyl-1-yl)triphenylamine (abbreviation: BBAβNαNB), 4,4'-diphenyl-4''-(5;2'- binaphthyl-1-yl)triphenylamine (abbreviation: BBAβNαNB-02), 4-(4-biphenylyl)-4'-(2-naphthyl)-4''-phenyltriphenylamine (abbreviation: TPBiAβNB), 4-(3-biphenylyl)-4'-[4-(2-naphthyl)phenyl]-4''-phenyltriphenylamine (abbreviation: mTPBiAβNBi), 4-(4-biphenylyl)-4'-[4-(2-naphthyl)phenyl]-4''-phenyltriphenylamine (abbreviation: TPBiAβNBi), 4-phenyl-4'-(1-naphthyl)triphenylamine 4,4'-bis(1-naphthyl)triphenylamine (abbreviation: αNBB1BP), 4,4'-diphenyl-4''-[4'-(carbazol-9-yl)biphenyl-4-yl]triphenylamine (abbreviation: YGTBi1BP), 4'-[4-(3-phenyl-9H-carbazol-9-yl)phenyl]tris(1,1'-biphenyl-4-yl)amine (abbreviation: YGTBi1BP-02), 4-diphenyl-4'-(2-naphthyl)-4''-{9-(4-biphenylyl)carbazole}triphenylamine N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-N-[4-(1-naphthyl)phenyl]-9,9'-spirobi[9H-fluorene]-2-amine (abbreviation: PCBNBSF), N,N-bis(4-biphenylyl)-9,9'-spirobi[9H-fluorene]-2-amine (abbreviation: BBASF), N,N-bis(1,1'-biphenyl-4-yl)-9,9'-spirobi[9H-fluorene]-4-amine (abbreviation: BBASF(4)), N-(1,1'-biphenyl-2-yl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi[9H-fluorene]-4-amine (abbreviation: oFBiSF), N-(4-biphenyl)-N-(dibenzofuran-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (abbreviation: FrBiF), N-[4-(1-naphthyl)phenyl]-N-[3-(6-phenyldibenzofuran-4-yl)phenyl]-1-naphthylamine (abbreviation: mPDBfBNBN), 4-phenyl-4'-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP), 4 -phenyl-3'-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: mBPAFLP), 4-phenyl-4'-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine (abbreviation: BPAFLBi), 4-phenyl-4'-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBA1BP), 4,4'-diphenyl-4''-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBBi1BP), 4-(1-naphthyl)-4'-(9-phenyl-9H N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]spiro-9,9'-bifluoren-2-amine (abbreviation: PCBASF), N-(1,1'-biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9-dimethyl-9H-fluoren-2-amine (abbreviation: PCBANB), 4,4'-di(1-naphthyl)-4''-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBNBB), N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]spiro-9,9'-bifluoren-2-amine (abbreviation: PCBASF), N-(1,1'-biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9-dimethyl-9H-fluoren-2-amine (abbreviation: PCBBiF), N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi-9H-fluoren-4-amine, N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi-9H-fluoren-3-amine, N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi-9H-fluoren-2-amine, N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi-9H-fluoren-1-amine, and the like can be mentioned.
[0217] Note that the material having hole-transporting properties used in the composite material is more preferably a substance having a relatively deep HOMO level of -5.7 eV or more and -5.4 eV or less. When the material having hole-transporting properties used in the composite material has a relatively deep HOMO level, injection of holes into the hole-transport layer 112 becomes easy, and an organic EL device having a long lifetime can be easily obtained. Furthermore, when the material having hole-transporting properties used in the composite material is a substance having a relatively deep HOMO level, induction of holes is appropriately suppressed, and an organic EL device having a long lifetime can be obtained.
[0218] The refractive index of the layer can be reduced by further mixing an alkali metal or alkaline earth metal fluoride with the composite material (preferably with a fluorine atom ratio of 20% or more in the layer), which also allows a layer with a low refractive index to be formed inside the EL layer 103, thereby improving the external quantum efficiency of the organic EL device.
[0219] By forming the hole injection layer 111, the hole injection property is improved, and an organic EL device with a low driving voltage can be obtained.
[0220] The hole transport layer 112 is formed by containing a material having a hole transport property. −6 cm 2 It is preferable that the material has a hole mobility of 1.0 V or more.
[0221] Examples of the material having a hole transport property include 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4,4′-bis[N-(spiro-9,9′-bifluoren-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB), 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP), 4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP), and 4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP). 4,4'-diphenyl-4''-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBA1BP), 4,4'-diphenyl-4''-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBBi1BP), 4-(1-naphthyl)-4''-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBANB), 4,4'-di(1-naphthyl)-4''-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBANB), compounds having an aromatic amine skeleton such as 9,9-dimethyl-N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]fluoren-2-amine (abbreviation: PCBAF), N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]spiro-9,9'-bifluoren-2-amine (abbreviation: PCBASF); 1,3-bis(N-carbazolyl)benzene (abbreviation: mCP), 4,4'-di(N-carbazolyl)biphenyl; carbazole (abbreviation: CBP), 3,6-bis(3,5-diphenylphenyl)-9-phenylcarbazole (abbreviation: CzTP), 3,3'-bis(9-phenyl-9H-carbazole) (abbreviation: PCCP), 9,9'-bis(biphenyl-4-yl)-3,3'-bi-9H-carbazole (abbreviation: BisBPCz), 9,9'-bis(1,1'-biphenyl-3-yl)-3,3'-bi-9H-carbazole (abbreviation: BismBPCz), 9-(1,1'-biphenyl-3-yl)-9'-(1,1'-biphenyl-4-yl)-9H,9'H-3,3'-Bicarbazole (abbreviation: mBPCCBP), 9-(2-naphthyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole (abbreviation: βNCCP), 9-(3-biphenyl)-9'-(2-naphthyl)-3,3'-bi-9H-carbazole (abbreviation: βNCCmBP), 9-(4-biphenyl)-9'-(2-naphthyl)-3,3'-bi-9H-carbazole (abbreviation: βNCCBP), 9,9'-di-2-naphthyl-3,3'-9H,9'H-bicarbazole (abbreviation: BisβNCz), 9-(2-naphthyl)-9'-[1,1':4',1"- terphenyl]-3-yl-3,3'-9H,9'H-bicarbazole, 9-(2-naphthyl)-9'-[1,1':3',1"-terphenyl]-3-yl-3,3'-9H,9'H-bicarbazole, 9-(2-naphthyl)-9'-[1,1':3',1"-terphenyl]-5'-yl-3,3'-9H,9'H-bicarbazole, 9-(2-naphthyl)-9'-[1,1':4',1"-terphenyl]-4-yl-3,3'-9H,9'H-bicarbazole, 9-(2-naphthyl)-9'-[1,1':3',1"-terphenyl]-4-yl- 3,3'-9H,9'H-bicarbazole, 9-(2-naphthyl)-9'-(triphenylen-2-yl)-3,3'-9H,9'H-bicarbazole, 9-phenyl-9'-(triphenylen-2-yl)-3,3'-bi-9H-carbazole (abbreviation: PCCzTp), 9,9'-bis(triphenylen-2-yl)-3,3'-9H,9'H-bicarbazole, 9-(4-biphenyl)-9'-(triphenylen-2-yl)-3,3'-9H,9'H-bicarbazole, 9-(triphenylen-2-yl)-9'-[1,1':3',1"-taphene compounds having a carbazole skeleton such as 4,4',4''-(benzene-1,3,5-triyl)tri(dibenzothiophene) (abbreviation: DBT3P-II), 2,8-diphenyl-4-[4-(9-phenyl-9H-fluoren-9-yl)phenyl]dibenzothiophene (abbreviation: DBTFLP-III), and 4-[4-(9-phenyl-9H-fluoren-9-yl)phenyl]-6-phenyldibenzothiophene (abbreviation: DBTFLP-IV);Examples of compounds having a furan skeleton include 4',4''-(benzene-1,3,5-triyl)tri(dibenzofuran) (abbreviation: DBF3P-II) and 4-{3-[3-(9-phenyl-9H-fluoren-9-yl)phenyl]phenyl}dibenzofuran (abbreviation: mmDBFFLBi-II). Among the above, compounds having an aromatic amine skeleton and compounds having a carbazole skeleton are preferred because they have good reliability, high hole-transport properties, and contribute to reducing driving voltage. Note that the substances listed as materials having hole-transport properties used in the composite material of the hole-injection layer 111 can also be suitably used as materials for the hole-transport layer 112.
[0222] The light-emitting layer 113 preferably contains a light-emitting substance and a first organic compound. It may further contain a second organic compound. The light-emitting layer 113 may also contain other materials. It may also be a stack of two layers with different compositions. It is preferable that the first organic compound is an organic compound having an electron-transporting property, and the second organic compound is an organic compound having a hole-transporting property.
[0223] The light-emitting substance may be a fluorescent substance, a phosphorescent substance, or a substance that exhibits thermally activated delayed fluorescence (TADF).
[0224] Examples of materials that can be used as the fluorescent substance in the light-emitting layer 113 include the following: In addition, fluorescent substances other than these can also be used.
[0225] 5,6-bis[4-(10-phenyl-9-anthryl)phenyl]-2,2'-bipyridine (abbreviation: PAP2BPy), 5,6-bis[4'-(10-phenyl-9-anthryl)biphenyl-4-yl]-2,2'-bipyridine (abbreviation: PAPP2BPy), N,N'-diphenyl-N,N'-bis[4-(9-phenyl-9H-fluoren-9-yl)phenyl]pyrene-1,6-diamine (abbreviation: 1,6FLPAPrn), N,N'-bis(3-methylphenyl)-N,N'-bis[3-(9-phenyl-9H-fluoren-9-yl)phenyl]pyrene-1,6-diamine )phenyl]pyrene-1,6-diamine (abbreviation: 1,6mMemFLPAPrn), N,N'-bis[4-(9H-carbazol-9-yl)phenyl]-N,N'-diphenylstilbene-4,4'-diamine (abbreviation: YGA2S), 4-(9H-carbazol-9-yl)-4'-(10-phenyl-9-anthryl)triphenylamine (abbreviation: YGAPA), 4-(9H-carbazol-9-yl)-4'-(9,10-diphenyl-2-anthryl)triphenylamine (abbreviation: 2YGAPPA), N,9-diphenyl-N-[4-( 10-phenyl-9-anthryl)phenyl]-9H-carbazol-3-amine (abbreviation: PCAPA), perylene, 2,5,8,11-tetra-tert-butylperylene (abbreviation: TBP), 4-(10-phenyl-9-anthryl)-4'-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBAPA), N,N''-(2-tert-butylanthracene-9,10-diyldi-4,1-phenylene)bis[N,N',N'-triphenyl-1,4-phenylenediamine] (abbreviation: DPABPA), N,9 -diphenyl-N-[4-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazol-3-amine (abbreviation: 2PAPPA), N-[4-(9,10-diphenyl-2-anthryl)phenyl]-N,N',N'-triphenyl-1,4-phenylenediamine (abbreviation: 2DPAPPA), N,N,N',N',N'',N'',N''',N'''-octaphenyldibenzo[g,p]chrysene-2,7,10,15-tetraamine (abbreviation: DBC1), Coumarin 30, N-(9,10-diphenyl-2-anthryl)-N,9-Diphenyl-9H-carbazole-3-amine (abbreviation: 2PCAPA), N-[9,10-bis(1,1'-biphenyl-2-yl)-2-anthryl]-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCABPhA), N-(9,10-diphenyl-2-anthryl)-N,N',N'-triphenyl-1,4-phenylenediamine (abbreviation: 2DPAPA), N-[9,10-bis(1,1'-biphenyl-2-yl)-2-anthryl]-N,N',N'-triphenyl-1,4-phenylenediamine (abbreviation: 2DPA BPhA), 9,10-bis(1,1'-biphenyl-2-yl)-N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylanthracen-2-amine (abbreviation: 2YGABPhA), N,N,9-triphenylanthracen-9-amine (abbreviation: DPhAPhA), Coumarin 545T, N,N'-diphenylquinacridone (abbreviation: DPQd), rubrene, 5,12-bis(1,1'-biphenyl-4-yl)-6,11-diphenyltetracene (abbreviation: BPT), 2-(2-{2-[4-(dimethylamino)phenyl]ethenyl}-6 -methyl-4H-pyran-4-ylidene)propanedinitrile (abbreviation: DCM1), 2-{2-methyl-6-[2-(2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: DCM2), N,N,N',N'-tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation: p-mPhTD), 7,14-diphenyl-N,N,N',N'-tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluoranthene-3,10-diamine amine (abbreviation: p-mPhAFD), 2-{2-isopropyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: DCJTI), 2-{2-tert-butyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: DCJTB), 2-(2,6-bis{2-[4-(dimethylamino)phenyl]ethenyl}-4H-pyran-4-ylidene)propanedinitrile (abbreviation: BisDCM), 2-{2,6-bis[2-(8-methoxy-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: BisDCJ™), N,N'-diphenyl-N,N'-(1,6-pyren-diyl)bis[(6-phenylbenzo[b ]naphtho[1,2-d]furan)-8-amine] (abbreviation: 1,6BnfAPrn-03), 3,10-bis[N-(9-phenyl-9H-carbazol-2-yl)-N-phenylamino]naphtho[2,3-b;6,7-b']bisbenzofuran (abbreviation: 3,10PCA2Nbf(IV)-02), and 3,10-bis[N-(dibenzofuran-3-yl)-N-phenylamino]naphtho[2,3-b;6,7-b']bisbenzofuran (abbreviation: 3,10FrA2Nbf(IV)-02). In particular, condensed aromatic diamine compounds typified by pyrene diamine compounds such as 1,6FLPAPrn, 1,6mMemFLPAPrn, and 1,6BnfAPrn-03 are preferred because of their high hole-trapping properties, excellent luminous efficiency, and excellent reliability. ,
[0226] When a phosphorescent material is used as the light-emitting material in the light-emitting layer 113, examples of materials that can be used include the following.
[0227] (Diisobutyrylmethanato)bis[4,6-bis(3-methylphenyl)pyrimidinato]iridium(III) (abbreviation: [Ir(5mdppm) 2 (dibm)]), bis[4,6-bis(3-methylphenyl)pyrimidinato](dipivaloylmethanato)iridium(III) (abbreviation: [Ir(5mdppm) 2 (dpm)]), bis[4,6-di(naphthalen-1-yl)pyrimidinato](dipivaloylmethanato)iridium(III) (abbreviation: [Ir(dpm) 2organometallic iridium complexes having a pyrimidine skeleton, such as (acetylacetonato)bis(2,3,5-triphenylpyrazinato)iridium(III) (abbreviation: [Ir(tppr) 2 (acac)]), bis(2,3,5-triphenylpyrazinato)(dipivaloylmethanato)iridium(III) (abbreviation: [Ir(tppr) 2 (dpm)]), (acetylacetonato)bis[2,3-bis(4-fluorophenyl)quinoxalinato]iridium(III) (abbreviation: [Ir(Fdpq) 2 organometallic iridium complexes having a pyrazine skeleton, such as tris(1-phenylisoquinolinato-N,C(acac)]); 2’ ) Iridium(III) (abbreviation: [Ir(piq) 3 ]), bis(1-phenylisoquinolinato-N,C 2’ ) iridium(III) acetylacetonate (abbreviation: [Ir(piq) 2 (acac)]), (3,7-diethyl-4,6-nonanedionato-κO4,κO6)bis[2,4-dimethyl-6-[7-(1-methylethyl)-1-isoquinolinyl-κN]phenyl-κC]iridium(III), (3,7-diethyl-4,6-nonanedionato-κO4,κO6)bis[2,4-dimethyl-6-[5-(1-methylethyl)-2-quinolinyl-κN]phenyl-κC]iridium(III). In addition to organometallic iridium complexes having a pyridine skeleton such as [ru-κC]iridium(III), platinum complexes such as 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrinplatinum(II) (abbreviation: PtOEP), tris(1,3-diphenyl-1,3-propanedionato)(monophenanthroline)europium(III) (abbreviation: [Eu(DBM) 3 (Phen)]), tris[1-(2-thenoyl)-3,3,3-trifluoroacetonato](monophenanthroline)europium(III) (abbreviation: [Eu(TTA) 3Examples of suitable iridium complexes include rare earth metal complexes such as iridium fluoride (Phen). These have emission peaks in the wavelength range of 600 nm to 700 nm. Organometallic iridium complexes having a pyrazine skeleton can emit red light with good chromaticity. Other known substances that exhibit red phosphorescence can also be used.
[0228] Tris{2-[5-(2-methylphenyl)-4-(2,6-dimethylphenyl)-4H-1,2,4-triazol-3-yl-κN]phenyl-κC}iridium(III) (abbreviation: [Ir(mpptz-dmp) 3 ]), tris(5-methyl-3,4-diphenyl-4H-1,2,4-triazolato)iridium(III) (abbreviation: [Ir(Mptz) 3 organometallic iridium complexes having a 4H-triazole skeleton, such as tris[3-methyl-1-(2-methylphenyl)-5-phenyl-1H-1,2,4-triazolato]iridium(III) (abbreviation: [Ir(Mptz1-mp) 3 ]), tris(1-methyl-5-phenyl-3-propyl-1H-1,2,4-triazolato)iridium(III) (abbreviation: [Ir(Prptz1-Me) 3 organometallic iridium complexes having a 1H-triazole skeleton, such as fac-tris[1-(2,6-diisopropylphenyl)-2-phenyl-1H-imidazole]iridium(III) (abbreviation: [Ir(iPrpmi) 3 ]), tris[3-(2,6-dimethylphenyl)-7-methylimidazo[1,2-f]phenanthridinato]iridium(III) (abbreviation: [Ir(dmpimpt-Me) 3 organometallic iridium complexes having an imidazole skeleton, such as tris(2-[1-{2,6-bis(1-methylethyl)phenyl}-1H-imidazol-2-yl-κN]-4-cyanophenyl-κC) (abbreviation: CNImIr), tris[(6-tert-butyl-3-phenyl-2H-imidazo[4,5-b]pyrazin-1-yl-κC)phenyl-κC]iridium(III) (abbreviation: [Ir(cb) 3organometallic complexes having a benzimidazolidene skeleton, such as bis[2-(4',6'-difluorophenyl)pyridinato-N,C 2’ ]iridium(III) tetrakis(1-pyrazolyl)borate (abbreviation: FIr6), bis[2-(4',6'-difluorophenyl)pyridinato-N,C 2’ ]iridium(III) picolinate (abbreviation: FIrpic), bis{2-[3',5'-bis(trifluoromethyl)phenyl]pyridinato-N,C 2’} Iridium(III) picolinate (abbreviation: [Ir(CF 3 ppy) 2 (pic)]), bis[2-(4',6'-difluorophenyl)pyridinato-N,C 2’ ] Organometallic iridium complexes having a phenylpyridine derivative having an electron-withdrawing group as a ligand, such as iridium(III) acetylacetonate (abbreviation: FIracac), are examples of such compounds that exhibit blue phosphorescence and have an emission peak in the wavelength range of 440 nm to 520 nm.
[0229] Also, tris(4-methyl-6-phenylpyrimidinato)iridium(III) (abbreviation: [Ir(mppm) 3 ]), tris(4-t-butyl-6-phenylpyrimidinato)iridium(III) (abbreviation: [Ir(tBuppm) 3 ]), (acetylacetonato)bis(6-methyl-4-phenylpyrimidinato)iridium(III) (abbreviation: [Ir(mppm) 2 (acac)]), (acetylacetonato)bis(6-tert-butyl-4-phenylpyrimidinato)iridium(III) (abbreviation: [Ir(tBuppm) 2 (acac)]), (acetylacetonato)bis[6-(2-norbornyl)-4-phenylpyrimidinato]iridium(III) (abbreviation: [Ir(nbppm) 2 (acac)]), (acetylacetonato)bis[5-methyl-6-(2-methylphenyl)-4-phenylpyrimidinato]iridium(III) (abbreviation: [Ir(mpmppm) 2(acac)]), (acetylacetonato)bis(4,6-diphenylpyrimidinato)iridium(III) (abbreviation: [Ir(dppm) 2 organometallic iridium complexes having a pyrimidine skeleton, such as (acetylacetonato)bis(3,5-dimethyl-2-phenylpyrazinato)iridium(III) (abbreviation: [Ir(mppr-Me) 2 (acac)]), (acetylacetonato)bis(5-isopropyl-3-methyl-2-phenylpyrazinato)iridium(III) (abbreviation: [Ir(mppr-iPr) 2 organometallic iridium complexes having a pyrazine skeleton, such as tris(2-phenylpyridinato-N,C(acac)]); 2’ ) Iridium(III) (abbreviation: [Ir(ppy) 3 ]), bis(2-phenylpyridinato-N,C 2’ ) Iridium(III) acetylacetonate (abbreviation: [Ir(ppy) 2 (acac)]), bis(benzo[h]quinolinato)iridium(III) acetylacetonate (abbreviation: [Ir(bzq) 2 (acac)]), tris(benzo[h]quinolinato)iridium(III) (abbreviation: [Ir(bzq) 3 ]), tris(2-phenylquinolinato-N,C 2’ ) Iridium(III) (abbreviation: [Ir(pq) 3 ]), bis(2-phenylquinolinato-N,C 2’ ) iridium(III) acetylacetonate (abbreviation: [Ir(pq) 2 (acac)]), [2-d3-methyl-8-(2-pyridinyl-κN)benzofuro[2,3-b]pyridine-κC]bis[2-(5-d3-methyl-2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: Ir(5mppy-d3) 2(mbfpypy-d3)), [2-(methyl-d3)-8-[4-(1-methylethyl-1-d)-2-pyridinyl-κN]benzofuro2,[3-b]pyridin-7-yl-κC]bis[5-(methyl-d3)-2-[5-(methyl-d3)-2-pyridinyl-κN]phenyl-κC]iridium(III) (abbreviation: Ir(5mtpy-d6) 2 (mbfpypy-iPr-d4)), [2-d3-methyl-(2-pyridinyl-κN)benzofuro[2,3-b]pyridine-κC]bis[2-(2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: Ir(ppy) 2 (mbfppypy-d3)), [2-(4-d3-methyl-5-phenyl-2-pyridinyl-κN2)phenyl-κC]bis[2-(5-d3-methyl-2-pyridinyl-κN2)phenyl-κC]iridium(III) (abbreviation: [Ir(5mppy-d3)2(mdppy-d3)]), [2-methyl-(2-pyridinyl-κN)benzofuro[ [2,3-b]pyridine-κC]bis[2-(2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: [Ir(ppy)2(mbfpypy)]), [2-(4-methyl-5-phenyl-2-pyridinyl-κN)phenyl-κC]bis[2-(2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: Ir(ppy) 2 In addition to organometallic iridium complexes having a pyridine skeleton, such as tris(acetylacetonato)(monophenanthroline)terbium(III) (abbreviation: [Tb(acac) 3 These compounds mainly exhibit green phosphorescence, with an emission peak in the wavelength range of 500 nm to 600 nm. Organometallic iridium complexes having a pyrimidine skeleton are particularly preferred because they are remarkably excellent in reliability and luminous efficiency.
[0230] Examples of TADF materials that can be used include fullerene and its derivatives, acridine and its derivatives, and eosin derivatives. Other examples include metal-containing porphyrins containing magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), platinum (Pt), indium (In), or palladium (Pd). Examples of metal-containing porphyrins include protoporphyrin-tin fluoride complexes (SnF) represented by the following structural formula: 2 (Proto IX)), mesoporphyrin-tin fluoride complex (SnF 2 (Meso IX)), hematoporphyrin-tin fluoride complex (SnF 2 (Hemato IX)), coproporphyrin tetramethyl ester-tin fluoride complex (SnF 2 (Copro III-4Me)), octaethylporphyrin-tin fluoride complex (SnF 2 (OEP)), etioporphyrin-tin fluoride complex (SnF 2 (Etio I)), octaethylporphyrin-platinum chloride complex (PtCl 2 OEP) and the like.
[0231]
[0232] Further, 2-(biphenyl-4-yl)-4,6-bis(12-phenylindolo[2,3-a]carbazol-11-yl)-1,3,5-triazine (abbreviation: PIC-TRZ), 9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9′-phenyl-9H,9′H-3,3′-bicarbazole (abbreviation: PCCzTzn), 2-{4-[3-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}-4,6-diphenyl-1,3,5-triazine (abbreviation: PCCzPTzn), 2-[4-(10H-phenoxazin-10-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (abbreviation: PCCzPTzn), and Heterocyclic compounds having one or both of a π-electron rich heteroaromatic ring and a π-electron deficient heteroaromatic ring, such as 3-[4-(5-phenyl-5,10-dihydrophenazin-10-yl)phenyl]-4,5-diphenyl-1,2,4-triazole (abbreviation: PPZ-3TPT), 3-(9,9-dimethyl-9H-acridin-10-yl)-9H-xanthen-9-one (abbreviation: ACRXTN), bis[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]sulfone (abbreviation: DMAC-DPS), and 10-phenyl-10H,10′H-spiro[acridine-9,9′-anthracene]-10′-one (abbreviation: ACRSA), can also be used. The heterocyclic compound has a π-electron-rich heteroaromatic ring and a π-electron-deficient heteroaromatic ring, and therefore has high electron transport and hole transport properties, and is therefore preferred. Among the skeletons having a π-electron-deficient heteroaromatic ring, pyridine skeleton, diazine skeleton (pyrimidine skeleton, pyrazine skeleton, pyridazine skeleton), and triazine skeleton are preferred because they are stable and reliable. In particular, benzofuropyrimidine skeleton, benzothienopyrimidine skeleton, benzofuropyrazine skeleton, and benzothienopyrazine skeleton are preferred because they have high acceptor properties and good reliability. Furthermore, among the skeletons having a π-electron-rich heteroaromatic ring, acridine skeleton, phenoxazine skeleton, phenothiazine skeleton, furan skeleton, thiophene skeleton, and pyrrole skeleton are preferred because they are stable and reliable.The furan skeleton is preferably a dibenzofuran skeleton, and the thiophene skeleton is preferably a dibenzothiophene skeleton. The pyrrole skeleton is particularly preferably an indole skeleton, a carbazole skeleton, an indolocarbazole skeleton, a bicarbazole skeleton, or a 3-(9-phenyl-9H-carbazol-3-yl)-9H-carbazole skeleton. A substance in which a π-electron-rich heteroaromatic ring and a π-electron-deficient heteroaromatic ring are directly bonded is particularly preferred because the electron-donating property of the π-electron-rich heteroaromatic ring and the electron-accepting property of the π-electron-deficient heteroaromatic ring are both enhanced, reducing the energy difference between the S1 level and the T1 level, thereby enabling efficient thermally activated delayed fluorescence. Instead of the π-electron-deficient heteroaromatic ring, an aromatic ring bonded to an electron-withdrawing group such as a cyano group may be used. The π-electron-rich skeleton may be, for example, an aromatic amine skeleton or a phenazine skeleton. Examples of usable π-electron-deficient skeletons include a xanthene skeleton, a thioxanthene dioxide skeleton, an oxadiazole skeleton, a triazole skeleton, an imidazole skeleton, an anthraquinone skeleton, a boron-containing skeleton such as phenylborane or boranthrene, an aromatic ring having a nitrile group or a cyano group such as benzonitrile or cyanobenzene, a heteroaromatic ring, a carbonyl skeleton such as benzophenone, a phosphine oxide skeleton, a sulfone skeleton, etc. In this way, a π-electron-deficient skeleton and a π-electron-rich skeleton can be used in place of at least one of a π-electron-deficient heteroaromatic ring and a π-electron-rich heteroaromatic ring.
[0233]
[0234] Alternatively, a TADF material may be used, which is capable of extremely fast and reversible intersystem crossing and emits light according to a thermal equilibrium model between a singlet excited state and a triplet excited state. Such a TADF material has an extremely short emission lifetime (excitation lifetime) for a TADF material, and can suppress a decrease in efficiency in the high-brightness region of a light-emitting device. Specifically, a material with the molecular structure shown below may be used.
[0235]
[0236] The TADF material is a material that has a small difference between the S1 level and the T1 level and has the function of converting triplet excitation energy to singlet excitation energy by reverse intersystem crossing. Therefore, triplet excitation energy can be upconverted to singlet excitation energy (reverse intersystem crossing) with a small amount of thermal energy, and a singlet excited state can be efficiently generated. Furthermore, triplet excitation energy can be converted into luminescence.
[0237] Furthermore, an exciplex (also called an exciplex) that forms an excited state with two types of substances has an extremely small difference between the S1 level and the T1 level, and functions as a TADF material that can convert triplet excitation energy into singlet excitation energy.
[0238] The T1 level can be determined by using a phosphorescence spectrum observed at low temperatures (e.g., 77 K to 10 K). When a tangent line is drawn at the base of the fluorescence spectrum on the short wavelength side of the TADF material, and the energy of the wavelength of the extrapolated line is defined as the S1 level, and when a tangent line is drawn at the base of the phosphorescence spectrum on the short wavelength side of the TADF material, and the energy of the wavelength of the extrapolated line is defined as the T1 level, the difference between S1 and T1 is preferably 0.3 eV or less, and more preferably 0.2 eV or less.
[0239] When a TADF material is used as a light-emitting material, the S1 level of the host material is preferably higher than the S1 level of the TADF material, and the T1 level of the host material is preferably higher than the T1 level of the TADF material.
[0240] Examples of electron transport materials used as the host material include bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeBq 2), bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III) (abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Znq), bis[2-(2-benzoxazolyl)phenolato]zinc(II) (abbreviation: ZnPBO), bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ), or other metal complexes; and organic compounds having a π-electron-deficient heteroaromatic ring can be used. Examples of organic compounds having a π-electron-deficient heteroaromatic ring include 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (abbreviation: TAZ), 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene (abbreviation: OXD-7), 9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9H-carbazole (abbreviation: CO11), 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole) (abbreviation: TPBI), 2-[3-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: mDBTBIm-II), and other polyazole skeletons. and organic compounds containing a heteroaromatic ring having the formula: 2-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTPDBq-II), 2-[3-(3′-dibenzothiophen-4-yl)biphenyl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTBPDBq-II), 2-[3′-(9H-carbazol-9-yl)biphenyl-3-yl]dibenzo[f,h]quinoxaline (abbreviation: 2mCz BPDBq), 4,6-bis[3-(phenanthrene-9-yl)phenyl]pyrimidine (abbreviation: 4,6mPnP2Pm), 4,6-bis[3-(4-dibenzothienyl)phenyl]pyrimidine (abbreviation: 4,6mDBTP2Pm-II), 2,6-bis(4-naphthalen-1-ylphenyl)-4-[4-(3-pyridyl)phenyl]pyrimidine (abbreviation: 2,4NP-6PyPPm), 6-(1,1′-biphenyl-3-yl)-4-[3,5-bis(9H-carbazol-9-yl)phenyl]-2-phenylpyrimidine (abbreviation: 6mBP-4Cz2PPm), 4-[3,5-bis(9H-carbazol-9-yl)phenyl]-2-phenyl-6-(1,1'-biphenyl-4-yl)pyrimidine (abbreviation: 6BP-4Cz2PPm), 7-[4-(9-phenyl-9H-carbazol-2-yl)quinazolin-2-yl]-7H-dibenzo[c,g]carbazole (abbreviation: PC-cgDBCzQz), 11-[(3'-dibenzothiophen-4-yl)biphenyl-3-yl]phenanthroline 11-[(3'-dibenzothiophen-4-yl)biphenyl-4-yl]phenanthro[9',10':4,5]furo[2,3-b]pyrazine (abbreviation: 11mDBtBPPnfpr), 11-[(3'-dibenzothiophen-4-yl)biphenyl-4-yl]phenanthro[9',10':4,5]furo[2,3-b]pyrazine, 11-[(3'-(9H-carbazol-9-yl)biphenyl-3-yl]phenanthro[9',10':4,5]furo[2,3-b]pyrazine, 12-(9'-phenyl-3,3'-bi-9H-carbazol-9-yl)phenanthro[9',10':4,5]furo[2,3-b]pyrazine (abbreviation 9-(9'-phenyl-3,3'-bi-9H-carbazol-9-yl)naphtho[1',2':4,5]furo[2,3-b]pyrazine (abbreviation: 9pmPCBPNfpr), 9-(9'-phenyl-3,3'-bi-9H-carbazol-9-yl)naphtho[1',2':4,5]furo[2,3-b]pyrazine (abbreviation: 9PCCzNfpr), 10-(9'-phenyl-3,3'-bi-9H-carbazol-9-yl)naphtho[1',2':4,5]furo[2,3-b]pyrazine (abbreviation: 10PCCzNf pr), 9-[3'-(6-phenylbenzo[b]naphtho[1,2-d]furan-8-yl)biphenyl-3-yl]naphtho[1',2':4,5]furo[2,3-b]pyrazine (abbreviation: 9mBnfBPNfpr), 9-{3-[6-(9,9-dimethylfluoren-2-yl)dibenzothiophen-4-yl]phenyl}naphtho[1',2':4,5]furo[2,3-b]pyrazine (abbreviation: 9mFDBtPNfpr), 9-[3'-(6-phenyldibenzothiophen-4-yl)biphenyl-3-yl]naphtho[1',2':4,5]furo[2,3-b]pyrazine (abbreviation: 9mDBtBPNfpr-02), 9-[3-(9'-phenyl-3,3'-bi-9H-carbazol-9-yl)phenyl]naphtho[1',2':4,5]furo[2,3-b]pyrazine (abbreviation: 9mPCCzPNfpr), 9-{(3'-[2,8-diphenyldibenzothiophen-4-yl]biphenyl)-3-yl}naphtho[1',2':4,5]furo[2,3-b]pyrazine, 11-{3'-[2,8-diphenyldibenzothiophen-4-yl]biphenyl-3-yl}phenanthro[9',10':4 organic compounds containing heteroaromatic rings having a diazine skeleton, such as 3,5-bis[3-(9H-carbazol-9-yl)phenyl]pyridine (abbreviation: 35DCzPPy) and 1,3,5-tri[3-(3-pyridyl)phenyl]benzene (abbreviation: TmPyPB); organic compounds containing heteroaromatic rings having a pyridine skeleton, such as 2-[3′-(9,9-dimethyl-9H-fluoren-2-yl)-1,1′-biphenyl-3-yl]-4,6-diphenyl-1,3,5-triazine (abbreviation: mFBPTzn); ,1'-biphenyl)-4-yl]-4-phenyl-6-[9,9'-spirobi(9H-fluoren)-2-yl]-1,3,5-triazine (abbreviation: BP-SFTzn), 2-{3-[3-(benzo[b]naphtho[1,2-d]furan-8-yl)phenyl]phenyl}-4,6-diphenyl-1,3,5-triazine (abbreviation: mBnfBPTzn), 2-{3-[3-(benzo[b]naphtho[1,2-d]furan-6-yl)phenyl]phenyl}-4,6-diphenyl-1,3,5-triazine (abbreviation: mBnfBPTzn-02), 5 -[3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-7,7-dimethyl-5H,7H-indeno[2,1-b]carbazole (abbreviation: mINc(II)PTzn), 2-[3'-(triphenylen-2-yl)-1,1'-biphenyl-3-yl]-4,6-diphenyl'1,3,5-triazine (abbreviation: mTpBPTzn), 9-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-2-dibenzothiophenyl]-2-phenyl-9H-carbazole (abbreviation: PCDBfTzn), 2-[1,Examples of suitable organic compounds include organic compounds containing a heteroaromatic ring having a triazine skeleton, such as [1'-biphenyl]-3-yl-4-phenyl-6-(8-[1,1':4',1''-terphenyl]-4-yl-1-dibenzofuranyl)-1,3,5-triazine (abbreviation: mBP-TPDBfTzn). Among the above, organic compounds containing a heteroaromatic ring having a diazine skeleton, organic compounds containing a heteroaromatic ring having a pyridine skeleton, and organic compounds containing a heteroaromatic ring having a triazine skeleton are preferred due to their high reliability. In particular, organic compounds containing a heteroaromatic ring having a diazine (pyrimidine, pyrazine) skeleton and organic compounds containing a heteroaromatic ring having a triazine skeleton have high electron transport properties and contribute to reducing driving voltage.
[0241] As the hole transport material used as the host material, an organic compound having an amine skeleton and a π-electron-rich heteroaromatic ring can be used. Examples of the organic compound having an amine skeleton and a π-electron-rich heteroaromatic ring include 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4,4′-bis[N-(spiro-9,9′-bifluoren-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB), 4-phenyl-4′-(9-phenylfluoren-9-yl)triamine, and the like. triphenylamine (abbreviation: BPAFLP), 4-phenyl-3'-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: mBPAFLP), 4-phenyl-4'-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBA1BP), 4,4'-diphenyl-4''-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBBi1BP), 4-(1-naphthyl)-4'-(9-phenyl-9H-carbazol-3-yl)triphenylamine aromatic amines such as 4,4'-di(1-naphthyl)-4''-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBANB), 4,4'-di(1-naphthyl)-4''-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBNBB), 9,9-dimethyl-N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]fluoren-2-amine (abbreviation: PCBAF), and N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]spiro-9,9'-bifluoren-2-amine (abbreviation: PCBASF) compounds having an amine skeleton, 1,3-bis(N-carbazolyl)benzene (abbreviation: mCP), 4,4′-di(N-carbazolyl)biphenyl (abbreviation: CBP), 3,6-bis(3,5-diphenylphenyl)-9-phenylcarbazole (abbreviation: CzTP), 3,3′-bis(9-phenyl-9H-carbazole) (abbreviation: PCCP), N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-bis(9,9-dimethyl-9H-fluoren-2-yl)amine (abbreviation: PCBFF), N-(1,1'-biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9-dimethyl-9H-fluoren-4-amine, N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluoren-4-amine, N-(1,1'-biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9-diphenyl-9H-fluoren- N-(1,1'-biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9-diphenyl-9H-fluoren-4-amine, N-(1,1'-biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9'-spirobi(9H-fluorene)-2-amine (abbreviation: PCBBiSF), N-(1,1'-biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9'-spirobi(9H-fluorene)-2-amine (abbreviation: PCBBiSF), N-(1,1'-biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9'-diphenyl-9H-fluoren-4-amine N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-N-(1,1':3',1"-terphenyl-4-yl)-9,9-dimethyl-9H-fluoren-2-amine, N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-N-(1,1':4',1"-terphenyl-4-yl)-9,9-dimethyl-9H-fluoren-2-amine, N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-N-(1,1':4',1"-terphenyl-4-yl)-9,9-dimethyl-9H-fluoren-2-amine, N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-N-(1,1':4',1"-terphenyl-4-yl)-9,9-dimethyl-9H-fluoren-2-amine compounds having a carbazole skeleton such as N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-N-(1,1':3',1''-terphenyl-4-yl)-9,9-dimethyl-9H-fluoren-4-amine and N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-N-(1,1':4',1''-terphenyl-4-yl)-9,9-dimethyl-9H-fluoren-4-amine; 4,4',4''-(benzene-1,3,5-triyl)tri(dibenzothiophene) (abbreviation: DBT3P-II);Examples of suitable compounds include compounds having a thiophene skeleton, such as 8-diphenyl-4-[4-(9-phenyl-9H-fluoren-9-yl)phenyl]dibenzothiophene (abbreviation: DBTFLP-III) and 4-[4-(9-phenyl-9H-fluoren-9-yl)phenyl]-6-phenyldibenzothiophene (abbreviation: DBTFLP-IV), and compounds having a furan skeleton, such as 4,4′,4″-(benzene-1,3,5-triyl)tri(dibenzofuran) (abbreviation: DBF3P-II) and 4-{3-[3-(9-phenyl-9H-fluoren-9-yl)phenyl]phenyl}dibenzofuran (abbreviation: mmDBFFLBi-II). Among the compounds listed above, compounds having an aromatic amine skeleton and compounds having a carbazole skeleton are preferred because they have good reliability, high hole transport properties, and contribute to reducing driving voltage. In addition, the organic compounds listed as examples of the material having hole transport properties in the hole transport layer 112 can also be used as the hole transport material of the host.
[0242] By mixing an electron transport material and a hole transport material, the transport property of the light-emitting layer 113 can be easily adjusted, and the recombination region can be easily controlled. In addition, a TADF material can also be used as an electron transport material or a hole transport material.
[0243] The TADF materials that can be used as the host material can be the same as those listed above. When a TADF material is used as the host material, triplet excitation energy generated in the TADF material is converted into singlet excitation energy by reverse intersystem crossing, and the energy is further transferred to the light-emitting substance, thereby improving the luminous efficiency of the organic EL device. In this case, the TADF material functions as an energy donor, and the light-emitting substance functions as an energy acceptor.
[0244] This is very effective when the luminescent material is a fluorescent luminescent material. Furthermore, in this case, in order to obtain high luminous efficiency, it is preferable that the S1 level of the TADF material is higher than the S1 level of the fluorescent luminescent material. Furthermore, it is preferable that the T1 level of the TADF material is higher than the S1 level of the fluorescent luminescent material. Therefore, it is preferable that the T1 level of the TADF material is higher than the T1 level of the fluorescent luminescent material.
[0245] It is also preferable to use a TADF material that emits light that overlaps with the wavelength of the lowest-energy absorption band of the fluorescent material, since this allows for smooth transfer of excitation energy from the TADF material to the fluorescent material, resulting in efficient light emission.
[0246] Furthermore, in order to efficiently generate singlet excitation energy from triplet excitation energy through reverse intersystem crossing, it is preferable that carrier recombination occurs in the TADF material. It is also preferable that the triplet excitation energy generated in the TADF material does not transfer to the triplet excitation energy of the fluorescent material. To this end, it is preferable that the fluorescent material has a protecting group around the luminophore (the skeleton responsible for light emission) possessed by the fluorescent material. The protecting group is preferably a substituent without a π bond, and is preferably a saturated hydrocarbon. Specific examples include alkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 10 carbon atoms, and trialkylsilyl groups having 3 to 10 carbon atoms. It is even more preferable that the protecting group has multiple protecting groups. Substituents without a π bond have poor carrier transport function, so the distance between the TADF material and the luminophore of the fluorescent material can be increased without significantly affecting carrier transport or carrier recombination. Here, the luminophore refers to the atomic group (skeleton) responsible for light emission in the fluorescent material. The luminophore preferably has a skeleton having a π bond, preferably contains an aromatic ring, and preferably has a fused aromatic ring or a fused heteroaromatic ring. Examples of the fused aromatic ring or the fused heteroaromatic ring include a phenanthrene skeleton, a stilbene skeleton, an acridone skeleton, a phenoxazine skeleton, and a phenothiazine skeleton. In particular, fluorescent substances having a naphthalene skeleton, an anthracene skeleton, a fluorene skeleton, a chrysene skeleton, a triphenylene skeleton, a tetracene skeleton, a pyrene skeleton, a perylene skeleton, a coumarin skeleton, a quinacridone skeleton, or a naphthobisbenzofuran skeleton are preferred because of their high fluorescence quantum yield.
[0247] When a fluorescent light-emitting substance is used as the light-emitting substance, a material having an anthracene skeleton is suitable as the host material. Using a substance having an anthracene skeleton as the host material for a fluorescent light-emitting substance makes it possible to realize an emitting layer with both excellent luminous efficiency and durability. As a substance having an anthracene skeleton to be used as the host material, a substance having a diphenylanthracene skeleton, particularly a 9,10-diphenylanthracene skeleton, is preferred because it is chemically stable. Furthermore, a host material having a carbazole skeleton is preferred because it enhances hole injection and transport properties. However, a host material containing a benzocarbazole skeleton in which a benzene ring is further condensed to carbazole is more preferred because its HOMO is shallower by about 0.1 eV than that of carbazole, making it easier for holes to enter. In particular, a host material containing a dibenzocarbazole skeleton is preferred because its HOMO is shallower by about 0.1 eV than that of carbazole, making it easier for holes to enter, and it also has excellent hole transport properties and high heat resistance. Therefore, a more preferable host material is a substance having both a 9,10-diphenylanthracene skeleton and a carbazole skeleton (or a benzocarbazole skeleton or a dibenzocarbazole skeleton). Note that, in view of the hole injection / transport properties, a benzofluorene skeleton or a dibenzofluorene skeleton may be used instead of the carbazole skeleton.Examples of such substances include 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: PCzPA), 3-[4-(1-naphthyl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: PCPN), 9-[4-(10-phenyl-9-anthracenyl)phenyl]-9H-carbazole (abbreviation: CzPA), 7-[4-(10-phenyl-9-anthryl)phenyl]-7H-dibenzo[c,g]carbazole (abbreviation: cgDBCzPA), 6-[3-(9,10-diphenyl-2 -anthryl)phenyl]-benzo[b]naphtho[1,2-d]furan (abbreviation: 2mBnfPPA), 9-phenyl-10-{4-(9-phenyl-9H-fluoren-9-yl)biphenyl-4'-yl}anthracene (abbreviation: FLPPA), 9-(1-naphthyl)-10-[4-(2-naphthyl)phenyl]anthracene (abbreviation: αN-βNPAnth), 9-(1-naphthyl)-10-(2-naphthyl)anthracene (abbreviation: α,βADN), 2-(10-phenylanthracen-9-yl)dibenzofuran, 2-(10-phenyl- 9-anthracenyl)-benzo[b]naphtho[2,3-d]furan (abbreviation: Bnf(II)PhA), 9-(2-naphthyl)-10-[3-(2-naphthyl)phenyl]anthracene (abbreviation: βN-mβNPAnth), 1-[4-(10-[,1,1′-biphenyl]-4-yl-9-anthracenyl)phenyl]-2-ethyl-1H-benzimidazole (abbreviation: EtBImPBPhA), 2,9-di(1-naphthyl)-10-phenylanthracene (abbreviation: 2αN-αNPhA), 9-(1-naphthyl)-10-[3-(1-naphthyl)phenyl]anthracene (abbreviation: βN-mβNPAnth),
[0033] 9-(2-naphthyl)-10-[3-(1-naphthyl)phenyl]anthracene (abbreviation: αN-mαNPAnth), 9-(1-naphthyl)-10-[4-(1-naphthyl)phenyl]anthracene (abbreviation: αN-αNPAnth), 9-(2-naphthyl)-10-[4-(2-naphthyl)phenyl]anthracene (abbreviation: βN-βNPAnth), 2-(1-naphthyl)-9-(2-naphthyl)-10-phenylanthracene (abbreviation: 2αN-βNPh), and the like.In particular, CzPA, cgDBCzPA2mBnfPPA, and PCzPA are preferable choices because they exhibit very good properties.
[0248] A phosphorescent material can be used as part of the mixed material. The phosphorescent material can be used as an energy donor that provides excitation energy to a fluorescent material when the fluorescent material is used as a light-emitting material.
[0249] The mixed materials may also form an exciplex. The exciplex is preferably selected from a combination that forms an exciplex that emits light that overlaps with the wavelength of the lowest-energy absorption band of the light-emitting material, because this allows for smooth energy transfer and efficient light emission. Furthermore, this configuration is also preferable because it reduces the driving voltage.
[0250] At least one of the materials forming the exciplex may be a phosphorescent material, which allows efficient conversion of triplet excitation energy into singlet excitation energy through reverse intersystem crossing.
[0251] As a combination of materials that efficiently form an exciplex, it is preferable that the HOMO level of the material having hole transport properties is equal to or higher than the HOMO level of the material having electron transport properties. Also, it is preferable that the LUMO level of the material having hole transport properties is equal to or higher than the LUMO level of the material having electron transport properties. Note that the LUMO level and HOMO level of the material can be derived from the electrochemical properties (reduction potential and oxidation potential) of the material measured by cyclic voltammetry (CV).
[0252] The formation of exciplexes can be confirmed, for example, by comparing the emission spectra of a material having hole transport properties, a material having electron transport properties, and a mixed film obtained by mixing these materials, and observing the phenomenon in which the emission spectrum of the mixed film is shifted to longer wavelengths than the emission spectra of each material (or has a new peak on the longer wavelength side). Alternatively, the formation of exciplexes can be confirmed by comparing the transient photoluminescence (PL) of a material having hole transport properties, the transient PL of a material having electron transport properties, and a mixed film obtained by mixing these materials, and observing differences in transient response, such as the transient PL lifetime of the mixed film having a longer-lifetime component or a larger proportion of delayed components than the transient PL lifetimes of the individual materials. The above-mentioned transient PL may also be interpreted as transient electroluminescence (EL). In other words, the formation of exciplexes can also be confirmed by comparing the transient EL of a material having hole transport properties, the transient EL of a material having electron transport properties, and a mixed film obtained by mixing these materials, and observing the differences in transient response.
[0253] When a hole-blocking layer is provided, the hole-blocking layer is in contact with the light-emitting layer 113 and is formed by containing an organic compound having an electron-transporting property and capable of blocking holes. The organic compound constituting the hole-blocking layer is preferably a material having an excellent electron-transporting property, a low hole-transporting property, and a deep HOMO level. Specifically, the hole-blocking layer has a HOMO level that is 0.5 eV or more deeper than the HOMO level of the material contained in the light-emitting layer 113, and an electron mobility at a square root of an electric field strength [V / cm] of 600 is 1×10 −6 cm 2 A substance having an electron mobility of 1 / Vs or more is preferred.
[0254] In particular, 2-{3-[3-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}dibenzo[f,h]quinoxaline (abbreviation: 2mPCCzPDBq), 2-{3-[2-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}dibenzo[f,h]quinoxaline (abbreviation: 2mPCCzPDBq-02), 2-{3-[3-(N-phenyl-9H-carbazol-2-yl)-9H-carbazol-9-yl]phenyl}dibenzo[f,h]quinoxaline (abbreviation: 2 mPCCzPDBq-03), 2-{3-[3-(N-(3,5-di-tert-butylphenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}dibenzo[f,h]quinoxaline, 9-[3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-9'-phenyl-3,3'-bi-9H-carbazole (abbreviation: mPCCzPTzn), 9-[3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-9'-phenyl-2,3'-bi-9H-carbazole (abbreviation: mPC CzPTzn-02), 2-{4-[3-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}-4,6-diphenyl-1,3,5-triazine (abbreviation: PCCzPTzn), 9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9'-phenyl-3,3'-bi-9H-carbazole (abbreviation: PCCzTzn(CzT)), 9-[3-(4,6-diphenyl-pyrimidin-2-yl)phenyl]-9'-phenyl-3,3'-bi-9H-carbazole (abbreviation: 2PCCzPPm), 9- (4,6-diphenyl-pyrimidin-2-yl)-9'-phenyl-3,3'-bi-9H-carbazole (abbreviation: 2PCCzPm), 4-[2-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]benzofuro[3,2-d]pyrimidine (abbreviation: 4PCCzBfpm-02), 4-{3-[3-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}benzo[h]quinazoline, 9-[3-(2,6-diphenyl-pyridin-4-yl)phenyl]-9'-phenyl-3,3'-bi-9H-carbazole is preferred because it has good heat resistance.
[0255] When another material is used for the hole blocking layer, an organic compound having a HOMO level deeper than the HOMO level of the material contained in the light-emitting layer 113 may be used from among materials that can be used for the hole transport layer described later.
[0256] The electron transport layer 114 is an organic compound having electron transport properties, and has an electron mobility of 1×10 at a square root of an electric field strength [V / cm] of 600. −6 cm 2 A substance having an electron mobility of 1 / Vs or more is preferred. Note that other substances can be used as long as they have a higher electron transporting property than holes. Note that the organic compound is preferably an organic compound having a π-electron-deficient heteroaromatic ring. The organic compound having a π-electron-deficient heteroaromatic ring is preferably, for example, one or more of an organic compound having a heteroaromatic ring with a polyazole skeleton, an organic compound having a heteroaromatic ring with a pyridine skeleton, an organic compound having a heteroaromatic ring with a diazine skeleton, and an organic compound having a heteroaromatic ring with a triazine skeleton.
[0257] Specific examples of the organic compound having a π-electron-deficient heteroaromatic ring that can be used in the electron transport layer include 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (abbreviation: TAZ), 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene (abbreviation: OXD-7), 9-[4-(5-phenyl-1, organic compounds having an azole skeleton, such as 3,5-bis[3-(9H-carbazole)-3,4-oxadiazol-2-yl]phenyl]-9H-carbazole (abbreviation: CO11), 2,2',2''-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole) (abbreviation: TPBI), 2-[3-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: mDBTBIm-II), and 4,4'-bis(5-methylbenzoxazol-2-yl)stilbene (abbreviation: BzOs); organic compounds containing a heteroaromatic ring having a pyridine skeleton, such as 1,3,5-tri[3-(3-pyridyl)phenyl]pyridine (abbreviation: 35DCzPPy), 1,3,5-tri[3-(9H-carbazol-9-yl)phenyl]pyridine (abbreviation: 35DCzPPy), 1,3,5-tri[3-(3-pyridyl)phenyl]benzene (abbreviation: TmPyPB), 3,5-bis[3-(9H-carbazol-9-yl)phenyl]pyridine (abbreviation: 35DCzPPy), bathophenanthroline (abbreviation: Bphen), bathocuproine (abbreviation: BCP), and 2,9-di(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline (abbreviation: NBphen) , 2-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTPDBq-II), 2-[3-(3′-dibenzothiophen-4-yl)biphenyl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTBPDBq-II), 2-[3′-(9H-carbazol-9-yl)biphenyl-3-yl]dibenzo[f,h]quinoxaline (abbreviation: 2mCzBPDBq), 2-[4′-(9-phenyl-9H-carbazol-3-yl)-3,1′-biphenyl-1-yl]dibenzo[f,h]quinoxalineh]quinoxaline (abbreviation: 2mpPCBPDBq), 2-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTPDBq-II), 2-[3′-(9H-carbazol-9-yl)biphenyl-3-yl]dibenzo[f,h]quinoxaline (abbreviation: 2mCzBPDBq), 2-[4-(3,6-diphenyl-9H-carbazol-9-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 2CzPDBq-III), 7-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f ,h]quinoxaline (abbreviation: 7mDBTPDBq-II), 6-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 6mDBTPDBq-II), 9-[3'-(dibenzothiophen-4-yl)biphenyl-3-yl]naphtho[1',2':4,5]furo[2,3-b]pyrazine (abbreviation: 9mDBtBPNfpr), 9-[(3'-dibenzothiophen-4-yl)biphenyl-4-yl]naphtho[1',2':4,5]furo[2,3-b]pyrazine (abbreviation: 9pmDBtBPNfpr), 4,6-bis(dibenzothiophen-4-yl)phenyl [3-(phenanthrene-9-yl)phenyl]pyrimidine (abbreviation: 4,6mPnP2Pm), 4,6-bis[3-(4-dibenzothienyl)phenyl]pyrimidine (abbreviation: 4,6mDBTP2Pm-II), 4,6-bis[3-(9H-carbazol-9-yl)phenyl]pyrimidine (abbreviation: 4,6mCzP2Pm), 9,9'-[pyrimidine-4,6-diylbis(biphenyl-3,3'-diyl)]bis(9H-carbazole) (abbreviation: 4,6mCzBP2Pm), 8-(1,1'-biphenyl-4-yl)-4-[3-(dibenzothiophene)] 4,8-bis[3-(dibenzothiophen-4-yl)phenyl]-[1]benzofuro[3,2-d]pyrimidine (abbreviation: 8BP-4mDBtPBfpm), 3,8-bis[3-(dibenzothiophen-4-yl)phenyl]benzofuro[2,3-b]pyrazine (abbreviation: 3,8mDBtP2Bfpr), 4,8-bis[3-(dibenzothiophen-4-yl)phenyl]-[1]benzofuro[3,2-d]pyrimidine (abbreviation: 4,8mDBtP2Bfpm), 8-[3'-(dibenzothiophen-4-yl)(1,1'-biphenyl-3-yl)]naphtho[1',2':4,5]furo[3,2-d]pyrimidine (abbreviation: 8mDBtBPNfpm), 8-[(2,2'-binaphthalen)-6-yl]-4-[3-(dibenzothiophen-4-yl)phenyl]-[1]benzofuro[3,2-d]pyrimidine (abbreviation: 8(βN2)-4mDBtPBfpm), 2,2'-(pyridine-2,6-diyl)bis(4-phenylbenzo[h]quinazoline) (abbreviation: 2,6(P-Bqn)2Py), 2,2'-(pyridine-2,6-diyl)bis{4-[4-(2-naphthyl)phenyl]-6-phenylpyrimidine} (abbreviation: 2,6(NP-PPm)2P y), 6-(1,1'-biphenyl-3-yl)-4-[3,5-bis(9H-carbazol-9-yl)phenyl]-2-phenylpyrimidine (abbreviation: 6mBP-4Cz2PPm), 2,6-bis(4-naphthalen-1-ylphenyl)-4-[4-(3-pyridyl)phenyl]pyrimidine (abbreviation: 2,4NP-6PyPPm), 4-[3,5-bis(9H-carbazol-9-yl)phenyl]-2-phenyl-6-(1,1'-biphenyl-4-yl)pyrimidine (abbreviation: 6BP-4Cz2PPm), 7-[4-(9-phenyl-9H-carbazol- 8-(1,1':4',1"-terphenyl-3-yl)-4-[3-(dibenzothiophen-4-yl)phenyl]-benzofuro[3,2-d]pyrimidine (abbreviation: 8mpTP-4mDBtPBfpm), 4,8-bis[3-(dibenzofuran-4-yl)phenyl]benzofuro[3,2-d]pyrimidine, 8-(1,1':4',1"-terphenyl-3-yl)-4-[3-(dibenzothiophen-4-yl)biphenyl-4- yl]-benzofuro[3,2-d]pyrimidine, 4,8-bis[3-(9H-carbazol-9-yl)phenyl]benzofuro[3,2-d]pyrimidine (abbreviation: 4,8mCzP2Bfpm), 8-(1,1':4',1"-terphenyl-3-yl)-4-[3-(9-phenyl-9H-carbazol-3-yl)phenyl]-benzofuro[3,2-d]pyrimidine, 8-(1,1'-biphenyl-4-yl)-4-[3-(9-phenyl-9H-carbazol-3-yl)biphenyl-3-yl]-benzofuro[3,2-d]pyrimidine, 8-(1,organic compounds having a diazine skeleton such as 1'-biphenyl-4-yl)-4-{3-[2-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}benzofuro[3,2-d]pyrimidine, 8-phenyl-4-{3-[2-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}benzofuro[3,2-d]pyrimidine, and 8-(1,1'-biphenyl-4-yl)-4-(3,5-di-9H-carbazol-9-yl-phenyl)benzofuro[3,2-d]pyrimidine; -[3'-(9,9-dimethyl-9H-fluoren-2-yl)-1,1'-biphenyl-3-yl]-4,6-diphenyl-1,3,5-triazine (abbreviation: mFBPTzn), 2-[(1,1'-biphenyl)-4-yl]-4-phenyl-6-[9,9'-spirobi(9H-fluoren)-2-yl]-1,3,5-triazine (abbreviation: BP-SFTzn), 2-{3-[3-(benzo[b]naphtho[1,2-d]furan-8-yl)phenyl]phenyl}-4,6-diphenyl-1,3,5-triazine (abbreviation: mBnfBPTzn), 2-{ 3-[3-(benzo[b]naphtho[1,2-d]furan-6-yl)phenyl]phenyl}-4,6-diphenyl-1,3,5-triazine (abbreviation: mBnfBPTzn-02), 2-{4-[3-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}-4,6-diphenyl-1,3,5-triazine (abbreviation: PCCzPTzn), 9-[3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-9'-phenyl-2,3'-bi-9H-carbazole (abbreviation: mPCCzPTzn-02 ), 2-[3'-(9,9-dimethyl-9H-fluoren-2-yl)-1,1'-biphenyl-3-yl]-4,6-diphenyl-1,3,5-triazine (abbreviation: mFBPTzn), 5-[3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-7,7-dimethyl-5H,7H-indeno[2,1-b]carbazole (abbreviation: mINc(II)PTzn), 2-{3-[3-(dibenzothiophen-4-yl)phenyl]phenyl}-4,6-diphenyl-1,3,5-triazine (abbreviation: mDBtBPTzn), 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine (abbreviation: TmPPPyTz), 2-[3-(2,6-dimethyl-3-pyridyl)-5-(9-phenanthryl)phenyl]-4,6-diphenyl-1,3,5-triazine (abbreviation: mPn-mDMePyPTzn), 11-(4-[1,1'-diphenyl]-4-yl-6-phenyl-1,3,5-triazin-2-yl)-11,12-dihydro-12-phenyl-indolo[2,3-a]carbazole (abbreviation: BP-Icz(II)Tzn), 2-[3'-(triphenylene- Examples of organic compounds having a triazine skeleton include 9-[4-(4,6-diphenyl-1,3,5-triazine-2-yl)-2-dibenzothiophenyl]-2-phenyl-9H-carbazole (abbreviation: PCDBfTzn), and 2-[1,1'-biphenyl]-3-yl-4-phenyl-6-(8-[1,1':4',1"-terphenyl]-4-yl-1-dibenzofuranyl)-1,3,5-triazine (abbreviation: mBP-TPDBfTzn). Among the above, organic compounds having a heteroaromatic ring with a diazine skeleton, organic compounds having a heteroaromatic ring with a pyridine skeleton, and organic compounds having a heteroaromatic ring with a triazine skeleton are preferred due to their high reliability. In particular, organic compounds containing a heteroaromatic ring having a diazine (pyrimidine, pyrazine) skeleton and organic compounds containing a heteroaromatic ring having a triazine skeleton have high electron transport properties and also contribute to reducing the driving voltage.
[0258] The electron transport layer 114 having this structure may also serve as the electron injection layer 115 .
[0259] Between the electron transport layer 114 and the common electrode (cathode) 102, an electron injection layer 115 is formed using lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF 2It is preferable to provide a layer containing an alkali metal or alkaline earth metal, such as (8-quinolinolato)lithium (abbreviation: Liq), or a compound or complex thereof. A co-evaporation film of ytterbium (Yb) and lithium is also preferable. The electron injection layer 115 may be an electride, in which an alkali metal or alkaline earth metal or a compound thereof is contained in a layer made of a substance having electron transport properties. Examples of electrides include a substance in which electrons are added at a high concentration to a mixed oxide of calcium and aluminum.
[0260] Note that a layer containing a substance having electron transport properties (preferably an organic compound having a bipyridine skeleton) containing a fluoride of the alkali metal or alkaline earth metal at a concentration (50 wt % or more) sufficient to form a microcrystalline state can also be used as the electron-injection layer 115. Since this layer has a low refractive index, it is possible to provide an organic EL device with better external quantum efficiency.
[0261] The cathode may be made of a metal, alloy, electrically conductive compound, or mixture thereof having a small work function (specifically, 3.8 eV or less). Specific examples of such cathode materials include alkali metals such as lithium (Li) and cesium (Cs), elements belonging to Group 1 or Group 2 of the periodic table such as magnesium (Mg), calcium (Ca), and strontium (Sr), alloys containing these (MgAg, AlLi), rare earth metals such as europium (Eu) and ytterbium (Yb), and alloys containing these. However, by providing an electron injection layer between the cathode and the electron transport layer, various conductive materials such as Al, Ag, ITO, and indium oxide-tin oxide containing silicon or silicon oxide can be used as the cathode, regardless of the magnitude of the work function.
[0262] These conductive materials can be formed into films by dry methods such as vacuum deposition and sputtering, inkjet methods, spin coating, etc. Alternatively, they may be formed by a wet method using a sol-gel method, or by a wet method using a paste of a metal material.
[0263] The EL layer 103 may be formed by any of various methods, including dry and wet methods, such as vacuum deposition, gravure printing, offset printing, screen printing, inkjet printing, and spin coating.
[0264] Furthermore, the above-mentioned electrodes or layers may be formed using different film formation methods.
[0265] The configuration of the layer provided between the anode and cathode is not limited to the above, but a configuration in which the light-emitting region where holes and electrons recombine is provided at a location away from the anode and cathode is preferred so as to suppress quenching caused by the proximity of the light-emitting region to the electrodes and the metal used in the carrier injection layer.
[0266] Furthermore, the hole transport layer and electron transport layer in contact with the light-emitting layer 113, and particularly the carrier transport layer close to the recombination region in the light-emitting layer 113, are preferably made of a substance having a band gap larger than the band gap of the light-emitting material constituting the light-emitting layer or the light-emitting material contained in the light-emitting layer, in order to suppress energy transfer from excitons generated in the light-emitting layer.
[0267] Note that the structure of this embodiment mode can be used in appropriate combination with structures of other embodiments.
[0268] Embodiment 5 In this embodiment, a light-emitting device using an organic EL device manufactured by the manufacturing method of the organic EL device described in Embodiments 2 and 3 will be described with reference to FIGS. 11A and 11B. FIG. 11A is a top view showing the light-emitting device, and FIG. 11B is a cross-sectional view taken along dashed lines A-B and C-D in FIG. 11A. This light-emitting device includes a driver circuit section (source line driver circuit) 601, a pixel section 602, and a driver circuit section (gate line driver circuit) 603, all of which are shown by dotted lines, to control the light emission of the organic EL device. Also, 604 denotes a sealing substrate, 605 denotes a sealant, and the inside surrounded by the sealant 605 forms a space 607.
[0269] The routing wiring 608 is wiring for transmitting signals input to the source line driver circuit 601 and the gate line driver circuit 603, and receives video signals, clock signals, start signals, reset signals, etc. from an FPC (flexible printed circuit) 609, which serves as an external input terminal. Although only the FPC is shown here, a printed wiring board (PWB) may be attached to this FPC. In this specification, the light-emitting device includes not only the light-emitting device itself but also a state in which an FPC or PWB is attached to it.
[0270] Next, the cross-sectional structure will be described with reference to Fig. 11B. A driver circuit portion and a pixel portion are formed on an element substrate 610, but here, a source line driver circuit 601, which is the driver circuit portion, and one pixel in a pixel portion 602 are shown.
[0271] The element substrate 610 may be made of a substrate made of glass, quartz, organic resin, metal, alloy, semiconductor, or the like, or a plastic substrate made of FRP (Fiber Reinforced Plastics), PVF (Polyvinyl Fluoride), polyester, acrylic resin, or the like.
[0272] The structure of the transistors used in the pixels and driver circuits is not particularly limited. For example, they may be inverted staggered transistors or staggered transistors. Furthermore, they may be top-gate or bottom-gate transistors. The semiconductor material used for the transistors is not particularly limited, and examples thereof include silicon, germanium, silicon carbide, and gallium nitride. Alternatively, an oxide semiconductor containing at least one of indium, gallium, and zinc, such as an In—Ga—Zn-based metal oxide, may be used.
[0273] The crystallinity of a semiconductor material used for a transistor is not particularly limited, and any of an amorphous semiconductor and a crystalline semiconductor (a microcrystalline semiconductor, a polycrystalline semiconductor, a single crystal semiconductor, or a semiconductor having a crystalline region in part) may be used. The use of a crystalline semiconductor is preferable because it can suppress deterioration of transistor characteristics.
[0274] Here, it is preferable to use an oxide semiconductor for semiconductor devices such as transistors provided in the pixels and driver circuits, as well as transistors used in touch sensors, which will be described later. In particular, it is preferable to use an oxide semiconductor having a wider band gap than silicon. By using an oxide semiconductor having a wider band gap than silicon, the current in the off state of the transistor can be reduced.
[0275] The oxide semiconductor preferably contains at least indium (In) or zinc (Zn), and more preferably contains an oxide represented by In-M-Zn-based oxide (M is a metal such as Al, Ti, Ga, Ge, Y, Zr, Sn, La, Ce, or Hf).
[0276] In particular, it is preferable to use, as the semiconductor layer, an oxide semiconductor film which has a plurality of crystal parts whose c-axes are oriented perpendicular to a surface on which the semiconductor layer is formed or a top surface of the semiconductor layer and which does not have grain boundaries between adjacent crystal parts.
[0277] By using such a material for the semiconductor layer, fluctuations in electrical characteristics are suppressed, and a highly reliable transistor can be realized.
[0278] Furthermore, a transistor having the above-described semiconductor layer can retain charge stored in a capacitor through the transistor for a long period of time due to its low off-state current. By applying such a transistor to a pixel, it is possible to stop the driver circuit while maintaining the gray level of an image displayed in each display region. As a result, an electronic device with extremely low power consumption can be realized.
[0279] It is preferable to provide a base film to stabilize the characteristics of the transistor. The base film can be formed as a single layer or a stacked layer using an inorganic insulating film such as a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a silicon nitride oxide film. The base film can be formed by a sputtering method, a CVD (Chemical Vapor Deposition) method (such as a plasma CVD method, a thermal CVD method, or a MOCVD (Metal Organic CVD) method), an ALD (Atomic Layer Deposition) method, a coating method, a printing method, or the like. Note that the base film need not be provided if it is not necessary.
[0280] Note that the FET 623 represents one of the transistors formed in the source line driver circuit 601. The driver circuit may be formed of various CMOS circuits, PMOS circuits, or NMOS circuits. In addition, although this embodiment shows a driver-integrated type in which the driver circuit is formed on a substrate, this is not necessarily required, and the driver circuit may also be formed externally rather than on the substrate.
[0281] Furthermore, the pixel portion 602 is formed by a plurality of pixels including a switching FET 611, a current control FET 612, and a first electrode 613 electrically connected to the drain of the FET, but is not limited to this, and the pixel portion may be formed by combining three or more FETs and a capacitance element.
[0282] An insulator 614 is formed to cover an end portion of the first electrode 613. Here, the insulator 614 can be formed by using a positive photosensitive acrylic resin film.
[0283] Furthermore, in order to improve the coverage of the EL layer and the like to be formed later, a curved surface having a curvature is formed at the upper or lower end of the insulator 614. For example, when a positive photosensitive acrylic resin is used as the material of the insulator 614, it is preferable to provide a curved surface having a curvature radius (0.2 μm to 3 μm) only at the upper end of the insulator 614. Furthermore, either a negative photosensitive resin or a positive photosensitive resin can be used as the insulator 614.
[0284] An EL layer 616 and a second electrode 617 are formed on the first electrode 613. Here, the first electrode 613 functions as an anode. Materials that can be used for the anode are preferably those with a large work function. For example, a single layer film such as an ITO film, an indium tin oxide film containing silicon, an indium oxide film containing 2 to 20 wt % zinc oxide, a titanium nitride film, a chromium film, a tungsten film, a Zn film, or a Pt film can be used. Other examples include a laminated structure with a silver-based film, a laminated structure with a titanium nitride film and an aluminum-based film, and a three-layer structure with a titanium nitride film, an aluminum-based film, and a titanium nitride film. The laminated structure provides low wiring resistance, good ohmic contact, and the anode can function well.
[0285] The EL layer 616 can be formed by various methods such as evaporation using an evaporation mask, ink-jet printing, spin coating, etc. The EL layer 616 has the structure described in Embodiment Mode 1 and Embodiment Mode 3.
[0286] Furthermore, a material having a small work function (Al, Mg, Li, Ca, or an alloy or compound thereof (MgAg, MgIn, AlLi, etc.)) is preferably used as a material used for the second electrode 617 formed on the EL layer 616. Note that when light generated in the EL layer 616 is transmitted through the second electrode 617, it is preferable to use a stack of a thin metal or alloy film and a transparent conductive film (ITO, indium oxide containing 2 to 20 wt % zinc oxide, indium tin oxide containing silicon, zinc oxide (ZnO), etc.) as the second electrode 617.
[0287] An organic EL device is formed with the first electrode 613, the EL layer 616, and the second electrode 617. The organic EL device is an organic EL device fabricated by the manufacturing method of an organic EL device described in Embodiments 2 and 3. Note that the pixel portion is formed with a plurality of organic EL devices. However, the light-emitting device of this embodiment may include both organic EL devices fabricated by the manufacturing method of an organic EL device described in Embodiments 2 and 3 and organic EL devices having other structures. In this case, in the light-emitting device of one embodiment of the present invention, a common hole-transport layer can be used between the organic EL devices emitting light of different wavelengths, and therefore the light-emitting device can be manufactured with a simple manufacturing process and is cost-effective.
[0288] Furthermore, by bonding the sealing substrate 604 to the element substrate 610 with a sealing material 605, an organic EL device 618 is provided in a space 607 surrounded by the element substrate 610, the sealing substrate 604, and the sealing material 605. The space 607 is filled with a filler, and in some cases, it is filled with an inert gas (nitrogen, argon, etc.), or with a sealing material. A recess is formed in the sealing substrate, and by providing a desiccant therein, deterioration due to the influence of moisture can be suppressed, which is a preferable configuration.
[0289] It is preferable to use epoxy resin or glass frit for the sealing material 605. It is also desirable that these materials are as moisture- and oxygen-impermeable as possible. In addition to glass substrates and quartz substrates, plastic substrates made of FRP (Fiber Reinforced Plastics), PVF (Polyvinyl Fluoride), polyester, acrylic resin, or the like can be used for the sealing substrate 604.
[0290] Although not shown in Figures 11A and 11B, a protective film may be provided on the cathode. The protective film may be formed of an organic resin film or an inorganic insulating film. The protective film may also be formed so as to cover the exposed portion of the sealing material 605. The protective film may also be provided so as to cover the surfaces and side surfaces of the pair of substrates, the exposed side surfaces of the sealing layer, the insulating layer, etc.
[0291] The protective film can be made of a material that is impermeable to impurities such as water, and therefore can effectively prevent impurities such as water from diffusing from the outside to the inside.
[0292] The protective film may be made of an oxide, nitride, fluoride, sulfide, ternary compound, metal, polymer, or the like. For example, a material containing aluminum oxide, hafnium oxide, hafnium silicate, lanthanum oxide, silicon oxide, strontium titanate, tantalum oxide, titanium oxide, zinc oxide, niobium oxide, zirconium oxide, tin oxide, yttrium oxide, cerium oxide, scandium oxide, erbium oxide, vanadium oxide, indium oxide, or the like; a material containing aluminum nitride, hafnium nitride, silicon nitride, tantalum nitride, titanium nitride, niobium nitride, molybdenum nitride, zirconium nitride, or gallium nitride, or the like; a nitride containing titanium and aluminum, an oxide containing titanium and aluminum, an oxide containing aluminum and zinc, a sulfide containing manganese and zinc, a sulfide containing cerium and strontium, an oxide containing erbium and aluminum, or an oxide containing yttrium and zirconium, or the like.
[0293] The protective film is preferably formed using a film formation method that provides good step coverage. One such method is atomic layer deposition (ALD). It is preferable to use a material that can be formed using the ALD method for the protective film. By using the ALD method, it is possible to form a dense protective film with reduced defects such as cracks and pinholes, or with a uniform thickness. Furthermore, it is possible to reduce damage to the workpiece when forming the protective film.
[0294] For example, by forming a protective film using the ALD method, it is possible to form a uniform protective film with few defects on surfaces having complex uneven shapes, including the top, side, and back surfaces of the touch panel.
[0295] As described above, a light-emitting device can be obtained using an organic EL device manufactured using the method for manufacturing an organic EL device described in Embodiments 2 and 3.
[0296] The light-emitting device in this embodiment uses an organic EL device manufactured using the method for manufacturing an organic EL device described in embodiments 2 and 3, and therefore, a light-emitting device with excellent characteristics can be obtained.
[0297] 12A and 12B show an example of a light-emitting device in which color purity is improved by providing a colored layer (color filter), etc. Fig. 12A shows a substrate 1001, a base insulating film 1002, a gate insulating film 1003, gate electrodes 1006, 1007, and 1008, a first interlayer insulating film 1020, a second interlayer insulating film 1021, a peripheral portion 1042, a pixel portion 1040, a driving circuit portion 1041, first electrodes 1024R, 1024G, and 1024B of the organic EL device, a partition wall 1025, an EL layer 1028, a common electrode (cathode) 1029 of the organic EL device, a sealing substrate 1031, a sealant 1032, etc.
[0298] 12A , the colored layers (red colored layer 1034R, green colored layer 1034G, and blue colored layer 1034B) are provided on a transparent base material 1033. A black matrix 1035 may also be provided. The transparent base material 1033 provided with the colored layers and black matrix is aligned and fixed to the substrate 1001. The colored layers and black matrix 1035 are covered with an overcoat layer 1036.
[0299] 12B shows an example in which colored layers (a red colored layer 1034R, a green colored layer 1034G, and a blue colored layer 1034B) are formed between the gate insulating film 1003 and the first interlayer insulating film 1020. In this manner, the colored layers may be provided between the substrate 1001 and the sealing substrate 1031.
[0300] Furthermore, while the light-emitting device described above has a structure (bottom emission type) in which light is extracted from the substrate 1001 side on which the FET is formed, a light-emitting device with a structure (top emission type) in which light is extracted from the sealing substrate 1031 side may also be used. A cross-sectional view of a top emission type light-emitting device is shown in FIG. 13 . In this case, a light-opaque substrate can be used as the substrate 1001. The process is the same as for a bottom emission type light-emitting device until the connection electrode connecting the FET and the anode of the organic EL device is fabricated. Thereafter, a third interlayer insulating film 1037 is formed to cover the electrode 1022. This insulating film may also serve as a planarizing film. The third interlayer insulating film 1037 can be formed using the same material as the second interlayer insulating film, as well as other known materials.
[0301] The first electrodes 1024R, 1024G, and 1024B of the organic EL device are anodes in this example, but may be cathodes instead. In the case of a top-emission light-emitting device such as that shown in FIG. 13, it is preferable that the anodes be reflective electrodes. The EL layer 1028 has the same structure as that described for the EL layer 103 in the first embodiment.
[0302] In the top-emission structure shown in FIG. 13 , sealing can be performed using a sealing substrate 1031 provided with colored layers (a red colored layer 1034R, a green colored layer 1034G, and a blue colored layer 1034B). The sealing substrate 1031 may be provided with a black matrix 1035 positioned between pixels. The colored layers (the red colored layer 1034R, the green colored layer 1034G, and the blue colored layer 1034B) and the black matrix may be covered with an overcoat layer (not shown). Note that a light-transmitting substrate is used as the sealing substrate 1031.
[0303] A microcavity structure is suitable for use in top-emission light-emitting devices. An organic EL device with a microcavity structure can be obtained by using a reflective electrode as one electrode and a semi-transmissive / semi-reflective electrode as the other electrode. At least an EL layer is present between the reflective electrode and the semi-transmissive / semi-reflective electrode, and at least a light-emitting layer that serves as the light-emitting region is present.
[0304] The reflectance of the reflective electrode to visible light is 40% to 100%, preferably 70% to 100%, and the resistivity is 1×10 −2 The semi-transmitting and semi-reflective electrode has a visible light reflectance of 20% to 80%, preferably 40% to 70%, and a resistivity of 1×10 −2 It is assumed that the film has a resistivity of Ωcm or less.
[0305] Light emitted from the light-emitting layer included in the EL layer is reflected by the reflective electrode and the semi-transmissive and semi-reflective electrode, causing resonance.
[0306] In this organic EL device, the optical distance between the reflective electrode and the semi-transmissive / semi-reflective electrode can be changed by changing the thickness of the transparent conductive film, the composite material described above, the carrier transport material, etc. This makes it possible to intensify light of a resonating wavelength and attenuate light of a non-resonating wavelength between the reflective electrode and the semi-transmissive / semi-reflective electrode.
[0307] Note that, since the light reflected by the reflective electrode and returned (first reflected light) significantly interferes with the light (first incident light) that directly enters the semi-transmissive / semi-reflective electrode from the light-emitting layer, it is preferable to adjust the optical distance between the reflective electrode and the light-emitting layer to (2n-1)λ / 4 (where n is a natural number of 1 or more, and λ is the wavelength of the light emission to be amplified). By adjusting the optical distance, the phases of the first reflected light and the first incident light can be matched, thereby further amplifying the light emission from the light-emitting layer.
[0308] In the above configuration, the EL layer may have a structure having a plurality of light-emitting layers or a structure having a single light-emitting layer. For example, in combination with the above-described tandem organic EL device configuration, a single organic EL device may be provided with a plurality of EL layers sandwiching a charge generating layer therebetween, and one or more light-emitting layers may be formed in each EL layer.
[0309] The microcavity structure makes it possible to increase the light emission intensity of a specific wavelength in the front direction, thereby reducing power consumption. In the case of a light-emitting device that displays images using four sub-pixels of red, yellow, green, and blue, the yellow light emission has the effect of improving brightness, and the microcavity structure that matches the wavelength of each color can be applied to all sub-pixels, resulting in a light-emitting device with good characteristics.
[0310] The light-emitting device in this embodiment has good characteristics because it uses organic EL devices fabricated using the methods for fabricating organic EL devices described in Embodiments 2 and 3. The light-emitting device described above is capable of individually controlling a large number of minute organic EL devices arranged in a matrix, and therefore can be suitably used as a display device for displaying images.
[0311] This embodiment mode can be freely combined with other embodiment modes.
[0312] Embodiment 6 In this embodiment, examples of electronic devices that include an organic EL device manufactured by the manufacturing method of the organic EL device described in Embodiments 2 and 3 will be described.
[0313] Examples of electronic devices to which the organic EL devices are applied include television sets (also called televisions or television receivers), computer monitors, digital cameras, digital video cameras, digital photo frames, mobile phones (also called mobile phones or mobile phone devices), portable game machines, personal digital assistants, sound reproducing devices, large game machines such as pachinko machines, etc. Specific examples of these electronic devices are shown below.
[0314] 14A shows an example of a television set. The television set has a display portion 7103 built in a housing 7101. Here, the television set has a configuration in which the housing 7101 is supported by a stand 7105. The display portion 7103 can display an image, and is configured by arranging organic EL devices, which are manufactured by the manufacturing method of an organic EL device described in Embodiments 2 and 3, in a matrix.
[0315] The television set can be operated using operation switches provided on the housing 7101 or a separate remote control 7110. Using operation keys 7109 provided on the remote control 7110, channels and volume can be controlled, and an image displayed on the display portion 7103 can be operated. The remote control 7110 may be provided with a display portion 7107 that displays information output from the remote control 7110. Note that organic EL devices arranged in a matrix and manufactured by the manufacturing method of an organic EL device described in Embodiments 2 and 3 can also be applied to the display portion 7107.
[0316] The television device is configured to include a receiver, a modem, etc. The receiver can receive general television broadcasts, and by connecting to a wired or wireless communication network via the modem, it is also possible to perform one-way (from sender to receiver) or two-way (between sender and receiver, or between receivers, etc.) information communication.
[0317] FIG. 14B1 illustrates a computer including a main body 7201, a housing 7202, a display unit 7203, a keyboard 7204, an external connection port 7205, a pointing device 7206, and the like. This computer is fabricated by using organic EL devices fabricated using the fabrication methods for organic EL devices described in Embodiments 2 and 3, arranged in a matrix, in the display unit 7203. The computer of FIG. 14B1 may have a configuration as shown in FIG. 14B2. The computer of FIG. 14B2 is provided with a display unit 7210 instead of the keyboard 7204 and the pointing device 7206. The display unit 7210 is a touch panel type, and input can be performed by operating the input display displayed on the display unit 7210 with a finger or a dedicated pen. The display unit 7210 can display not only the input display but also other images. The display unit 7203 may also be a touch panel. The two screens are connected by a hinge, which prevents problems such as scratches or breakage of the screens during storage or transportation.
[0318] 14C shows an example of a mobile terminal. The mobile phone includes a display portion 7402 built into a housing 7401, operation buttons 7403, an external connection port 7404, a speaker 7405, a microphone 7406, and the like. Note that the mobile phone has the display portion 7402 formed by arranging organic EL devices, which are manufactured by the manufacturing method of an organic EL device described in Embodiments 2 and 3, in a matrix.
[0319] 14C can be configured so that information can be input by touching the display portion 7402 with a finger or the like. In this case, operations such as making a call or creating an email can be performed by touching the display portion 7402 with a finger or the like.
[0320] The screen of the display portion 7402 has three main modes. The first is a display mode mainly for displaying images, the second is an input mode mainly for inputting information such as characters, and the third is a display+input mode that combines the display mode and the input mode.
[0321] For example, when making a call or creating an email, the display portion 7402 may be set to a character input mode mainly for inputting characters, and characters displayed on the screen may be input. In this case, it is preferable to display a keyboard or number buttons on most of the screen of the display portion 7402.
[0322] In addition, by providing a detection device having a sensor that detects tilt, such as a gyro or an acceleration sensor, inside the mobile terminal, the orientation of the mobile terminal (portrait or landscape) can be determined and the screen display of the display portion 7402 can be automatically switched.
[0323] The screen mode can be switched by touching the display portion 7402 or by operating the operation buttons 7403 on the housing 7401. The screen mode can also be switched depending on the type of image displayed on the display portion 7402. For example, if the image signal to be displayed on the display portion is moving image data, the display mode is selected, and if it is text data, the input mode is selected.
[0324] In addition, in the input mode, a signal detected by an optical sensor in the display portion 7402 may be detected, and if there is no input by touch operation on the display portion 7402 for a certain period of time, the screen mode may be controlled to switch from the input mode to the display mode.
[0325] The display portion 7402 can also function as an image sensor. For example, personal authentication can be performed by touching the display portion 7402 with a palm or a finger to capture an image of a palm print, fingerprint, or the like. Furthermore, by using a backlight that emits near-infrared light or a sensing light source that emits near-infrared light for the display portion, finger veins, palm veins, or the like can also be captured.
[0326] As described above, the range of application of the light-emitting device including the organic EL device manufactured using the manufacturing method of the organic EL device described in Embodiments 2 and 3 is extremely wide, and this light-emitting device can be applied to electronic devices in all fields.
[0327] FIG. 15A is a schematic diagram showing an example of a cleaning robot.
[0328] The cleaning robot 5100 has a display 5101 arranged on its top surface, multiple cameras 5102 arranged on its side, a brush 5103, and an operation button 5104. Although not shown, the cleaning robot 5100 is also provided with tires, a suction port, and the like on its bottom surface. The cleaning robot 5100 is also provided with various other sensors, such as an infrared sensor, an ultrasonic sensor, an acceleration sensor, a piezoelectric sensor, an optical sensor, and a gyro sensor. The cleaning robot 5100 is also provided with wireless communication means.
[0329] The cleaning robot 5100 can move by itself, detect dust 5120, and suck up the dust from a suction port provided on the bottom surface.
[0330] The cleaning robot 5100 can also analyze the image captured by the camera 5102 to determine whether there are any obstacles such as walls, furniture, or steps. If the image analysis detects an object that may become tangled in the brush 5103, such as a wire, the cleaning robot 5100 can stop the rotation of the brush 5103.
[0331] The display 5101 can display the remaining battery level, the amount of dust sucked, etc. The route traveled by the cleaning robot 5100 may be displayed on the display 5101. The display 5101 may also be a touch panel, and an operation button 5104 may be provided on the display 5101.
[0332] The cleaning robot 5100 can communicate with a portable electronic device 5140 such as a smartphone. Images captured by the camera 5102 can be displayed on the portable electronic device 5140. This allows the owner of the cleaning robot 5100 to know the state of the room even when they are away from home. In addition, the display on the display 5101 can be confirmed on the portable electronic device such as a smartphone.
[0333] The light-emitting device of one embodiment of the present invention can be used for the display 5101 .
[0334] The robot 2100 shown in FIG. 15B includes a computing device 2110, an illuminance sensor 2101, a microphone 2102, an upper camera 2103, a speaker 2104, a display 2105, a lower camera 2106, an obstacle sensor 2107, and a movement mechanism 2108.
[0335] The microphone 2102 has a function of detecting the user's voice, environmental sounds, etc. The speaker 2104 has a function of emitting sound. The robot 2100 can communicate with the user using the microphone 2102 and the speaker 2104.
[0336] The display 2105 has a function of displaying various information. The robot 2100 can display information desired by the user on the display 2105. The display 2105 may be equipped with a touch panel. The display 2105 may also be a detachable information terminal, which can be installed in a fixed position on the robot 2100 to enable charging and data transfer.
[0337] The upper camera 2103 and the lower camera 2106 have a function of capturing images of the surroundings of the robot 2100. In addition, the obstacle sensor 2107 can detect the presence or absence of an obstacle in the moving direction when the robot 2100 moves forward using the moving mechanism 2108. The robot 2100 can recognize the surrounding environment and move safely using the upper camera 2103, the lower camera 2106, and the obstacle sensor 2107. The light-emitting device of one embodiment of the present invention can be used for the display 2105.
[0338] 15C is a diagram showing an example of a goggle-type display. The goggle-type display includes, for example, a housing 5000, a display unit 5001, a speaker 5003, an LED lamp 5004, a connection terminal 5006, a sensor 5007 (including a function for measuring force, displacement, position, velocity, acceleration, angular velocity, rotation speed, distance, light, liquid, magnetism, temperature, chemical substance, sound, time, hardness, electric field, current, voltage, power, radiation, flow rate, humidity, gradient, vibration, odor, or infrared ray), a microphone 5008, a second display unit 5002, a support unit 5012, and earphones 5013.
[0339] The light-emitting device of one embodiment of the present invention can be used for the display portion 5001 and the second display portion 5002 .
[0340] The organic EL device manufactured using the manufacturing method of the organic EL device described in Embodiments 2 and 3 can also be mounted on the windshield or dashboard of an automobile. Figure 16 shows one mode in which the organic EL device manufactured using the manufacturing method of the organic EL device described in Embodiments 2 and 3 is used in the windshield or dashboard of an automobile. Display regions 5200 to 5203 are display regions provided using the organic EL device manufactured using the manufacturing method of the organic EL device described in Embodiments 2 and 3.
[0341] Display region 5200 and display region 5201 are display devices mounted on the windshield of an automobile and equipped with an organic EL device fabricated using the fabrication method for an organic EL device described in Embodiments 2 and 3. The organic EL device fabricated using the fabrication method for an organic EL device described in Embodiments 2 and 3 can be a so-called see-through display device, in which the opposite side can be seen through, by fabricating both the anode and cathode using light-transmitting electrodes. A see-through display allows the device to be installed on the windshield of an automobile without obstructing the view. When a transistor or the like is provided for driving the device, it is preferable to use a light-transmitting transistor, such as an organic transistor made of an organic semiconductor material or a transistor using an oxide semiconductor.
[0342] The display area 5202 is a display device provided on a pillar and equipped with an organic EL device manufactured by the manufacturing method of an organic EL device described in Embodiments 2 and 3. By displaying an image from an imaging means provided on the vehicle body in the display area 5202, the view blocked by the pillar can be complemented. Similarly, the display area 5203 provided on the dashboard can complement the view blocked by the vehicle body by displaying an image from an imaging means provided on the outside of the vehicle, thereby compensating for blind spots and improving safety. By displaying an image to complement the invisible parts, safety can be confirmed more naturally and without discomfort.
[0343] The display area 5203 can also provide various other information such as navigation information, speed, engine speed, and air conditioning settings. The display items and layout can be changed as needed to suit the user's preferences. This information can also be provided in the display areas 5200 to 5202. The display areas 5200 to 5203 can also be used as lighting devices.
[0344] 17A and 17B show a foldable portable information terminal 5150. The foldable portable information terminal 5150 has a housing 5151, a display area 5152, and a bending portion 5153. Fig. 17A shows the portable information terminal 5150 in an unfolded state. Fig. 17B shows the portable information terminal in a folded state. Although the portable information terminal 5150 has a large display area 5152, it is compact and highly portable when folded.
[0345] The display area 5152 can be folded in half by a bending portion 5153. The bending portion 5153 is composed of an expandable member and a plurality of support members, and when folding, the expandable member stretches and the bending portion 5153 is folded with a curvature radius of 2 mm or more, preferably 3 mm or more.
[0346] Note that the display region 5152 may be a touch panel (input / output device) equipped with a touch sensor (input device). The light-emitting device of one embodiment of the present invention can be used for the display region 5152.
[0347] 18A to 18C show a foldable portable information terminal 9310. Fig. 18A shows the portable information terminal 9310 in an unfolded state. Fig. 18B shows the portable information terminal 9310 in a state in the process of changing from one of the unfolded state and the folded state to the other. Fig. 18C shows the portable information terminal 9310 in a folded state. The portable information terminal 9310 has excellent portability in a folded state, and has excellent display visibility due to a seamless, wide display area in an unfolded state.
[0348] The display panel 9311 is supported by three housings 9315 connected by hinges 9313. Note that the display panel 9311 may be a touch panel (input / output device) equipped with a touch sensor (input device). Furthermore, the display panel 9311 can be reversibly transformed from an unfolded state to a folded state by bending the two housings 9315 via the hinges 9313. The light-emitting device of one embodiment of the present invention can be used for the display panel 9311.
[0349] At least a part of the configuration examples exemplified in this embodiment and the corresponding drawings can be combined as appropriate with other configuration examples or drawings.
[0350] This embodiment mode can be implemented by appropriately combining at least a part thereof with other embodiment modes described in this specification.
[0351] In this example, a sample having a mask film formed on an organic semiconductor film was subjected to a mask film removal treatment using water or a liquid containing water as a solvent, and then the substances remaining in the sample were investigated. The structural formulas of the compounds used in this example are shown below.
[0352]
[0353] The sample was prepared by laminating a film 1 corresponding to the light-emitting layer of the organic EL device and films (films 2 and 3) corresponding to the electron transport layer on a glass substrate, followed by forming a mask film. Film 1 was formed by co-evaporating 40 nm of 8-(1,1'-biphenyl-4-yl)-4-[3-(dibenzothiophen-4-yl)phenyl]-[1]benzofuro[3,2-d]pyrimidine (abbreviation: 8BP-4mDBtPBfpm) represented by the above structural formula (i) and 3,3'-bis(9-phenyl-9H-carbazole) (abbreviation: PCCP) represented by the above structural formula (ii) in a weight ratio of 0.6:0.4 (=8BP-4mDBtPBfpm:PCCP). Film 2 was formed by evaporating 2-[3-(3'-dibenzothiophen-4-yl)biphenyl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTBPDBq-II) represented by the above structural formula (iii) onto Film 1 to a thickness of 20 nm. Film 3 was formed by evaporating 2,9-di(2-naphthyl)-4,7-diphenyl-1,10-phenanthroline (abbreviation: NBPhen) represented by the above structural formula (iv) onto Film 2 to a thickness of 15 nm. The mask film was formed by evaporating tris(8-quinolinolato)aluminum (abbreviation: Alq) represented by the above structural formula (v) onto Film 3. 3 ) was evaporated to a thickness of 50 nm.
[0354] The laminate structure of the sample is shown in the table below.
[0355]
[0356] Four samples having the above-described configuration were prepared, and the mask film was removed using water as a remover for Sample 1, an 8.5% aqueous solution of phosphoric acid as a remover for Sample 2, and a 5 wt % aqueous solution of tetramethylammonium hydroxide (TMAH) as a remover for Sample 3. Sample 4 was used as a reference.
[0357] The mask film was removed by immersing it in each removal solution for 5 minutes, rinsing it with pure water, and then drying it.
[0358] The sample after the removal treatment was cut into a 2 cm x 2 cm piece and sonicated for 15 minutes with 1 ml of a solution of acetonitrile:chloroform = 7:1 to elute the membrane. The eluted sample solution was measured by high performance liquid chromatography.
[0359] For the measurement by high performance liquid chromatography, a Waters Acquity UPLC (registered trademark) System was used. As a detector, a UV detector (Waters 2996PDA Detector, manufactured by Waters) was used, and detection was performed by ultraviolet-visible light absorption. The column used was a Waters ACQUITY UPLC CSH C18 Column (particle size 1.7 μm, 2.1 × 100 mm). For the measurement, the mobile phase was A: acetonitrile, B: water, and the flow rate was 0.5 mL / min. A was held at 85% for 10 minutes, and after 15 minutes, gradient analysis was performed in which A was increased at a constant rate to 95%, and then A was held at 95% for 20 minutes. The injection volume of the sample solution was 5 μL.
[0360] The chromatogram obtained by the measurement is shown in Figure 19 (absorption wavelength: 310 nm). As can be seen from the figure, only Sample 4, which was not subjected to the removal treatment, had a mask film of Alq 3 In the samples that had been subjected to other removal treatments, quinolinol derived from Alq 3 No quinolinol derived from Alq was detected. 3 It was found that the film could be easily removed using water or a liquid containing water as a solvent, while leaving behind the film formed underneath.
[0361] 100: substrate, 101R: first electrode, 101C: connection electrode, 101G: first electrode, 101B: first electrode, 101: first electrode, 102: second electrode, 103: EL layer, 107: mask layer, 108: insulating layer, 110R: organic EL device, 110G: organic EL device, 110B: organic EL device, 111: hole injection layer, 112: hole transport layer, 113: light-emitting layer, 114: electron transport layer, 115: electron injection layer, 120R: EL layer, 120Rb: EL film, 120G: EL layer, 120Gb: EL film, 120B: EL layer, 120Bb: EL film, 121: EL layer, 125: insulating layer, 125b: insulating layer, 126: insulating layer, 126b: insulating layer, 130: connecting portion, 131: barrier layer, 143a: resist mask, 144a: aluminum oxide film, 145a: aluminum oxide layer, 145b: aluminum oxide layer, 145c: aluminum oxide layer, 146a: metal film or metal compound film, 147a: metal layer or metal compound layer, 149a: mask layer, 149b: mask layer, 149c: mask layer, 150: undercoat film, 151: organic semiconductor film, 151a: organic semiconductor layer, 151s: surface, 152: mask layer, 152a: mask layer , 153: aluminum oxide film, 153a: aluminum oxide layer, 153r: aluminum oxide film, 154: metal film or metal compound film, 154a: metal layer or metal compound layer, 155: resin film, 155a: photomask layer, 160: insulating layer, 161: gate insulating layer, 162: gate electrode, 165: first electrode, 166: second electrode, 167: photoelectric conversion layer, 168: light-emitting layer, 450: light-emitting device, 601: source line driving circuit, 602: pixel portion, 603: gate line driving circuit, 604: sealing substrate, 605: sealing material, 607: space, 608: wiring, 6 10: element substrate, 611: switching FET, 612: current control FET, 613: first electrode, 614: insulator, 616: EL layer, 617: second electrode, 618: organic EL device, 623: FET, 1001: substrate, 1002: base insulating film, 1003: gate insulating film, 1006: gate electrode, 1007: gate electrode, 1008: gate electrode, 1020: first interlayer insulating film, 1021: second interlayer insulating film, 1022: electrode, 1024B: first electrode, 1024G: first electrode, 1024R: first electrode, 1024W: first electrode, 1025: partition wall,1028: EL layer, 1029: cathode, 1031: sealing substrate, 1032: sealing material, 1033: base material, 1034B: colored layer, 1034G: colored layer, 1034R: colored layer, 1035: black matrix, 1036: overcoat layer, 1037: third interlayer insulating film, 1040: pixel section, 1041: driving circuit section, 1042: peripheral section, 2100: robot, 2101: illuminance sensor, 2102: microphone, 2103: Upper camera, 2104: speaker, 2105: display, 2106: lower camera, 2107: obstacle sensor, 2108: movement mechanism, 2110: computing device, 5000: housing, 5001: display unit, 5002: second display unit, 5003: speaker, 5004: LED lamp, 5006: connection terminal, 5007: sensor, 5008: microphone, 5012: support unit, 5013: earphone, 5100: cleaning robot, 5 101: display, 5102: camera, 5103: brush, 5104: operation button, 5120: dust, 5140: portable electronic device, 5150: portable information terminal, 5151: housing, 5152: display area, 5153: bending portion, 5200: display area, 5201: display area, 5202: display area, 5203: display area, 7101: housing, 7103: display unit, 7105: stand, 7107: display unit, 7109: operation key, 7 110: remote control device, 7201: main body, 7202: housing, 7203: display unit, 7204: keyboard, 7205: external connection port, 7206: pointing device, 7210: display unit, 7401: housing, 7402: display unit, 7403: operation buttons, 7404: external connection port, 7405: speaker, 7406: microphone, 9310: mobile information terminal, 9311: display panel, 9313: hinge, 9315: housing,
Claims
1. used to remove an aluminum oxide film formed on an organic semiconductor layer, An organometallic compound for masking an organic semiconductor layer, represented by the following general formula (G1): 【Chemical 1】 (In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms; X represents oxygen or sulfur; M represents a metal; n represents an integer of 1 to 5; and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.)
2. In claim 1, The organometallic compound for masking an organic semiconductor layer, wherein the organometallic compound represented by the general formula (G1) is an organometallic compound represented by the following general formula (G2): 【Chemistry 2】 (In General Formula (G2), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms; M represents a metal; n represents an integer of 1 to 3; and n is the same as the valence of the metal M. Note that when n is 2 or greater, the multiple Ars may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may form a coordinate bond.)
3. A layer formed between an organic semiconductor layer and an aluminum oxide film, An organometallic compound represented by the following general formula (G1): A layer used to remove the aluminum oxide film. 【Chemistry 3】 (In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms; X represents oxygen or sulfur; M represents a metal; n represents an integer of 1 to 5; and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.)
4. forming an organic semiconductor layer on the first electrode; forming a mask layer containing an organometallic compound represented by the following general formula (G1) on the organic semiconductor layer; forming an aluminum oxide film on the mask layer; a step of processing the shape of the organic semiconductor layer using the aluminum oxide film; and removing the mask layer and the aluminum oxide film using water or a liquid containing water as a solvent. 【Chemistry 4】 (In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms; X represents oxygen or sulfur; M represents a metal; n represents an integer of 1 to 5; and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.)
5. In claim 4, The method for processing an organic semiconductor layer, wherein the organometallic compound represented by the general formula (G1) is an organometallic compound represented by the following general formula (G2): 【Chemistry 5】 (In General Formula (G2), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms; M represents a metal; n represents an integer of 1 to 3; and n is the same as the valence of the metal M. Note that when n is 2 or greater, the multiple Ars may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may form a coordinate bond.)
6. In claim 4 or claim 5, After the step of forming an aluminum oxide film on the mask layer, forming a metal film or a metal compound film on the aluminum oxide film; a step of processing the shape of the organic semiconductor layer by using the aluminum oxide film and the metal film or the metal compound film; A method for processing an organic semiconductor layer comprising:
7. In claim 6, After the step of processing the shape of the organic semiconductor layer, removing the metal film or the metal compound film; and removing the mask layer and the aluminum oxide film using water or a liquid containing water as a solvent.
8. forming an organic semiconductor film on the first electrode; forming a mask film containing an organometallic compound represented by the following general formula (G1) on the organic semiconductor film; forming a first aluminum oxide film on the mask film; forming a metal film or a metal compound film on the first aluminum oxide film; forming a photomask on the metal film or the metal compound film; etching the metal film or the metal compound film using the photomask to form a metal layer or a metal compound layer overlapping the first electrode; removing the photomask; a step of etching the first aluminum oxide film, the mask film, and the organic semiconductor film using the metal layer or the metal compound layer as a mask to form a first aluminum oxide layer, a mask layer, and an organic semiconductor layer; removing the metal layer or the metal compound layer; forming an organic resin film to cover the first electrode, the organic semiconductor layer, the mask layer, and the first aluminum oxide layer; forming an opening in the organic resin film so as to overlap the first electrode, the organic semiconductor layer, the mask layer, and the first aluminum oxide layer; and removing the mask layer and the first aluminum oxide layer that overlap the opening using water or a liquid containing water as a solvent. 【Chemistry 6】 (In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms; X represents oxygen or sulfur; M represents a metal; n represents an integer of 1 to 5; and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.)
9. In claim 8, The method for producing an organic semiconductor device, wherein the organometallic compound represented by the general formula (G1) is an organometallic compound represented by the following general formula (G2): 【Chemistry 7】 (In General Formula (G2), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms; M represents a metal; n represents an integer of 1 to 3; and n is the same as the valence of the metal M. Note that when n is 2 or greater, the multiple Ars may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may form a coordinate bond.)
10. forming an organic semiconductor film on the first electrode; forming a mask film containing an organometallic compound represented by the following general formula (G1) on the organic semiconductor film; forming a first aluminum oxide film on the mask film; forming a metal film or a metal compound film on the first aluminum oxide film; forming a photomask on the metal film or the metal compound film; etching the metal film or the metal compound film using the photomask to form a metal layer or a metal compound layer overlapping the first electrode; removing the photomask; a step of etching the first aluminum oxide film, the mask film, and the organic semiconductor film using the metal layer or the metal compound layer as a mask to form a first aluminum oxide layer, a mask layer, and an organic semiconductor layer; removing the metal layer or the metal compound layer; forming a second aluminum oxide film covering the first electrode, the organic semiconductor layer, the mask layer, and the first aluminum oxide layer; forming an organic resin film covering the first electrode, the organic semiconductor layer, the mask layer, the first aluminum oxide layer, and the second aluminum oxide film; forming an opening in the organic resin film so as to overlap the first electrode, the organic semiconductor layer, the mask layer, the first aluminum oxide layer, and the second aluminum oxide film; and removing the mask layer, the first aluminum oxide layer, and the second aluminum oxide film that overlap the opening using water or a liquid containing water as a solvent. 【Chemistry 8】 (In General Formula (G1), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms; X represents oxygen or sulfur; M represents a metal; n represents an integer of 1 to 5; and n is the same as the valence of the metal M. Note that when n is 2 or more, multiple Ars may be the same or different, and Xs may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may be coordinately bonded.)
11. In claim 10, The method for producing an organic semiconductor device, wherein the organometallic compound represented by the general formula (G1) is an organometallic compound represented by the following general formula (G2): 【Chemistry 9】 (In General Formula (G2), Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms; M represents a metal; n represents an integer of 1 to 3; and n is the same as the valence of the metal M. Note that when n is 2 or greater, the multiple Ars may be the same or different. When Ar is a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a heteroatom of the heteroaryl group and the metal M may form a coordinate bond.)