Light-emitting device and light-emitting apparatus
By using a metal oxide and organic compound with a phenanthroline ring in the electron-injection layer, the degradation of light-emitting devices due to atmospheric exposure is mitigated, ensuring efficient and reliable operation in high-resolution displays.
Patent Information
- Application Number
- PCT/IB2025/050752
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-01-31
- Filing Date
- 2025-01-24
- Publication Date
- 2025-08-07
AI Technical Summary
Existing light-emitting devices, particularly organic EL devices, face degradation and reduced electron injection properties when exposed to atmospheric components like water and oxygen during photolithography processes, leading to increased driving voltage and decreased reliability.
Incorporating a metal oxide and an organic compound with a phenanthroline ring having an electron-donating group in the electron-injection layer, forming a mixed layer that interacts to create a donor level, reducing the electron injection barrier and maintaining electron injection properties even after exposure to the atmosphere.
The solution maintains electron injection efficiency and reliability, allowing for high-resolution display devices to be manufactured through photolithography without significant degradation, similar to vacuum-integrated processes.
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Figure IB2025050752_07082025_PF_FP_ABST
Abstract
Description
Light-emitting device and light-emitting apparatus
[0001] One aspect of the present invention relates to a light-emitting device.
[0002] One embodiment of the present invention is not limited to the above technical field, and examples of the technical field of one embodiment of the present invention include semiconductor devices, display devices, light-emitting devices, power storage devices, memory devices, electronic devices, lighting devices, input devices (e.g., touch sensors), input / output devices (e.g., touch panels), driving methods thereof, and manufacturing methods thereof.
[0003] Display devices have been developed for a variety of applications in recent years. For example, applications of large display devices include home television devices (also referred to as televisions or television receivers), digital signage, and public information displays (PIDs), while applications of small display devices include smartphones and tablet terminals equipped with touch panels.
[0004] At the same time, display devices are also being demanded to have higher resolution. Devices requiring high-resolution display devices include, for example, devices for virtual reality (VR), augmented reality (AR), substitutional reality (SR), and mixed reality (MR).
[0005] As display elements used in display devices, the development of light-emitting devices (also referred to as light-emitting elements) has been actively promoted. Light-emitting devices (also referred to as EL devices or EL elements) utilizing the electroluminescence (hereinafter referred to as EL) phenomenon, particularly organic EL devices that mainly use organic compounds, are suitable for display devices because they have features such as being easily thin and lightweight, being capable of high-speed response to input signals, and being capable of being driven by a DC constant voltage power supply.
[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, it is possible to obtain a high-resolution display device with an interval of several micrometers between organic compound layers (see, for example, Patent Document 1).
[0007] Patent Publication No. 2018-521459 International Publication No. 2021 / 045178
[0008] It has long been known that exposure to atmospheric components such as water and oxygen can affect the initial characteristics and reliability of the cathode and organic compound layers of organic EL devices, and so it has been common practice to handle them in an inert gas atmosphere or a near-vacuum atmosphere. In particular, alkali metals, alkaline earth metals, or their compounds are often used for the electron injection layer. However, these metals and compounds are highly reactive with water and oxygen, and when the surface of the organic compound layer is exposed to the atmosphere, they quickly deteriorate and no longer function as an electron injection layer.
[0009] However, in the process of processing by photolithography as described above, it is necessary to expose the organic EL device to the atmosphere.
[0010] An object of one aspect of the present invention is to provide a novel light-emitting device. Alternatively, an object of another aspect of the present invention is to provide a light-emitting device having good efficiency. Alternatively, an object of one aspect of the present invention is to provide a light-emitting device having good reliability. Alternatively, an object of another aspect of the present invention is to provide a light-emitting device having good efficiency and reliability.
[0011] Alternatively, one embodiment of the present invention has an object to provide a novel light-emitting device manufactured through a photolithography process. Alternatively, another embodiment of the present invention has an object to provide a light-emitting device manufactured through a photolithography process and having good efficiency. Alternatively, one embodiment of the present invention has an object to provide a light-emitting device manufactured through a photolithography process and having good reliability. Alternatively, another embodiment of the present invention has an object to provide a light-emitting device manufactured through a photolithography process and having good luminous efficiency and reliability.
[0012] Another object of one embodiment of the present invention is to provide a novel light-emitting device that can be used in a high-resolution display device. Another object of another embodiment of the present invention is to provide a light-emitting device that can be used in a high-resolution display device and has good efficiency. Another object of one embodiment of the present invention is to provide a light-emitting device that can be used in a high-resolution display device and has good reliability. Another object of another embodiment of the present invention is to provide a light-emitting device that can be used in a high-resolution display device and has good emission efficiency and reliability.
[0013] Another object of another embodiment of the present invention is to provide a highly reliable display device.Another object of another embodiment of the present invention is to provide a high-definition display device.Another object of another embodiment of the present invention is to provide a high-definition and highly reliable display device.
[0014] Note that the description of these problems does not preclude the existence of other problems. One embodiment of the present invention does not necessarily have to solve all of these problems. Problems other than these can be extracted from the description in the specification, drawings, and claims.
[0015] One embodiment of the present invention is a light-emitting device having a first electrode, a second electrode, and an organic compound layer formed on a first insulating layer, wherein the first electrode is formed in contact with the first insulating layer, the organic compound layer is located between the first electrode and the second electrode, the second electrode and the organic compound layer are separated from at least one of a plurality of other light-emitting devices adjacent to the light-emitting device, when viewed from a direction approximately perpendicular to a surface of the first insulating layer on which the first electrode is formed, an outline of the second electrode and an outline of the organic compound layer approximately coincide with each other, and the organic compound layer has a light-emitting layer and an electron-injection layer, the electron-injection layer is a mixed layer of a metal oxide and a first organic compound, and the first organic compound is an organic compound having a phenanthroline ring having an electron-donating group.
[0016] Another embodiment of the present invention is a light-emitting device having the above structure, in which the organic compound layer has a P-type layer between the electron-injection layer and the second electrode, and the P-type layer includes a third organic compound having a hole-transporting property, and a fourth organic compound having at least one of a halogen group and a cyano group or a second metal oxide.
[0017] Another aspect of the present invention is a light-emitting device among a plurality of light-emitting devices included in a light-emitting device group, the light-emitting device having a first electrode group formed on the same insulating surface, a second electrode group facing the first electrode group, and a first layer group located between the first electrode group and the second electrode group, the light-emitting device having a first electrode, a second electrode, and a first layer, the first electrode being one of the first electrode group, the first electrode being independent for each of the plurality of light-emitting devices, the first layer being one of the first layer group, the first layer being independent for each of the plurality of light-emitting devices, and the second electrode being one of the second layer group. the second electrode is independent for each of the plurality of light-emitting devices, and the second electrode is a continuous conductive layer shared by the plurality of light-emitting devices; the second electrode and the first layer overlap the first electrode; the first layer has a light-emitting layer and an electron injection layer; the electron injection layer is a mixed layer of a metal oxide and a first organic compound; the first organic compound is an organic compound having a phenanthroline ring having an electron-donating group; and the distance between the first layer of the light-emitting device and the first layer of another light-emitting device adjacent to the light-emitting device is 0.5 μm or more and 5 μm or less.
[0018] Another embodiment of the present invention is a light-emitting device having the above structure, wherein the first layer has a P-type layer between the electron-injection layer and the second electrode, and the P-type layer includes a third organic compound having a hole-transporting property, and a fourth organic compound having at least one of a halogen group and a cyano group or the second metal oxide.
[0019] Another embodiment of the present invention is a light-emitting device having the above structure, in which an outline of the second electrode and an outline of the first layer are substantially aligned when viewed from a direction substantially perpendicular to the insulating surface.
[0020] Another embodiment of the present invention is a light-emitting device having the above structure, in which an end portion of the second electrode in a cross section and an end portion of the first layer in a cross section are aligned in a direction substantially perpendicular to the insulating surface.
[0021] Another embodiment of the present invention is a light-emitting device having any of the above structures, in which the metal oxide is an oxide containing an element belonging to Group 1, Group 2, Group 3, Group 11, or Group 13.
[0022] Alternatively, in the above structure, another embodiment of the present invention is a method for manufacturing a semiconductor device, wherein the minimum value of the electrostatic potential of the first organic compound is 0.0004 e / a when the threshold of the electron density distribution in atomic units is 0.0004 e / a. 0 3 In the case where h A light emitting device comprising:
[0023] Another embodiment of the present invention is a light-emitting device having the above structure, wherein the phenanthroline ring is a 1,10-phenanthroline ring and has an electron-donating group at least at one of the 4-position and the 7-position.
[0024] Another embodiment of the present invention is a light-emitting device having the above structure, wherein the electron-donating group is one or more of an alkyl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, and a heterocyclic amino group.
[0025] Alternatively, another embodiment of the present invention is a light-emitting device having the above structure, wherein the phenanthroline ring is a 1,10-phenanthroline ring and has an electron-donating group at at least one of the 4-position and the 7-position, and the electron-donating group is one or more of an alkyl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, and a heterocyclic amino group.
[0026] Another embodiment of the present invention is a light-emitting device having any of the above structures, in which the first organic compound has an acid dissociation constant pKa of 8 or more.
[0027] Another embodiment of the present invention is a light-emitting device having any of the above structures, in which the electron-injection layer further contains a second organic compound.
[0028] Another embodiment of the present invention is a light-emitting device having any of the above structures, in which the second organic compound is an organic compound having a π-electron-deficient heteroaromatic ring.
[0029] Another embodiment of the present invention is a light-emitting device having any of the above structures, in which the glass transition temperature of the second organic compound is 100° C. or higher.
[0030] Alternatively, in the above structure, the electron-injection layer may have a spin density of 5×10 or less as measured by electron spin resonance (ESR). 16 spins / cm 3 The above is a light-emitting device.
[0031] Another embodiment of the present invention is a light-emitting device having the above structure, further including a hole-injection layer located between the first electrode and the light-emitting layer, the hole-injection layer including a third organic compound having hole-transport properties and a first substance having acceptor properties for the third organic compound. Another embodiment of the present invention is a light-emitting device having the above structure, further including the hole-injection layer including the third organic compound having hole-transport properties and an organic compound having four or more halogen groups and / or cyano groups. Another embodiment of the present invention is a light-emitting device having the above structure, further including the hole-injection layer including the third organic compound having hole-transport properties and a metal oxide different from the metal oxide included in the electron-injection layer.
[0032] Alternatively, in another embodiment of the present invention, in the above structure, the hole-injection layer has a spin density of 1×10 or less as measured by electron spin resonance. 17 spins / cm 3 The above is a light-emitting device.
[0033] Alternatively, another embodiment of the present invention is a light-emitting device having a plurality of light-emitting devices, each of which is any one of the light-emitting devices described above, and each of the plurality of light-emitting devices has an organic compound layer including a light-emitting layer and an electron-injection layer between a first electrode and a second electrode, and the second electrode and the organic compound layer included in each of the plurality of light-emitting devices are independent from each other among the plurality of light-emitting devices.
[0034] Another embodiment of the present invention is a display module including the above-described light-emitting device and at least one of a connector and an integrated circuit.
[0035] Another embodiment of the present invention is an electronic device including the above-described light-emitting device and at least one of a housing, a battery, a camera, a speaker, and a microphone.
[0036] According to one embodiment of the present invention, a novel light-emitting device can be provided. Alternatively, according to another embodiment of the present invention, a light-emitting device having good efficiency can be provided. Alternatively, according to one embodiment of the present invention, a light-emitting device having good reliability can be provided. Alternatively, according to another embodiment of the present invention, a light-emitting device having good efficiency and reliability can be provided.
[0037] According to one embodiment of the present invention, a novel light-emitting device manufactured through a photolithography process can be provided. According to another embodiment of the present invention, a light-emitting device manufactured through a photolithography process and having high efficiency can be provided. According to one embodiment of the present invention, a light-emitting device manufactured through a photolithography process and having high reliability can be provided. According to another embodiment of the present invention, a light-emitting device manufactured through a photolithography process and having high emission efficiency and reliability can be provided.
[0038] According to one embodiment of the present invention, a novel light-emitting device that can be used in a high-resolution display device can be provided. According to another embodiment of the present invention, a light-emitting device that can be used in a high-resolution display device and has high emission efficiency can be provided. According to one embodiment of the present invention, a light-emitting device that can be used in a high-resolution display device and has high emission efficiency and reliability can be provided. According to another embodiment of the present invention, a light-emitting device that can be used in a high-resolution display device and has high emission efficiency and reliability can be provided.
[0039] According to another embodiment of the present invention, a highly reliable display device can be provided. According to another embodiment of the present invention, a high-definition display device can be provided. According to another embodiment of the present invention, a high-definition and highly reliable display device can be provided.
[0040] Alternatively, a novel organic compound, a novel light-emitting device, a novel display device, a novel display module, and a novel electronic device can be provided.
[0041] Note that the description of these effects does not preclude the existence of other effects. One embodiment of the present invention does not necessarily have all of these effects. Effects other than these can be extracted from the description in the specification, drawings, and claims.
[0042] FIGS. 1A to 1C are diagrams illustrating a light-emitting device. FIGS. 2A and 2B are diagrams illustrating a light-emitting device. FIGS. 3A and 3B are top views and cross-sectional views of a light-emitting device. FIGS. 4A to 4E are cross-sectional views illustrating an example of a manufacturing method of a display device. FIGS. 5A and 5B are cross-sectional views illustrating an example of a manufacturing method of a display device. FIGS. 6A to 6D are cross-sectional views illustrating an example of a manufacturing method of a display device. FIGS. 7A to 7C are cross-sectional views illustrating an example of a manufacturing method of a display device. FIGS. 8A to 8C are cross-sectional views illustrating an example of a manufacturing method of a display device. FIGS. 9A and 9B are cross-sectional views illustrating an example of a manufacturing method of a display device. FIGS. 10A and 10B are perspective views illustrating a structural example of a display module. FIGS. 11A and 11B are cross-sectional views illustrating a structural example of a display device. FIG. 12 is a perspective view illustrating a structural example of a display device. FIG. 13 is a cross-sectional view illustrating a structural example of a display device. FIG. 14 is a cross-sectional view illustrating a structural example of a display device. FIGS. 15A to 15C are cross-sectional views illustrating a structural example of a display device. FIG. 16 is a cross-sectional view showing an example of the configuration of a display device. FIGS. 17A to 17C are cross-sectional views showing an example of the configuration of a display device. FIGS. 18A to 18D are views showing an example of an electronic device. FIGS. 19A to 19F are views showing an example of an electronic device. FIGS. 20A to 20G are views showing an example of an electronic device. FIG. 21 shows a cross-sectional view of an organic film (sample 1-1) doped with indium and an indium oxide (In 2 O 322A to 22G are diagrams showing examples of pixel layouts. FIG. 23 is a diagram showing the luminance-current density characteristics of light-emitting device 1 and comparative light-emitting device 1. FIG. 24 is a diagram showing the luminance-voltage characteristics of light-emitting device 1 and comparative light-emitting device 1. FIG. 25 is a diagram showing the current efficiency-current density characteristics of light-emitting device 1 and comparative light-emitting device 1. FIG. 26 is a diagram showing the current density-voltage characteristics of light-emitting device 1 and comparative light-emitting device 1. FIG. 27 is a diagram showing the electroluminescence spectra of light-emitting device 1 and comparative light-emitting device 1.
[0043] The embodiments 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 can be made in form and detail 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.
[0044] 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.
[0045] (Embodiment 1) Vacuum deposition using a metal mask (mask deposition) is widely used as a method for forming 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 issues of alignment accuracy and spacing with the substrate. On the other hand, by processing the shape of an organic semiconductor film using a photolithography method, it is expected that organic semiconductor devices with more precise patterns will be realized. Furthermore, since photolithography can more easily be used to fabricate larger areas than mask deposition, research into processing organic semiconductor films using photolithography is underway.
[0046] Furthermore, it has long been known that exposure of the organic compound layers and cathodes in organic EL devices to atmospheric components such as water and oxygen can affect their initial characteristics or reliability, and it has been common knowledge that they should be handled in an inert gas atmosphere or a near-vacuum atmosphere.
[0047] In particular, alkali metals or alkaline earth metals, or compounds thereof (hereinafter also referred to as Li compounds, etc.) may be used in the electron injection layer of light-emitting devices. However, these Li compounds, etc., are highly reactive with water or oxygen, and deteriorate rapidly when exposed to the atmosphere, resulting in a significant decrease in electron injection properties. Furthermore, even when other metals with small work functions are used in the cathode, exposure to water, oxygen, etc. may also decrease electron injection properties, resulting in a significant increase in driving voltage.
[0048] However, the photolithography process described above inevitably requires that the light-emitting device be exposed to the atmosphere during fabrication. Furthermore, the photolithography process involves the use of various chemicals and a cleaning process, creating harsh conditions that further accelerate degradation.
[0049] Therefore, when the cathode and the organic compound layer are processed by photolithography, the electron injection properties of the cathode and the electron injection layer may be significantly reduced. As a result, organic EL devices processed by photolithography have a significantly increased driving voltage, making it difficult to obtain good characteristics.
[0050] To avoid this degradation, photolithography can be performed before the formation of the electron injection layer and cathode, and then the electron injection layer and cathode are formed afterward. However, performing photolithography after the formation of both electrodes minimizes the number of steps required for the photolithography process and offers significant cost benefits. Furthermore, the organic compound layer is significantly less likely to come into contact with chemicals and the atmosphere, achieving performance similar to that of a light-emitting device fabricated without exposure to the atmosphere.
[0051] Therefore, one embodiment of the present invention provides a light-emitting device having a first electrode, an organic compound layer, and a second electrode from the substrate side, which is manufactured by forming the second electrode and then performing a photolithography process, and has good characteristics.
[0052] As described above, if the high reactivity of alkali metal compounds and the like used in the electron injection layer is one of the factors that cause the layer to react sensitively to processes such as exposure to the atmosphere, etching, and cleaning, and thus to deteriorate, it is thought that if a less reactive substance can be used in place of the alkali metal compounds and the like, it would be possible to suppress an increase in driving voltage even after processing by photolithography.
[0053] Metal oxides (excluding oxides of alkali metals) are generally more stable than alkali metal compounds and are therefore easier to handle. Furthermore, because metal oxides are stable, they are also materials that are relatively less susceptible to deterioration even when exposed to the atmosphere. However, because metal oxides are stable, it has been difficult to obtain the same properties as alkali metal compounds in conventional light-emitting devices, even when they are used in place of alkali metal compounds in the electron injection layer. Therefore, it has not been possible to obtain organic EL devices with properties suitable for practical use.
[0054] Here, the present inventors have found that by using a layer containing a metal oxide and an organic compound having a phenanthroline ring with an electron-donating group as the electron-injection layer, it is possible to obtain an organic EL device in which the decrease in electron injection properties in the electron-injection layer is suppressed even after the device has undergone a photolithography step that involves exposure of the organic compound layer to the atmosphere.
[0055] This is because the first organic compound has a structure in which an electron-donating group is further added to the phenanthroline ring, which is likely to interact with metals and the like, thereby increasing the electron density of the phenanthroline ring and enabling it to interact with a stable metal oxide to such an extent that it exhibits donor properties to an adjacent material having electron-transport properties.
[0056] The metal oxide and the first organic compound interact with each other to form a donor level (a Singly Occupied Molecular Orbital (SOMO) level or a Highest Occupied Molecular Orbital (HOMO) level). This can reduce the barrier to electron injection into the electron transport layer.
[0057] Furthermore, because metal oxides are stable as described above, even if the organic EL device according to one embodiment of the present invention is processed by photolithography, which involves an air exposure step during the fabrication process, it can be an organic EL device having an electron injection layer that has good electron injection properties similar to those of an organic EL device fabricated by a so-called integrated vacuum process, which is fabricated without exposure to air.
[0058] In this way, by using a metal oxide and the first organic compound for the electron injection layer, it is possible to form an electron injection layer that is resistant to oxygen and water in the atmosphere, as well as to water and chemicals used in lithography processes.
[0059] The electron injection layer containing a metal oxide and an organic compound (first organic compound) having a phenanthroline ring with an electron-donating group is preferably a mixed layer of the metal oxide and the first organic compound. When the electron injection layer is a mixed layer of the metal oxide and the first organic compound, an organic EL device can be obtained that has good electron injection properties whether it is fabricated through a vacuum integrated process or via an air exposure process. Furthermore, the mixed layer can have fewer layers than a laminated structure, which increases productivity and facilitates mass production.
[0060] Here, lithium oxide (Li 2Unlike oxides of other metals, oxides of alkali metals or alkaline earth metals such as ZnO (Alkali Metal Oxide) exhibit good characteristics when used in the electron injection layer of organic EL devices fabricated through a vacuum integrated process. However, as mentioned above, when fabricated through a photolithography process involving exposure of the organic compound layer to the atmosphere, even tandem organic EL devices using alkali metal or alkaline earth metal oxides in the electron injection layer exhibit significantly higher driving voltages than organic EL devices fabricated through a vacuum integrated process. This is thought to be due to the deterioration of the alkali metal or alkaline earth metal oxides due to exposure to the atmosphere, as mentioned above, resulting in a decrease in donor properties.
[0061] In one aspect of the present invention, lithium oxide (Li 2 By using an organic compound (first organic compound) having an oxide of an alkali metal or alkaline earth metal and a phenanthroline ring having an electron-donating group in the electron injection layer, such as an oxide of an alkali metal or alkaline earth metal, it is possible to obtain an organic EL device in which the decrease in electron injection property in the electron injection layer is suppressed, similar to an organic EL device produced by an integrated vacuum process, even in an organic EL device produced through a photolithography process involving exposure to the atmosphere.
[0062] This is because the electron injection layer contains an oxide of an alkali metal or alkaline earth metal and a first organic compound having an electron-donating phenanthroline ring, and the donor level (SOMO level or HOMO level) is formed by interaction, and the high energy level reduces the electron injection barrier to the electron transport layer, allowing for smooth injection and transport of electrons into the electron transport layer. This makes it possible to obtain a tandem organic EL device in which the electron injection property of the electron injection layer is not deteriorated even when exposed to the atmosphere.
[0063] <Metal Oxide> The metal oxide used in one embodiment of the present invention will be described in detail. Examples of the metal oxide contained in the electron-injection layer include oxides containing alkali metals (Group 1 elements) such as Li, alkaline earth metals (Group 2 elements) such as Mg and Ca, Group 3 elements including lanthanoids such as Y, Eu, and Yb, Group 11 elements such as Cu, Ag, and Au, earth metals (Group 13 elements) such as Al and In, and Group 14 elements such as Sn.
[0064] The use of an oxide of an alkali metal or alkaline earth metal as the metal oxide is preferable because it can increase the energy level of the donor level formed by interaction with the first organic compound, allowing electrons to be smoothly injected and transported into the electron transport layer, thereby providing a light-emitting device with a low driving voltage and high light emission efficiency. Furthermore, transition metal oxides are preferable because they are stable and have low reactivity with components such as water and oxygen in the atmosphere. Among the above, the use of a metal oxide containing an element belonging to an odd group (Group 1, Group 3, Group 11, or Group 13) of the periodic table is preferable because it easily forms a donor level with the first organic compound.
[0065] In addition, metals or metal oxides that have a low melting point and can be formed into a film by vacuum deposition are preferred because they can easily form a mixed layer or laminate with an organic compound. Specifically, for example, metals and metal oxides of Group 11 elements and Group 13 elements have a low melting point and can be suitably used for vacuum deposition. Furthermore, metals and metal oxides of Group 11 elements and Group 13 elements are preferred because they are stable to oxygen and water in the atmosphere. For metals or metal oxides that can be formed into a film by vacuum deposition, the melting point at normal pressure is preferably 2000°C or less, preferably 1500°C or less, and more preferably 1000°C or less, or the sublimation temperature under reduced pressure (vacuum of 1 Pa or less) is preferably 1500°C or less, preferably 1000°C or less, and more preferably 500°C or less.
[0066] Specific examples of the metal oxide that can be used include lithium oxide, magnesium oxide, calcium oxide, silver oxide, and indium oxide. As described above, it is also possible to use a metal material that is oxidized to become a metal oxide during processes such as film formation and exposure to the atmosphere. Specific examples of such metal materials that can be used include lithium, magnesium, calcium, ytterbium, silver, aluminum, and indium.
[0067] As described above, when forming the electron injection layer, a film is formed using a metal element rather than a metal oxide, and the metal element is oxidized during or after film formation, so that the metal oxide is contained in the electron injection layer. For example, the metal element can be oxidized to form a metal oxide in a film formation process, an air exposure process during the manufacturing process, or a treatment process (heat treatment, etc.) in an atmosphere containing oxygen such as the air. Figure 21 shows a 1×10 −4 An organic film (sample 1-1) doped with indium by co-evaporation under reduced pressure of about Pa and an indium oxide (In 2 O 3 1 shows the results of measurement of an organic film (sample 1-2) doped with ZnO by XPS (X-ray photoelectron spectroscopy).
[0068] Sample 1-1 was prepared by depositing a film of 2,2'-(1,3-phenylene)bis(9-phenyl-1,10-phenanthroline) (abbreviation: mPPhen2P), 4,7-di-1-pyrrolidinyl-1,10-phenanthroline (abbreviation: Pyrrd-Phen), and indium on a quartz substrate in a volume ratio of 0.5:0.5:0.1 (mPPhen2P:Pyrrd-Phen:In) and to a thickness of 50 nm. Sample 1-2 was prepared by depositing a film of mPPhen2P, Pyrrd-Phen, and indium oxide In on a quartz substrate. 2 O 3 ) in a volume ratio of 0.5:0.5:0.1 (mPPhen2P:Pyrrd-Phen:In 2 O 3 ) and to a thickness of 50 nm.
[0069] 21, the measurement results of the indium In3d5 / 2 spectrum of Sample 1-1 and Sample 1-2 almost overlap, indicating that there is no difference in the state of indium between these two samples. The results of waveform analysis of this spectrum are shown in the table below. This indicates that almost all of the indium in the sample exists as indium oxide.
[0070]
[0071] In this way, even in an organic EL device in which a metal element is used instead of a metal oxide during film formation of the electron injection layer, the metal can be subsequently converted into an oxide, thereby making it possible to obtain an organic EL device according to one embodiment of the present invention.
[0072] As described above, by forming the electron injection layer as a layer containing a metal oxide and an organic compound having a phenanthroline ring with an electron-donating group (first organic compound), it is easy to obtain a device in which the decrease in electron injection property in the electron injection layer is suppressed, even in a tandem organic EL device fabricated via an air exposure step.
[0073] <First Organic Compound> The electron injection layer contains a first organic compound in addition to a metal oxide. As the first organic compound contained in the electron injection layer, an organic compound having a phenanthroline ring can be used. As the first organic compound, it is more preferable to use an organic compound having a phenanthroline ring with an electron-donating group, because this can increase the electron density of the phenanthroline ring.
[0074] Among phenanthroline rings, organic compounds having a 1,10-phenanthroline ring are particularly preferred because the two nitrogen atoms contained therein are located at positions that facilitate coordination with metal oxides, and therefore interaction with metal oxides occurs easily.
[0075] When an electron-donating group is introduced into the 1,10-phenanthroline ring, the electron-donating group is preferably substituted at positions 4 and 7 of the 1,10-phenanthroline ring. By introducing the electron-donating group into positions 4 and 7 of the 1,10-phenanthroline ring, the electron density of the nitrogen atoms at positions 1 and 10 can be increased, making it easier for the compound to interact with a metal oxide.
[0076] Specific examples of the electron-donating group include an alkyl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, and a heterocyclic amino group. However, the electron-donating group that is preferably introduced into the phenanthroline ring is not limited to these. Any group that can increase the electron density of the phenanthroline ring by being introduced into the phenanthroline ring can be used as the electron-donating group. In addition, the electron-donating group may be introduced into the phenanthroline ring via an arylene group such as a phenylene group, and the arylene group is preferably a p-phenylene group.
[0077] Specific examples of alkyl groups that can be used as the electron-donating group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, a hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a neohexyl group, a 3-methylpentyl group, a 2-methylpentyl group, a 2-ethylbutyl group, a 1,2-dimethylbutyl group, and a 2,3-dimethylbutyl group.
[0078] Specific examples of alkoxy groups that can be used as the electron-donating group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a neopentyloxy group, an n-hexyloxy group, an isohexyloxy group, a sec-hexyloxy group, a tert-hexyloxy group, and a neohexyloxy group.
[0079] Specific examples of the aryloxy group that can be used as the electron-donating group include a phenoxy group, an o-tolyloxy group, an m-tolyloxy group, a p-tolyloxy group, a mesityloxy group, an o-biphenyloxy group, an m-biphenyloxy group, a p-biphenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-fluorenyloxy group, etc. The aryloxy group may further have a substituent, and specific examples of the substituent include an alkyl group, an alkoxy group, a phenyl group, etc.
[0080] Specific examples of alkylamino groups that can be used as the electron-donating group include a dimethylamino group and a diethylamino group.
[0081] Specific examples of the arylamino group that can be used as the electron-donating group include a diphenylamino group, a bis(α-naphthyl)amino group, a bis(m-tolyl)amino group, etc. The arylamino group may further have a substituent, and specific examples of the substituent include an alkyl group, an alkoxy group, and a phenyl group.
[0082] Specific examples of heterocyclic amino groups that can be used as the electron-donating group include groups represented by the following structural formulas (R-1) to (R-26): The heterocyclic amino group may further have a substituent, and specific examples of the substituent include an alkyl group, an alkoxy group, and a phenyl group.
[0083]
[0084] In addition, the group represented by the structural formula (R-1), (R-2), (R-3), (R-4), (R-5), (R-8), (R-9), (R-10), (R-12), (R-14), (R-15), (R-16), (R-17) or (R-21) is more preferred as the electron-donating group.Among them, the group represented by the structural formula (R-3), (R-4), (R-8) or (R-21) is preferred because it has high electron-donating property and can further increase the electron density of the phenanthroline ring.
[0085] Specific examples of the electron-donating group include groups represented by the following structural formulae (R-27) and (R-28).
[0086]
[0087] The organic compound having a phenanthroline ring that can be used as the first organic compound may have both the above-mentioned electron-donating group and other substituents.In addition to the above-mentioned electron-donating group, a specific example of a substituent that can be introduced into the phenanthroline ring is an aryl group.Specific examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a mesityl group, an o-biphenyl group, an m-biphenyl group, a p-biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 2-fluorenyl group.The aryl group may further have a substituent, and specific examples of the substituent include an alkyl group, an alkoxy group, and a phenyl group.
[0088] Specific examples of organic compounds having a phenanthroline ring that can be used as the first organic compound are shown in structural formulas (100) to (107). Note that the organic compounds that can be used as the first organic compound are not limited to these.
[0089]
[0090] It is preferable that the minimum negative value of the electrostatic potential (ESP) of the first organic compound is small (the absolute negative value is large), since this increases the efficiency of interaction with the metal oxide.
[0091] In organic compounds having a phenanthroline ring, the electrostatic potential around the nitrogen atom of the phenanthroline ring tends to be negative. However, by introducing an electron-donating group into the phenanthroline ring, the electrostatic potential around the nitrogen atom of the phenanthroline ring can be further reduced (the absolute value of the negative potential can be increased).
[0092] The electrostatic potential is the interaction energy between a positive point charge with a unit charge and the electron distribution of a molecule. The value of the electrostatic potential also changes depending on the threshold of the electron density.
[0093] In order to increase the efficiency of interaction with the metal oxide, the minimum value of the electrostatic potential of the first organic compound is preferably smaller (more negative) than the minimum value of the electrostatic potential of the phenanthroline ring having no substituent.
[0094] Specifically, the threshold value of the electron density distribution in atomic units is set to 0.0004 e / a 0 3 (e is the elementary charge (1e = 1.60218 x 10 −19 C) by a 0 is the Bohr radius (1a 0 = 5.29177 x 10 −11 m)), the minimum value of the electrostatic potential of the first organic compound is −0.085 E h (E h is the Hartree energy (1E h = 27.211 eV) or less is preferred, and -0.090 E h Further, it is more preferable that the threshold value of the electron density distribution in the atomic unit system is 0.003 e / a 0 3 When the electrostatic potential of the first organic compound is h Preferably, it is less than -0.13E h Further, the ESP of the first organic compound is more preferably 0.0004 e / a or less. 0 3 The minimum value is -0.085E h and the threshold of the electron density distribution in atomic units is 0.003 e / a 0 3 The minimum value is -0.12E h It is even more preferable that:
[0095] The minimum electrostatic potential (ESP) values of the organic compounds represented by the structural formulas (100) to (107) and BPhen, mPPhen2P, NBPhen, Phen, and Hid2Phen, which are shown as organic compounds that can be suitably used for the first organic compound, were estimated by quantum chemical calculation. The structural formulas of the organic compounds represented by the structural formulas (100) to (107), BPhen, mPPhen2P, NBPhen, Phen, and Hid2Phen are shown below.
[0096]
[0097] Gaussian09 was used as the quantum chemistry calculation program. Calculations were performed using an SGI8600 manufactured by HPE. The most stable structure of the first organic compound in the ground state was calculated using density functional theory (DFT). 6-311G(d,p) was used as the basis function, and B3LYP was used as the functional.
[0098] Table 2 shows the analysis results of the electrostatic potential in the ground state of the first organic compound. The electrostatic potential is the interaction energy between a positive point charge with a unit charge and the electron distribution of the molecule. The value of the electrostatic potential also changes depending on the threshold of the electron density. In Table 2, the threshold of the electron density in the atomic unit system is set to 0.0004 e / a. 0 3 or 0.003 e / a 0 3 The electrostatic potential in the electron density distribution in atomic units is shown.
[0099]
[0100] From the above table, the organic compounds represented by the structural formulas (100) to (103) and Hid2Phen have an electron density distribution threshold of 0.0004 e / a in atomic units. 0 3 When this is done, the minimum value of ESP is -0.085E hThe organic compounds represented by the structural formulas (100) to (103) and Hid2Phen have an electron density distribution threshold of 0.003 e / a in atomic units. 0 3 When this is done, the minimum value of ESP is -0.12E h These are the following and have been found to be more preferable as the first organic compound.
[0101] This is because the organic compounds represented by structural formulas (100) to (103) and Hid2Phen have electron-donating groups introduced at the 4- and 7-positions of the 1,10-phenanthroline ring, and therefore have high electron-donating properties to the nitrogens at the 1- and 10-positions of the phenanthroline ring.
[0102] The organic compounds represented by the structural formulas (100) and (103) and Hid2Phen have an electron density distribution threshold of 0.0004 e / a in atomic units. 0 3 When this is done, the minimum value of ESP is -0.090E h The organic compound represented by the structural formula (103) and Hid2Phen have an electron density distribution threshold of 0.003 e / a in atomic units. 0 3 When this is done, the minimum value of ESP is -0.13E h The following compounds were found to be particularly preferable as the first organic compound.
[0103] In addition, the organic compound represented by the structural formula (103) and Hid2Phen have an electron density distribution threshold of 0.0004 e / a in the atomic unit system. 0 3 When this is done, the minimum value of ESP is -0.090E h and the threshold of the electron density distribution in atomic units is 0.003 e / a 0 3 When this is done, the minimum value of ESP is -0.13E h The following compounds were found to be preferable as the first organic compound.
[0104] Furthermore, when the first organic compound has high basicity, it can interact with holes to significantly reduce the hole transport property in the electron injection layer, thereby enabling to obtain a light-emitting device with high efficiency and low driving voltage, which is preferable. Specifically, the acid dissociation constant pKa of the first organic compound is preferably 8 or more, more preferably 10 or more, and even more preferably 12 or more.
[0105] In addition, when the acid dissociation constant pKa of an organic compound is unknown, the acid dissociation constant pKa of each skeleton of the organic compound is examined, and the largest acid dissociation constant pKa selected from the examined acid dissociation constants can be regarded as the acid dissociation constant pKa of the organic compound.
[0106] Alternatively, the acid dissociation constant may be calculated. For example, the acid dissociation constant pKa can be calculated using the following calculation method.
[0107] The initial molecular structure of each molecule used as a calculation model is the most stable structure (singlet ground state) obtained from first-principles calculations.
[0108] The first-principles calculation uses Jaguar, a quantum chemistry calculation software manufactured by Schrödinger, to calculate the most stable structure in the singlet ground state using density functional theory (DFT). 6-31G** is used as the basis function, and B3LYP-D3 is used as the functional. The structure to be subjected to quantum chemistry calculation is subjected to conformational analysis and sampling using the Maestro GUI manufactured by Schrödinger, using mixed torsional / low-mode sampling.
[0109] In the pKa calculation, one or more atoms of each molecule are designated as basic sites, and Macro Model is used to search for the stable structure of the protonated molecule in water. A conformational search is performed using the OPLS2005 force field, and the lowest energy conformer is used. Using the Jaguar pKa calculation module, the structure is optimized with B3LYP / 6-31G*, followed by a single-point calculation with cc-pVTZ(+), and the pKa value is calculated using empirical corrections for functional groups. For molecules with one or more atoms designated as basic sites, the largest value obtained is used as the pKa value. The obtained pKa values are shown below.
[0110] The acid dissociation constant pKa of 2,9hpp2Phen is 13.35, the acid dissociation constant pKa of 4,7hpp2Phen is 13.42, the acid dissociation constant pKa of Pyrrd-Phen is 11.23, the acid dissociation constant pKa of mPPhen2P is 5.16, the acid dissociation constant pKa of NBPhen is 5.59, and the acid dissociation constant pKa of BPhen is 5.62.
[0111] The electron injection layer is a layer provided in contact with the second electrode and the electron transport layer as described above, and contains a metal oxide and an organic compound having a phenanthroline ring with an electron-donating group (first organic compound). The electron injection layer may contain a second organic compound in addition to the metal oxide and the organic compound having a phenanthroline ring with an electron-donating group (first organic compound).
[0112] <Second Organic Compound> The electron injection layer preferably contains a second organic compound in addition to the metal oxide and the first organic compound. The presence of the second organic compound can improve heat resistance and electron transport properties.
[0113] The second organic compound can be an organic compound having an electron transport property. The organic compound having an electron transport property has an electron mobility of 1×10 or less at a square root of an electric field strength [V / cm] of 600. −7 cm 2 / Vs or more, preferably 1×10 −6 cm 2A 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 a hole transporting property.
[0114] An example of a material having electron transport properties is bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeBq 2 Preferred are metal complexes such as 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), and bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ), as well as organic compounds having a π-electron-deficient heteroaromatic ring. Examples of organic compounds having a π-electron-deficient heteroaromatic ring skeleton include organic compounds having a heteroaromatic ring with an azole skeleton, organic compounds having a heteroaromatic ring with a pyridine skeleton, organic compounds having a heteroaromatic ring with a diazine skeleton, and organic compounds having a heteroaromatic ring with a triazine skeleton.
[0115] Among these, organic compounds containing a heteroaromatic ring having a diazine skeleton (pyrimidine skeleton, pyrazine skeleton, pyridazine skeleton), organic compounds containing a heteroaromatic ring having a pyridine skeleton, and organic compounds containing a heteroaromatic ring having a triazine skeleton are preferred because of their high reliability. In particular, organic compounds containing a heteroaromatic ring having a diazine (pyrimidine or pyrazine) skeleton and organic compounds containing a heteroaromatic ring having a triazine skeleton have high electron transport properties and contribute to reducing driving voltage. In addition, benzofuropyrimidine skeletons, benzothienopyrimidine skeletons, benzofuropyrazine skeletons, and benzothienopyrazine skeletons are preferred because of their high acceptor properties and high reliability.
[0116] Examples of organic compounds having a π-electron-deficient heteroaromatic ring skeleton 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-oxadiazole- organic compounds having an azole skeleton, such as 2-[3-(dibenzothiophen-4-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); )phenyl]pyridine (abbreviation: 35DCzPPy), 1,3,5-tri[3-(3-pyridyl)phenyl]benzene (abbreviation: TmPyPB), bathophenanthroline (abbreviation: BPhen), bathocuproine (abbreviation: BCP), 2,9-di(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline (abbreviation: NBPhen), 2,2'-(1,3-phenylene)bis(9-phenyl-1,10-phenanthroline) (abbreviation: mPPhen2P), 2-[3-(2-triphenylenyl)phenyl]-1,10 organic compounds containing a heteroaromatic ring having a pyridine skeleton, such as 2-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTPDBq-II), 2-[3'-(dibenzothiophen-3-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]quinoxaline (abbreviation: 2mpPCBPDBq), 2-[4-(3,6-diphenyl-9H-carbazol-3-yl)-3,1'-biphenyl-1-yl]dibenzo[f,h]quinoxaline (abbreviation: 2mpPCBPDBq),
[0033] 2-{3-[3-(N-phenyl-9H-carbazol-3-yl)-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), and 6-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 6mDBTPDBq-II), 2-{3-[3-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}dibenzo[f,h]quinoxaline (abbreviation: 2mPCCzPDBq) , 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[3-(phenanthren-9-yl)phenyl]pyrimidine (abbreviation: 4,6mPnP2Pm), 4,6-bis[3-(dibenzothiophen-4-yl)phenyl]pyrimidine (abbreviation: 4,6mD BTP2Pm-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-(biphenyl-4-yl)-4-[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)(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]benzfuro[3,2-d]pyrimidine 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)2Py), 6-(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-(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), etc. organic compounds having a diazine skeleton, such as 2-(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), and 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)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-pyridinyl)-5-(9-phenanthrenyl)phenyl]-4,6-diphenyl-1,3,5-triazine (abbreviation: mPn-mDMePyPTzn), 11-[4-(biphenyl-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′-(triphenylen-2-yl)biphenyl-3-yl]-4,6-diphenyl-1,3,5-triazine (abbreviation: mTpB PTzn), 3-[9-(4,6-diphenyl-1,3,5-triazin-2-yl)-2-dibenzofuranyl]-9-phenyl-9H-carbazole (abbreviation: PCDBfTzn), 2-(biphenyl-3-yl)-4-phenyl-6-{8-[(1,1':4',1''-terphenyl)-4-yl]-1-dibenzofuranyl}-1,3,5-triazine (abbreviation: mBP-TPDBfTzn), 2-[4-(2-naphthalenyl)phenyl]-4-phenyl-6-spiro[9H-fluorene-9,9'-[9H]xanthene]-4-yl-1,3,Examples of suitable organic compounds include organic compounds containing a heteroaromatic ring with a triazine skeleton, such as 5-triazine (abbreviated as βNP-SFx(4)Tzn). Organic compounds containing a heteroaromatic ring with a diazine skeleton, organic compounds containing a heteroaromatic ring with a pyridine skeleton, and organic compounds containing a heteroaromatic ring with a triazine skeleton are preferred due to their high reliability. In particular, organic compounds containing a heteroaromatic ring with a diazine (pyrimidine or pyrazine) skeleton and organic compounds containing a heteroaromatic ring with a triazine skeleton have high electron transport properties and contribute to reducing driving voltage.
[0117] Among the above, organic compounds having a phenanthroline ring such as BPhen, BCP, NBPhen and mPPhen2P are preferred, and organic compounds having a phenanthroline ring dimer structure such as mPPhen2P are more preferred due to their excellent heat resistance and stability.
[0118] The number of carbon atoms in the second organic compound is preferably from 25 to 100. By setting the number of carbon atoms in this range, the organic compound can be made to have excellent sublimation properties, and therefore thermal decomposition of the organic compound can be suppressed during vacuum deposition, thereby achieving good material usage efficiency.
[0119] The second organic compound is preferably an organic compound having a glass transition temperature Tg of 100° C. or higher. This allows the electron injection layer to have good heat resistance and be resistant to crystallization. Therefore, the organic compound layer can be resistant to crystallization even when a portion of the organic compound layer is processed by lithography.
[0120] Examples of organic compounds having a phenanthroline ring and a glass transition temperature (Tg) of 100°C or higher include NBPhen (Tg: 165°C), mPPhen2P (Tg: 135°C), 2,2'-(biphenyl-4,4'-diyl)bis(9-phenyl-1,10-phenanthroline) (abbreviation: PPhen2BP) (Tg: 166°C), 2,2'-biphenyl-3,3'-diyl Examples include rubis(9-phenyl-1,10-phenanthroline) (abbreviation: mPPhen2BP) (Tg: 144°C), 2,8-bis(phenanthrolin-5-yl)dibenzofuran (abbreviation: 2,8Phen2DBf) (Tg: 210°C), and 5,5',5''-(benzene-1,3,5-triyl)tri-1,10-phenanthroline (abbreviation: Phen3P) (Tg: 257°C).
[0121] Furthermore, the second organic compound can be an organic compound having an acid dissociation constant pKa of 4 or more and less than 8. This makes it possible to improve resistance to water and chemicals used in lithography processes.
[0122] It is more preferable that the LUMO level of the second organic compound is lower than the LUMO level of the first organic compound. This makes it easier for the donor level formed by the first organic compound and the metal oxide to donate electrons to the second organic compound. It is also preferable that the second organic compound has electron transport properties, and for this reason, it is also preferable that the LUMO level of the second organic compound is lower than the LUMO level of the first organic compound.
[0123] The LUMO level of the second organic compound is preferably −3.0 eV or more and −2.0 eV or less, more preferably −3.0 eV or more and −2.5 eV or less, and the LUMO level of the first organic compound is preferably −3.0 eV or more and −2.0 eV or less, more preferably −2.7 eV or more and −2.0 eV or less.
[0124] This can facilitate electron donation from the donor level formed by the first organic compound and the metal oxide to the second organic compound, and also facilitate electron transport in the second organic compound.
[0125] The HOMO level and LUMO level of an organic compound are generally estimated by CV (cyclic voltammetry), photoelectron spectroscopy, optical absorption spectroscopy, inverse photoelectron spectroscopy, etc. When comparing values between different compounds, it is preferable to use values estimated by the same measurement.
[0126] Furthermore, it is preferable that the electron injection layer contains a second organic compound in addition to the metal oxide and the first organic compound, because this allows for efficient interaction between the materials, which can be confirmed by measuring the spin density using electron spin resonance.
[0127] For example, the spin density measured by ESR of a film containing a metal oxide and a first organic compound is preferably higher than the spin density measured by ESR of a film containing a metal oxide and a second organic compound.Furthermore, the spin density measured by ESR of a film containing a metal oxide, a first organic compound, and a second organic compound is preferably higher than the spin density measured by ESR of a film containing only two of the metal oxide, the first organic compound, and the second organic compound, and in this case, it can be confirmed that the interaction between the materials occurs efficiently.
[0128] More specifically, the film containing the metal oxide and the first organic compound has a spin density of 5×10 due to a signal observed at a g value of about 2.00 by electron spin resonance. 16 spins / cm 3 More preferably, 1×10 17 spins / cm 3 In such a case, it can be confirmed that an interaction between the materials occurs efficiently in the film containing the metal oxide and the first organic compound. Alternatively, the film containing the metal oxide, the first organic compound, and the second organic compound has a spin density of 5×10 or less due to a signal observed in the vicinity of a g-value of 2.00 by electron spin resonance. 16 spins / cm 3 More preferably, 1×10 17 spins / cm 3In such a case, it can be confirmed that in a film containing a metal oxide, a first organic compound, and a second organic compound, the interaction between the materials occurs more efficiently than in a layer containing only two of these materials. In this case, for a mixed film containing a metal oxide and a second organic compound, the spin density resulting from a signal observed in the vicinity of a g-value of 2.00 by electron spin resonance is, for example, 2×10 16 spins / cm 3 For a mixed film containing the first organic compound and the second organic compound, the spin density resulting from a signal observed in the vicinity of a g-value of 2.00 by electron spin resonance is 2×10 or less. 16 spins / cm 3 The following is the result.
[0129] In the electron injection layer, the molar ratio of the metal oxide to the first organic compound (or the sum of the first organic compound and the second organic compound) is preferably 0.1 to 10, more preferably 0.2 to 5, and even more preferably 0.5 to 2. Alternatively, the volume ratio is preferably 0.01 to 0.3, more preferably 0.02 to 0.2, and even more preferably 0.05 to 0.1. By having an electron injection layer containing the metal oxide and the first organic compound (or the first organic compound and the second organic compound) in such a ratio, an electron injection layer with good electron injection properties can be provided. Furthermore, the second organic compound does not necessarily have to be used, but when the second organic compound is used, the volume ratio of the first organic compound to the second organic compound is preferably 0.1 to 10, more preferably 0.2 to 5, and even more preferably 0.5 to 2. By mixing the first organic compound and the second organic compound in such a ratio, an electron injection layer having good electron transport properties can be provided. Furthermore, by using an organic compound having a high Tg and good thermal properties as the second organic compound, it is possible to provide an organic EL device having good reliability.
[0130] The thickness of the electron injection layer is preferably 2 nm to 20 nm, more preferably 5 nm to 10 nm. When the electron injection layer has a stacked structure of a metal oxide layer and a layer containing the first organic compound, the thickness of the metal oxide layer is preferably 0.1 nm to 5 nm, more preferably 0.2 nm to 2 nm. When the electron injection layer has a stacked structure of a metal oxide layer and a layer containing the first organic compound, the thickness of the layer containing the first organic compound is preferably 2 nm to 20 nm, more preferably 5 nm to 10 nm.
[0131] <Second Electrode> The second electrode is an electrode that forms a pair with the first electrode, and the light-emitting device has the previously formed first electrode, the second electrode, and an organic compound layer located between the first electrode and the second electrode. In addition, it is preferable that the organic compound layer has a light-emitting layer and an electron-injection layer, the electron-injection layer is located between the light-emitting layer and the second electrode, and the electron-injection layer and the second electrode are in contact with each other.
[0132] The second electrode is preferably made of a conductive metal oxide such as indium tin oxide (ITO), indium tin oxide containing silicon or silicon oxide (ITSO), indium zinc oxide, or indium oxide containing tungsten oxide and zinc oxide (IWZO). Other examples of the metal material that can be used include gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti), aluminum (Al), yttrium (Y), zirconium (Zr), tantalum (Ta), silver (Ag), and magnesium (Mg), as well as alloys containing these metal materials. Alternatively, nitrides of metal materials (e.g., titanium nitride) can be used. These materials are less likely to be deteriorated by the photolithography process, and therefore it is possible to obtain a light-emitting device with good characteristics even after the photolithography process.
[0133] Note that by forming the second electrode to be light-transmitting, the device can be a top-emission light-emitting device that emits light from the second electrode side. In the case of a bottom-emission light-emitting device, the second electrode is preferably an electrode having high reflectivity for visible light (40% to 100%, preferably 70% to 100%).
[0134] In addition, some of these materials have a high work function and are therefore difficult to use as a cathode. However, in one embodiment of the present invention, a light-emitting device with favorable characteristics can be provided by using the second electrode and the electron-injection layer having the above structure.
[0135] Thus, an organic EL device according to one embodiment of the present invention, which includes an electron injection layer containing a metal oxide and an organic compound (first organic compound) having a phenanthroline ring with an electron-donating group and a second electrode having the above-described structure in contact with the electron injection layer, can achieve an organic EL device with excellent characteristics even after a process of exposing the organic compound layer to the atmosphere after forming the second electrode. That is, by applying the configuration of one embodiment of the present invention, an organic EL device with excellent characteristics can be realized, which is fabricated by a photolithography method including a process of exposing the organic compound layer to the atmosphere. Specifically, an electron injection layer that is resistant to oxygen and water in the atmosphere, as well as water and chemicals used in the lithography process, can be formed. Therefore, one embodiment of the present invention can provide a light-emitting device with excellent moisture resistance, water resistance, oxygen resistance, and chemical resistance, a low driving voltage, and excellent luminous efficiency.
[0136] That is, by applying the structure of one embodiment of the present invention, an organic EL device with excellent characteristics can be realized, which is manufactured by a photolithography method including a step of exposing an organic compound layer to the atmosphere, thereby making it possible to provide a display device with extremely high definition and excellent characteristics.
[0137] Note that the light-emitting device of one embodiment of the present invention is particularly suitable for a light-emitting device that has undergone a photolithography process. However, a light-emitting device that has not undergone a photolithography process is also highly stable against the atmosphere, which improves yield and contributes to cost reduction by eliminating the need for stricter atmosphere control during the manufacturing process.
[0138] Embodiment 2 In this embodiment, a light-emitting device according to one embodiment of the present invention will be described in detail.
[0139] 1 is a schematic diagram of a light-emitting device according to one embodiment of the present invention. The light-emitting device includes a first electrode 101 over an insulator 1000, and an organic compound layer 103 between the first electrode 101 and a second electrode 102. The organic compound layer 103 includes at least a light-emitting layer 113 and an electron-injection layer 115. The light-emitting layer 113 is a layer containing a light-emitting substance, and the light-emitting device according to one embodiment of the present invention emits light when a voltage is applied between the first electrode 101 and the second electrode 102.
[0140] 1A , the organic compound layer 103 preferably has functional layers such as a hole injection layer 111, a hole transport layer 112, and an electron transport layer 114 in addition to the light-emitting layer 113 and the electron injection layer 115. The organic compound layer 103 may also include functional layers other than the above-mentioned functional layers, such as a hole blocking layer, an exciton blocking layer, and an intermediate layer. Conversely, any of the above-mentioned layers may not be provided.
[0141] The electron injection layer 115 is a layer containing a metal oxide and an organic compound (first organic compound) having a phenanthroline ring with an electron-donating group, as described in Embodiment 1. The electron injection layer 115 may further contain another organic compound (second organic compound).
[0142] The specific configuration of the electron injection layer 115 has been described in detail in the first embodiment, so a repeated description will be omitted.
[0143] The first electrode 101 and the second electrode 102 may be formed to have a single layer structure or a stacked layer structure.
[0144] Note that the light-emitting device of one embodiment of the present invention is characterized in that, since the second electrode 102 is formed by photolithography and then processed, an end portion of the second electrode 102 in a cross section and an end portion of the organic compound layer 103 in a cross section are aligned in a direction approximately perpendicular to the surface of the insulating layer 1000, as shown in Figure 1. The end portions of the second electrode and the organic compound layer may be located inside the end portions of the first electrode as shown in Figures 1A and 1B or outside the first electrode as shown in Figure 1C.
[0145] The first electrode 101 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 (ITSO), 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 formed by applying a sol-gel method or the like. For example, 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 first electrode 101 include, for example, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti), aluminum (Al), and nitrides of metal materials (e.g., titanium nitride). A layer formed by stacking these materials may also be used as the anode. For example, a film formed by stacking Al, Ti, and ITSO in this order on Ti is preferable because it has good reflectivity, is highly efficient, and enables high resolution of several thousand ppi. Alternatively, graphene can be used as the material for the first electrode 101. In addition, by using a composite material capable of forming the hole injection layer 111 described later as a layer in contact with the anode (typically, a hole injection layer), it becomes possible to select an electrode material regardless of the work function.
[0146] The hole injection layer 111 is provided in contact with the anode and has a function of facilitating injection of holes into the organic compound layer 103. The hole injection layer 111 is made of phthalocyanine (abbreviation: H 2phthalocyanine compounds or complex compounds such as 4,4'-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB) and 4,4'-bis(N-{4-[N'-(3-methylphenyl)-N'-phenylamino]phenyl}-N-phenylamino)biphenyl (abbreviation: DNTPD), or polymers such as poly(3,4-ethylenedioxythiophene) / (polystyrenesulfonic acid) (abbreviation: PEDOT / PSS).
[0147] The hole-injection layer 111 may be formed using a substance having electron acceptor properties. Examples of the substance having acceptor properties include organic compounds having an electron-withdrawing group (such as a halogen group or a cyano group), such as 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F4-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), and 2-(7-dicyanomethylene-1,3,4,5,6,8,9,10-octafluoro-7H-pyren-2-ylidene)malononitrile. 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. Also, [3]radialene derivatives having an electron-withdrawing group (especially a halogen group such as a fluoro group, a cyano group, etc.) are preferred because they have very high electron-accepting properties, and specific examples thereof 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]. As the substance having acceptor properties, in addition to the organic compounds described above, transition metal oxides such as molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, and manganese oxide can be used.
[0148] The hole-injection layer 111 is preferably formed using a composite material containing the above-mentioned material having an acceptor property and an organic compound having a hole-transport property.
[0149] As the organic compound having a hole transport property used in the composite material, various organic compounds can be used, such as aromatic amine compounds, heteroaromatic compounds, aromatic hydrocarbons, and polymer compounds (oligomers, dendrimers, polymers, etc.). −6 cm 2 / Vs or more. The organic compound having hole transport properties used in the composite material is preferably a compound having a fused aromatic hydrocarbon ring or a π-electron-rich heteroaromatic ring. As the fused aromatic hydrocarbon ring, an anthracene ring, a naphthalene ring, or the like is preferred. As the π-electron-rich heteroaromatic ring, a fused aromatic ring containing at least one of a pyrrole skeleton, a furan skeleton, and a thiophene skeleton in the ring is preferred, and specifically, a carbazole ring, a dibenzothiophene ring, or a ring in which an aromatic ring or a heteroaromatic ring is further fused to the above ring is preferred.
[0150] Such organic compounds having hole-transporting properties preferably have a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, or an anthracene skeleton. In particular, aromatic amines having a substituent containing a dibenzofuran ring or a dibenzothiophene ring, aromatic monoamines having a naphthalene ring, or aromatic monoamines in which a 9-fluorenyl group is bonded to the nitrogen of the amine via an arylene group may be used. It is preferable that these organic compounds having hole-transporting properties are substances having an N,N-bis(4-biphenyl)amino group, since this allows the fabrication of light-emitting devices with a long lifetime.
[0151] Specific examples of the organic compound having hole transport properties as described above 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-yl)-4″-phenyltriphenylamine (abbreviation: BnfBB1BP), N,N-bis(4-biphenyl)benzylamine (abbreviation: BnfBB1BP), and N,N-bis(4-biphenyl)benzylamine (abbreviation: BnfBB1BP). 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-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]-4-amino-p-terphenyl] ]-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: BBAαNβ NB-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'-(3-phenyl-9H-carbazol-9-yl)biphenyl-4''-[ ... 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(biphenyl-4-yl)-9,9'-spirobi[9H-fluorene]-2-amine (abbreviation: BBASF), N,N-bis(biphenyl-4-yl)-9,9'-spirobi[9H-fluorene]-4-amine (abbreviation: BBASF(4)), N-(biphenyl-2-yl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi[9H-fluorene]-4-amine (abbreviation: oFBiSF), N-(biphenyl-4-yl)-N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzofuran-4-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-carbazol-3-yl)triphenylamine (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]-9,9'-spirobi[9H-fluorene]-2-amine (abbreviation: PCBASF), N-(biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9-dimethyl-9H-fluorene-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, etc.
[0152] Other aromatic amine compounds that can be used as the material having hole transport properties include N,N'-di(p-tolyl)-N,N'-diphenyl-p-phenylenediamine (abbreviation: DTDPPA), 4,4'-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), 4,4'-bis(N-{4-[N'-(3-methylphenyl)-N'-phenylamino]phenyl}-N-phenylamino)biphenyl (abbreviation: DNTPD), and 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene (abbreviation: DPA3B).
[0153] By forming the hole injection layer 111, the hole injection property becomes good, and a light emitting device with a low driving voltage can be obtained.
[0154] 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.
[0155] The hole transport layer 112 is formed by containing an organic compound having a hole transport property. −6 cm 2 It is preferable that the material has a hole mobility of 1.0 V or more.
[0156] Examples of the material having a hole transport property include 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N′-diphenyl-N,N′-bis(3-methylphenyl)-4,4′-diaminobiphenyl (abbreviation: TPD), N,N′-bis(9,9′-spirobi[9H-fluoren]-2-yl)-N,N′-diphenyl-4,4′-diaminobiphenyl (abbreviation: BSPB), 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP), and 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 (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), and N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9'-spirobi[9H-fluorene]-2-amine (abbreviation: PCBASF); 1,3-bis(N-carbazolyl)benzene (abbreviation: mCP); 4,4'-di(N-carbazol-3-yl)triphenylamine (abbreviation: PCBNBB); 9,9'-bis(biphenyl-4-yl)-3,3'-bi-9H-carbazole (abbreviation: BisBPCz), 9,9'-bis(biphenyl-3-yl)-3,3'-bi-9H-carbazole (abbreviation: BismBPCz), 9-(biphenyl-3-yl)-9'-(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'-9H,9'H-bicarbazole (abbreviation: PCCzTp), 9,9'-bis(triphenylene-2 compounds having a carbazole skeleton such as 9-(4-biphenyl)-9'-(triphenylen-2-yl)-3,3'-9H,9'H-bicarbazole, 9-(triphenylen-2-yl)-9'-[1,1':3',1"-terphenyl]-4-yl-3,3'-9H,9'H-bicarbazole, 4,4',4''-(benzene-1,3,5-triyl)tri(dibenzothiophene) (abbreviation: DBT3P-II), 2,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. Note that the substances listed as the materials having hole transport properties used in the composite material of the hole injection layer 111 can also be suitably used as materials for forming the hole transport layer 112.
[0157] The light-emitting layer 113 is a layer containing a light-emitting substance, and preferably contains a light-emitting substance and a host material. The light-emitting layer may also contain other materials. Alternatively, the light-emitting layer may be a stack of two or more layers having different compositions.
[0158] The luminescent material may be a fluorescent material, a phosphorescent material, a material exhibiting thermally activated delayed fluorescence (TADF), or any other luminescent material.
[0159] Examples of materials that can be used as fluorescent materials in the light-emitting layer include the following: In addition, fluorescent materials other than these can also be used.
[0160] 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(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(biphenyl-2-yl)-2-anthryl]-N,N',N'-triphenyl-1,4-phenylenediamine (abbreviation: 2DPABPhA) , 9,10-bis(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(biphenyl-4-yl)-6,11-diphenyltetracene (abbreviation: BPT), 2-(2-{2-[4-(dimethylamino)phenyl]ethenyl}-6-methyl-4H-pyra N,N,N',N'-tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluoranthene-3,10-diamine (abbreviation: p-mPhTD), 2-{2-methyl-6-[2-(2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-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 (abbreviation: p-mPhTD), Name: 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]naphthyl)benzo[b]naphthyl] ... 6,7-b']bisbenzofuran-3,10-diamine (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, such as pyrene diamine compounds 1,6FLPAPrn, 1,6mMemFLPAPrn, and 1,6BnfAPrn-03, are preferred because they have high hole trapping properties and excellent luminous efficiency or reliability.
[0161] Furthermore, 5,9-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene (abbreviation: DABNA1), 9-(biphenyl-3-yl)-N,N,5,11-tetraphenyl-5H,9H-[1,4]benzazaborino[2,3,4-kl]phenazaborin-3-amine (abbreviation: DABNA2), 2,12-di(tert-butyl)-5,9-di(4-tert-butylphenyl)-N,N-diphenyl-5H,9H-[1,4]benzazaborino[2,3,4-kl]phenazaborin-7-amine (abbreviation: DABNA3), amine (abbreviation: DPhA-tBu4DABNA), 2,12-di(tert-butyl)-N,N,5,9-tetra(4-tert-butylphenyl)-5H,9H-[1,4]benzazaborino[2,3,4-kl]phenazaborin-7-amine (abbreviation: tBuDPhA-tBu4DABNA), 2,12-di(tert-butyl)-5,9-di(4-tert-butylphenyl)-7-methyl-5H,9H-[1,4]benzazaborino[2,3,4-kl]phenazaborin (abbreviation: Me-tBu4DABNA), N 7 , N 7 , N 13 , N 13 Condensed heteroaromatic compounds containing nitrogen and boron, such as 5,9,11,15-octaphenyl-5H,9H,11H,15H-[1,4]benzazaborino[2,3,4-kl][1,4]benzazaborino[4',3',2':4,5][1,4]benzazaborino[3,2-b]phenazaborine-7,13-diamine (abbreviation: v-DABNA), and 2-(4-tert-butylphenyl)benz[5,6]indolo[3,2,1-jk]benzo[b]carbazole (abbreviation: tBuPBibc), in particular compounds having a diazaboranaphthoanthracene skeleton, can be suitably used because they have a narrow emission spectrum and can emit blue light with good color purity.
[0162] In addition to these, 9,10,11-tris[3,6-bis(1,1-dimethylethyl)-9H-carbazolyl-9-yl]-2,5,15,18-tetrakis(1,1-dimethylethyl)indolo[3,2,1-de]indolo[3',2',1':8,1][1,4]benzazaborino[2,3,4-kl]phenazaborine (abbreviation: BBCz-G), 9,11-bis[3,6-bis(1,1-dimethylethyl)-9H-carbazolyl-9-yl]-2,5,15,18-tetrakis(1,1-dimethylethyl)indolo[3,2,1-de]indolo[3',2',1':8,1][1,4]benzazaborino[2,3,4-kl]phenazaborine (abbreviation: BBCz-Y) and the like can be preferably used.
[0163] When a phosphorescent material is used as the light-emitting material in the light-emitting layer, examples of materials that can be used include the following.
[0164] 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(iPrpim) 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) 3 organometallic 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 450 nm to 520 nm.
[0165] 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-κ]iridium(III) (abbreviation: [Ir(5mppy-d 3 ) 2 (mbfpypy-d 3 ) )]), [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 (mbfpypy-d 3 ) ]), [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-d 3 ) 2 (mdppy-d 3 ) )]), [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 (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.
[0166] Also, (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) 2 organometallic 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) 3 Examples of rare earth metal complexes include iridium complexes such as iridium complexes containing pyrazine skeletons and iridium complexes containing iridium ions. These compounds exhibit red phosphorescence and have an emission peak in the wavelength range of 600 nm to 700 nm. Organometallic iridium complexes containing pyrazine skeletons exhibit red emission with good chromaticity.
[0167] In addition to the phosphorescent compounds described above, known phosphorescent compounds may be selected and used.
[0168] 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.
[0169]
[0170] 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.
[0171]
[0172] The TADF material is S 1 Level and T 1 This material has a small difference in energy level between triplet and singlet excitations, and has the ability to convert energy from triplet excitation to singlet excitation through reverse intersystem crossing. Therefore, triplet excitation energy can be upconverted to singlet excitation energy (reverse intersystem crossing) with a small amount of thermal energy, allowing for efficient generation of a singlet excited state. In addition, triplet excitation energy can be converted into luminescence.
[0173] In addition, an excited complex (also called an exciplex) that forms an excited state with two kinds of substances is S 1 Level and T 1 The difference between the triplet excitation energy and the singlet excitation energy is extremely small, and the TADF material functions as a TADF material that can convert triplet excitation energy into singlet excitation energy.
[0174] In addition, T 1 The phosphorescence spectrum observed at low temperatures (for example, 77 K to 10 K) can be used as an index of the level. For the TADF material, a tangent line is drawn at the base of the fluorescence spectrum on the short wavelength side, and the energy of the wavelength of the extrapolated line is expressed as S 1 The energy level is set as the level, and a tangent line is drawn at the base of the phosphorescence spectrum on the short wavelength side. The energy of the wavelength of the extrapolated line is T 1 When the level is reached, the S 1 and T 1 The difference is preferably 0.3 eV or less, and more preferably 0.2 eV or less.
[0175] In addition, when a TADF material is used as a light-emitting material, the S 1 The level is S of the TADF material. 1 It is preferable that the T level of the host material is higher than that of the 1 The level is the T 1 It is preferable that the level is higher.
[0176] As the host material of the light-emitting layer, various carrier transport materials such as a material having an electron transport property and / or a material having a hole transport property, and the above-mentioned TADF material can be used.
[0177] The material having hole transport properties is preferably an organic compound having an amine skeleton or a π-electron-rich heteroaromatic ring skeleton. The π-electron-rich heteroaromatic ring is preferably a fused aromatic ring containing at least one of an acridine skeleton, a phenoxazine skeleton, a phenothiazine skeleton, a furan skeleton, a thiophene skeleton, and a pyrrole skeleton, and specifically preferably a carbazole ring, a dibenzothiophene ring, or a ring in which an aromatic ring or a heteroaromatic ring is further fused to the carbazole ring, a dibenzothiophene ring, or the ring in which the π-electron-rich heteroaromatic ring is further fused to the carbazole ring, a dibenzothiophene ring, or the ring in which ... a dibenzothiophene ring, or the ring in which the carbazole ring, a dibenzothiophene ring, a dibenzothiophene ring, or the ring in which the carbazole ring, a dibenzothiophene ring, a dibenzothiophene ring, a dibenzothiophene ring, a dibenzothiophene ring, a dibenzothiophene ring, a dibenzothiophene ring, a dibenzothiophene ring, a dibenzothiophene ring, a dibenzothiophene
[0178] Such organic compounds having hole-transporting properties preferably have a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, or an anthracene skeleton. In particular, aromatic amines having a substituent containing a dibenzofuran ring or a dibenzothiophene ring, aromatic monoamines having a naphthalene ring, or aromatic monoamines in which a 9-fluorenyl group is bonded to the nitrogen of the amine via an arylene group may be used. It is preferable that these organic compounds having hole-transporting properties are substances having an N,N-bis(4-biphenyl)amino group, since this allows the fabrication of light-emitting devices with a long lifetime.
[0179] Examples of such organic compounds include 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N′-diphenyl-N,N′-bis(3-methylphenyl)-4,4′-diaminobiphenyl (abbreviation: TPD), N,N′-bis(9,9′-spirobi[9H-fluoren]-2-yl)-N,N′-diphenyl-4,4′-diaminobiphenyl (abbreviation: BSPB), and 4-phenyl-4′-(9-phenylfluoren-9-yl)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 (abbreviation: PC aromatic amines such as 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]-9,9'-spirobi[9H-fluorene]-2-amine (abbreviation: PCBASF). compounds having a carbazole skeleton such as 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), and 9,9'-diphenyl-9H,9'H-3,3'-bicarbazole (abbreviation: PCCP); compounds having a carbazole skeleton such as 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 or 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 materials having hole transport properties in the hole transport layer can also be used.
[0180] An example of a material having electron transport properties is bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeBq 2 Preferred are metal complexes such as 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), and bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ), as well as organic compounds having a π-electron-deficient heteroaromatic ring. Examples of organic compounds having a π-electron-deficient heteroaromatic ring skeleton include organic compounds having a heteroaromatic ring with an azole skeleton, organic compounds having a heteroaromatic ring with a pyridine skeleton, organic compounds having a heteroaromatic ring with a diazine skeleton, and organic compounds having a heteroaromatic ring with a triazine skeleton.
[0181] Among these, organic compounds containing a heteroaromatic ring having a diazine skeleton (pyrimidine skeleton, pyrazine skeleton, pyridazine skeleton), organic compounds containing a heteroaromatic ring having a pyridine skeleton, and organic compounds containing a heteroaromatic ring having a triazine skeleton are preferred because of their high reliability. In particular, organic compounds containing a heteroaromatic ring having a diazine (pyrimidine or pyrazine) skeleton and organic compounds containing a heteroaromatic ring having a triazine skeleton have high electron transport properties and contribute to reducing driving voltage. In addition, benzofuropyrimidine skeletons, benzothienopyrimidine skeletons, benzofuropyrazine skeletons, and benzothienopyrazine skeletons are preferred because of their high acceptor properties and high reliability.
[0182] Examples of organic compounds having a π-electron-deficient heteroaromatic ring skeleton 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-oxadiazole- organic compounds having an azole skeleton, such as 2-[3-(dibenzothiophen-4-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); )phenyl]pyridine (abbreviation: 35DCzPPy), 1,3,5-tri[3-(3-pyridyl)phenyl]benzene (abbreviation: TmPyPB), bathophenanthroline (abbreviation: BPhen), bathocuproine (abbreviation: BCP), 2,9-di(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline (abbreviation: NBPhen), 2,2'-(1,3-phenylene)bis(9-phenyl-1,10-phenanthroline) (abbreviation: mPPhen2P), 2-[3-(2-triphenylenyl)phenyl]-1,10 organic compounds containing a heteroaromatic ring having a pyridine skeleton, such as 2-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTPDBq-II), 2-[3'-(dibenzothiophen-4-yl)biphenyl-3-yl]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]quinoxaline (abbreviation: 2mpPCBPDBq), 2-[4-(3,6-diphenyl 1-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 2CzPDBq-III), 7-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 7mDBTPDBq-II), and 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: 9mDBtBPNf pr), 9-[3'-(dibenzothiophen-4-yl)biphenyl-4-yl]naphtho[1',2':4,5]furo[2,3-b]pyrazine (abbreviation: 9pmDBtBPNfpr), 4,6-bis[3-(phenanthrene-9-yl)phenyl]pyrimidine (abbreviation: 4,6mPnP2Pm), 4,6-bis[3-(dibenzothiophen-4-yl)phenyl]pyrimidine (abbreviation: 4,6mDBTP2Pm-II), 4,6-bis[3-(9H-carbazol-9-yl)phenyl]pyrimidine (abbreviation: 4,6mCzP2Pm), 9,9'-[pyrimidinyl 4,6-diphenyl-4,6-diylbis(biphenyl-3,3′-diyl)]bis(9H-carbazole) (abbreviation: 4,6mCzBP2Pm), 8-(biphenyl-4-yl)-4-[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)(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)2Py), 6-(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-carbazole-9 organic compounds having a diazine skeleton such as 2-(biphenyl-4-yl)-4-phenyl-6-(9,9'-spirobi[9H-fluoren]-2-yl)-pyrimidine (abbreviation: 6BP-4Cz2PPm), 7-[4-(9-phenyl-9H-carbazol-2-yl)quinazolin-2-yl]-7H-dibenzo[c,g]carbazole (abbreviation: PC-cgDBCzQz), 2-(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] 2-{3-[3-(benzo[b]naphtho[1,2-d]furan-6-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)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 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-pyridinyl)-5-(9-phenanthrenyl)phenyl]-4,6-diphenyl-1,3,5-triazine (abbreviation: TmPPPyTz), Phenyl-1,3,5-triazine (abbreviation: mPn-mDMePyPTzn), 11-[4-(biphenyl-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′-(triphenylen-2-yl)biphenyl-3-yl]-4,6-diphenyl-1,3,5-triazine (abbreviation: mTpBPTzn), 3 Examples of suitable organic compounds include organic compounds containing a heteroaromatic ring with a triazine skeleton, such as 2-(biphenyl-3-yl)-4-phenyl-6-{8-[(1,1':4',1''-terphenyl)-4-yl]-1-dibenzofuranyl}-1,3,5-triazine (mBP-TPDBfTzn). Organic compounds containing a heteroaromatic ring with a diazine skeleton, organic compounds containing a heteroaromatic ring with a pyridine skeleton, and organic compounds containing a heteroaromatic ring with a triazine skeleton are preferred due to their high reliability. In particular, organic compounds containing a heteroaromatic ring with a diazine (pyrimidine or pyrazine) skeleton and organic compounds containing a heteroaromatic ring with a triazine skeleton have high electron transport properties and contribute to reduced driving voltage.
[0183] 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 a 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 a light-emitting substance, thereby improving the luminous efficiency of the light-emitting device. In this case, the TADF material functions as an energy donor, and the light-emitting substance functions as an energy acceptor.
[0184] This is very effective when the luminescent material is a fluorescent luminescent material. 1 The level is the S of the fluorescent material. 1 It is preferable that the T of the TADF material is higher than the T level. 1 The level is the S of the fluorescent material. 1 Therefore, the T 1 The level is the T 1 It is preferable that the level is higher.
[0185] 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.
[0186] 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 such luminophores include a phenanthrene skeleton, a stilbene skeleton, an acridone skeleton, a phenoxazine skeleton, a phenothiazine skeleton, 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, and a naphthobisbenzofuran skeleton. In particular, fluorescent materials 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.
[0187] 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 used as the host material, a diphenylanthracene skeleton, particularly a substance having 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 level is about 0.1 eV higher than that of the carbazole skeleton, making it easier for holes to enter. In particular, a host material containing a dibenzocarbazole skeleton is preferred because its HOMO level is about 0.1 eV higher than that of the carbazole skeleton, 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 property, 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′- 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 Examples include zo[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-(biphenyl-4-yl)-9-anthracenyl]phenyl}-2-ethyl-1H-benzimidazole (abbreviation: EtBImPBPhA), etc. In particular, CzPA, cgDBCzPA, 2mBnfPPA, and PCzPA are preferred choices because they exhibit very good properties.
[0188] The host material may be a mixture of a plurality of substances. When a mixture of host materials is used, it is preferable to mix a material having electron transport properties with a material having hole transport properties. By mixing a material having electron transport properties with a material having hole transport properties, the transport properties of the light-emitting layer 113 can be easily adjusted, and the recombination region can also be easily controlled. The weight ratio of the content of the material having hole transport properties to the material having electron transport properties is preferably 1:19 to 19:1 (material having hole transport properties:material having electron transport properties).
[0189] 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.
[0190] Furthermore, these mixed materials may form an exciplex. It is preferable to select 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, using this structure is also preferable because it reduces the driving voltage.
[0191] 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.
[0192] 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).
[0193] 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.
[0194] The electron transport layer 114 is a layer containing a substance having an electron transport property. The material having an electron transport property is a material having an electron mobility of 1×10 or less at a square root of an electric field strength [V / cm] of 600. −7 cm 2 / Vs or more, preferably 1×10 −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, as the organic compound, an organic compound having a π-electron-deficient heteroaromatic ring is preferred. As the organic compound having a π-electron-deficient heteroaromatic ring, for example, one or more of an organic compound including a heteroaromatic ring having an azole skeleton, an organic compound including a heteroaromatic ring having a pyridine skeleton, an organic compound including a heteroaromatic ring having a diazine skeleton, and an organic compound including a heteroaromatic ring having a triazine skeleton are preferred.
[0195] As organic compounds having electron transport properties that can be used in the electron transport layer 114, the organic compounds having electron transport properties in the light-emitting layer 113 and the organic compounds listed as organic compounds that can be used as the second organic compound in the electron injection layer 115 in Embodiment 1 can be used. Among these, organic compounds containing a heteroaromatic ring with a diazine skeleton, organic compounds containing a heteroaromatic ring with a pyridine skeleton, and organic compounds containing a heteroaromatic ring with a triazine skeleton are preferred because of their excellent reliability. In particular, organic compounds containing a heteroaromatic ring with a diazine (pyrimidine or pyrazine) skeleton and organic compounds containing a heteroaromatic ring with a triazine skeleton have high electron transport properties and contribute to reduced driving voltage. Among these, organic compounds having a phenanthroline ring, such as mTpPPhen, PnNPhen, and mPPhen2P, are preferred, and organic compounds having a phenanthroline dimer structure, such as mPPhen2P, are more preferred because of their excellent stability.
[0196] The electron transport layer preferably contains an organic compound having an acid dissociation constant pKa of less than 4 and having electron transport properties.
[0197] The electron transport layer 114 may have a stacked structure. When the electron transport layer 114 has a stacked structure, a layer in contact with the light-emitting layer 113 may function as a hole-blocking layer. When the electron transport layer in contact with the light-emitting layer is made to function as a hole-blocking layer, it is preferable to use a material whose HOMO level is lower by 0.5 eV or more than the HOMO level of a material contained in the light-emitting layer.
[0198] The electron injection layer 115 is formed between the electron transport layer 114 and the second electrode 102. The structure of the electron injection layer 115 has been described in detail in Embodiment 1, and therefore, repeated description will be omitted.
[0199] The second electrode 102 is preferably formed in contact with the electron-injection layer 115. The structure of the second electrode has been described in detail in Embodiment 1, and therefore, repeated description will be omitted.
[0200] When the second electrode 102 is formed using a material that is transparent to visible light, a light-emitting device can be formed that emits light from the second electrode 102 side, and when the first electrode 101 is formed using a material that is transparent to visible light, a light-emitting device can be formed that emits light from the first electrode 101 side.
[0201] The conductive material forming the second electrode 102 can be formed into a film by a dry method such as a vacuum deposition method or a sputtering method, an ink-jet method, a spin coating method, etc. Alternatively, the second electrode 102 may be formed by a wet method using a sol-gel method, or may be formed by a wet method using a paste of a metal material.
[0202] In the case of a top-emission light-emitting device, the light extraction efficiency can be improved by forming a capping layer by vapor-depositing an organic compound on the second electrode. The capping layer may have a single-layer structure or a multilayer structure. In the case of a multilayer structure, the light extraction efficiency can be further improved by using organic compounds with different refractive indices.
[0203] In addition, various methods, whether dry or wet, can be used to form the organic compound layer 103. For example, vacuum deposition, gravure printing, offset printing, screen printing, inkjet printing, spin coating, or the like may be used.
[0204] Furthermore, the above-mentioned electrodes or layers may be formed using different film formation methods.
[0205] 1B , in order to protect the electron injection layer 115, a P-type layer 117 may be provided as shown in FIG. 1B in order to protect the electron injection layer 115 when a film formation method that causes significant damage to a base, such as a sputtering method, is used to form the second electrode 102. The P-type layer 117 can be formed using the composite material described above as a material that can be used for the hole injection layer 111. Transition metal oxides such as molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, and manganese oxide are more robust than organic compounds, and therefore, by using them as a substance having acceptor properties to be used for the P-type layer, damage during the formation of the second electrode 102 can be prevented, which is preferable.
[0206] Although not shown, an electron relay layer may be provided between the electron injection layer 115 and the P-type layer 117. The electron relay layer contains at least a substance having electron transport properties and has the function of preventing interaction between the electron injection layer 115 and the P-type layer 117 and smoothly transferring electrons. The LUMO level of the substance having electron transport properties contained in the electron relay layer is preferably between the LUMO level of the acceptor substance in the P-type layer 117 and the LUMO level of the substance contained in the layer of the electron transport layer 114 that is in contact with the electron injection layer 115. The specific energy level of the LUMO level of the substance having electron transport properties used in the electron relay layer is −5.0 eV or higher, preferably −5.0 eV or higher and −3.0 eV or lower. The substance having electron transport properties used in the electron relay layer is preferably a phthalocyanine-based material or a metal complex having a metal-oxygen bond and an aromatic ligand. Specific examples of the substance having electron transport properties that can be used in the electron relay layer include diquinoxalino[2,3-a:2′,3′-c]phenazine (abbreviation: HATNA), 2,3,8,9,14,15-hexafluorodiquinoxalino[2,3-a:2′,3′-c]phenazine (abbreviation: HATNA-F6), perylene tetracarboxylic acid derivatives such as 3,4,9,10-perylene tetracarboxylic diimide (abbreviation: PTCDI) and 3,4,9,10-perylene tetracarboxylic bis-benzimidazole (abbreviation: PTCBI), (C60-Ih)[5,6]fullerene (abbreviation: C60), and (C70-D5h)[5,6]fullerene (abbreviation: C70). Furthermore, a compound having a heterophane skeleton, which is a cyclophane skeleton containing a heterocycle, can be used. Examples of such a compound include phthalocyanine (abbreviation: H 2Phthalocyanine compounds such as copper phthalocyanine (abbreviated as CuPc), zinc phthalocyanine (abbreviated as ZnPc), cobalt phthalocyanine (abbreviated as CoPc), iron phthalocyanine (abbreviated as FePc), tin phthalocyanine (abbreviated as SnPc), tin oxide phthalocyanine (abbreviated as SnOPc), titanium oxide phthalocyanine (abbreviated as TiOPc), vanadium oxide phthalocyanine (abbreviated as VOPc), and their derivatives can also be used. Phthalocyanine-based metal complexes such as copper phthalocyanine or zinc phthalocyanine, or 2,3,8,9,14,15-hexafluorodiquinoxalino[2,3-a:2',3'-c]phenazine are particularly preferred.
[0207] The thickness of the electron relay layer is preferably 1 nm or more and 10 nm or less, more preferably 2 nm or more and 5 nm or less.
[0208] Next, an embodiment of a light-emitting device having a configuration in which multiple light-emitting units are stacked (also referred to as a stacked device or a tandem device) will be described with reference to FIG. 1C . This light-emitting device has multiple light-emitting units between an anode and a cathode. One light-emitting unit has a configuration substantially similar to that of the organic compound layer 103 shown in FIG. 1A . In other words, the light-emitting device shown in FIG. 1C is a light-emitting device having multiple light-emitting units, and the light-emitting device shown in FIG. 1A can be said to be a light-emitting device having one light-emitting unit.
[0209] 1C , a first light-emitting unit 511 and a second light-emitting unit 512 are stacked between a first electrode 501 and a second electrode 502, and an intermediate layer 513 is provided between the first light-emitting unit 511 and the second light-emitting unit 512. The first electrode 501 and the second electrode 502 correspond to the first electrode 101 and the second electrode 102 in FIG. 1A , respectively, and the same materials as those described in the description of FIG. 1A can be applied. Furthermore, the layer configurations of the first light-emitting unit 511 and the second light-emitting unit 512 may be the same or different. Furthermore, the materials constituting the layers of the first light-emitting unit 511 and the second light-emitting unit 512 may be the same or different.
[0210] The intermediate layer 513 has a function of injecting electrons into one light-emitting unit and injecting holes into the other light-emitting unit when a voltage is applied between the first electrode 501 and the second electrode 502. That is, when a voltage is applied to the intermediate layer so that the potential of the anode is higher than the potential of the cathode in FIG. 1C , the intermediate layer 513 injects electrons into the first light-emitting unit 511 and injects holes into the second light-emitting unit 512.
[0211] The intermediate layer 513 includes a charge generation layer. The charge generation layer also includes at least a P-type layer 117. The P-type layer 117 is preferably formed using the composite material listed above as a material that can be used to form the hole injection layer 111. The P-type layer 117 may also be formed by laminating a film containing an acceptor material and a film containing a hole transport material, both of which are materials that can be used to form the composite material. By applying a potential to the P-type layer 117, electrons are injected into the electron transport layer 114 and holes are injected into the cathode, causing the light-emitting device to operate.
[0212] In addition, the intermediate layer 513 preferably includes one or both of an electron relay layer 118 and an N-type layer 119 in addition to the P-type layer 117 .
[0213] The electron relay layer 118 has the same configuration as the electron relay layer mentioned in the description of FIG. 1B, and therefore a repeated description will be omitted.
[0214] The N-type layer 119 can be made of a material with high electron injection properties, such as an alkali metal, an alkaline earth metal, a rare earth metal, or a compound thereof (an alkali metal compound (including an oxide such as lithium oxide, a halide, or a carbonate such as lithium carbonate or cesium carbonate), an alkaline earth metal compound (including an oxide, a halide, or a carbonate), or a rare earth metal compound (including an oxide, a halide, or a carbonate)).
[0215] When the N-type layer 119 is formed to contain a substance having an electron-transporting property and a donor substance, examples of the donor substance include alkali metals, alkaline earth metals, rare earth metals, and compounds thereof (alkali metal compounds (including oxides such as lithium oxide, halides, and carbonates such as lithium carbonate and cesium carbonate), alkaline earth metal compounds (including oxides, halides, and carbonates), and rare earth metal compounds (including oxides, halides, and carbonates)), as well as organic compounds such as tetrathianaphthacene (abbreviation: TTN), nickelocene, and decamethylnickelocene. Note that the substance having an electron-transporting property can be formed using the same material as the material constituting the electron-transporting layer 114 described above.
[0216] Alternatively, instead of the N-type layer 119, a layer containing the metal oxide described as being used for the electron injection layer in Embodiment 1 and an organic compound having a phenanthroline ring with an electron-donating group may be formed at the same position as the N-type layer 119. Even with this configuration, a tandem light-emitting device with excellent characteristics can be fabricated.
[0217] When the anode side surface of the light-emitting unit is in contact with the intermediate layer 513, the charge generation layer of the intermediate layer 513 can also function as the hole injection layer of the light-emitting unit, so the light-emitting unit does not need to be provided with a hole injection layer. When the cathode side surface of the light-emitting unit is in contact with the intermediate layer 513, the intermediate layer 513 can also function as the electron injection layer of the light-emitting unit, so the light-emitting unit does not need to be provided with an electron injection layer.
[0218] 1C illustrates a light-emitting device having two light-emitting units, but the present invention can be applied to a light-emitting device having three or more stacked light-emitting units. By arranging a plurality of light-emitting units between a pair of electrodes and separating them with an intermediate layer 513, as in the light-emitting device according to this embodiment, it is possible to realize a device that can emit high-luminance light while maintaining a low current density and has a long life. Furthermore, it is possible to realize a light-emitting device that can be driven at a low voltage and consumes low power.
[0219] Furthermore, by making the emission colors of the respective light-emitting units different, it is possible to obtain light emission of a desired color from the light-emitting device as a whole. For example, in a light-emitting device having two light-emitting units, it is possible to obtain a light-emitting device that emits white light from the entire device by obtaining red and green emission colors from the first light-emitting unit and blue emission color from the second light-emitting unit.
[0220] Furthermore, the layers and electrodes of the organic compound layer 103, the first light-emitting unit 511, the second light-emitting unit 512, and the intermediate layer can be formed by, for example, a vapor deposition method (including a vacuum vapor deposition method), a droplet discharge method (also called an ink-jet method), a coating method, a gravure printing method, etc. Furthermore, they may contain a low-molecular-weight material, a medium-molecular-weight material (including an oligomer and a dendrimer), or a polymer material.
[0221] FIG. 2A shows two adjacent light-emitting devices (light-emitting device 130a and light-emitting device 130b) included in a display device of one embodiment of the present invention.
[0222] The light-emitting device 130a has an organic compound layer 103a between a first electrode 101a on an insulating layer 175 and an opposing second electrode 102, and the organic compound layer 103a has an electron injection layer 115a. The organic compound layer 103a has a configuration including a hole injection layer 111a, a hole transport layer 112a, a light-emitting layer 113a, an electron transport layer 114a, and an electron injection layer 115a, but may have a different layer structure.
[0223] The light-emitting device 130b has an organic compound layer 103b between a first electrode 101b on an insulating layer 175 and an opposing second electrode 102, and the organic compound layer 103b has an electron injection layer 115b. The organic compound layer 103b has a configuration including a hole injection layer 111b, a hole transport layer 112b, a light-emitting layer 113b, an electron transport layer 114b, and an electron injection layer 115b, but may have a different layer structure.
[0224] The configurations of the electron injection layer 115a and the second electrode 102a in the light-emitting device 130a, and the configurations of the electron injection layer 115b and the second electrode 102b in the light-emitting device 130b are preferably the same as those described in the first embodiment.
[0225] The organic compound layers 103 a and 103 b and the second electrodes 102 a and 102 b are processed by photolithography after the second electrode 102 a and the second electrode 102 b are formed, respectively, and are therefore independent from each other. A light-emitting device according to one embodiment of the present invention can have favorable characteristics even when processed by photolithography after the second electrode 102 a and the second electrode 102 b are formed, respectively.
[0226] The edge (outline) of the second electrode 102a and the edge (outline) of the organic compound layer 103a are processed by photolithography, so they are roughly aligned in the direction perpendicular to the substrate. The edge (outline) of the second electrode 102b and the edge (outline) of the organic compound layer 103b are processed by photolithography, so they are roughly aligned in the direction perpendicular to the substrate.
[0227] Furthermore, since the organic compound layer 103 a is processed by photolithography, a gap d exists between the organic compound layer 103 a and the organic compound layer 103 d. Furthermore, since the organic compound layer is processed by photolithography, the distance between the first electrode 101 c and the first electrode 101 d can be made smaller than that in the case of mask vapor deposition, and can be set to 0.5 μm or more and 5 μm or less.
[0228] FIG. 2B shows two adjacent tandem light-emitting devices (light-emitting device 130c, light-emitting device 130d) fabricated by photolithography.
[0229] The light-emitting device 130c has an organic compound layer 103c between a first electrode 101c and a second electrode 102 on an insulating layer 175. The organic compound layer 103c has a structure in which a first light-emitting unit 501c and a second light-emitting unit 502c are stacked with an intermediate layer 116c sandwiched therebetween. Note that, although an example in which two light-emitting units are stacked is shown in FIG. 2B, a structure in which three or more light-emitting units are stacked may also be used. 2B shows a configuration in which the first light-emitting unit 501c includes a hole injection layer 111c, a first hole transport layer 112c_1, a first light-emitting layer 113c_1, and a first electron transport layer 114c_1, a configuration in which the intermediate layer 116c includes a P-type layer 117c, an electron relay layer 118c, and an N-type layer 119c, and a configuration in which the second light-emitting unit 502c includes a second hole transport layer 112c_2, a second light-emitting layer 113c_2, a second electron transport layer 114c_2, and an electron injection layer 115c. The electron relay layer 118c may or may not be present.
[0230] The light-emitting device 130d has an organic compound layer 103d between a first electrode 101d and a second electrode 102 on an insulating layer 175. The organic compound layer 103d has a configuration in which a first light-emitting unit 501d and a second light-emitting unit 502d are stacked with an intermediate layer 116d sandwiched therebetween. Note that, although an example in which two light-emitting units are stacked is shown in FIG. 2B , a configuration in which three or more light-emitting units are stacked may also be used. 2B , the first light-emitting unit 501d includes a hole injection layer 111d, a first hole transport layer 112d_1, a first light-emitting layer 113d_1, and a first electron transport layer 114d_1, the intermediate layer 116d includes a P-type layer 117d, an electron relay layer 118d, and an N-type layer 119d, and the second light-emitting unit 502d includes a second hole transport layer 112d_2, a second light-emitting layer 113d_2, a second electron transport layer 114d_2, and an electron injection layer 115d. The electron relay layer 118d may or may not be present.
[0231] In the light-emitting devices 130c and 130d, the electron injection layers 115c and 115d and the second electrodes 102c and 102d preferably have the structures described in the first embodiment.
[0232] Note that the organic compound layer 103c and the organic compound layer 103d are independent from each other because they are processed by photolithography after the second electrode 102c and the second electrode 102d are formed, respectively. A light-emitting device according to one embodiment of the present invention can have favorable characteristics even when processed by photolithography after the second electrode 102c and the second electrode 102d are formed, respectively.
[0233] The edges (outlines) of the second electrode 102c and the organic compound layer 103c are processed by photolithography, and therefore are generally aligned in the vertical direction relative to the substrate. The edges (outlines) of the second electrode 102d and the organic compound layer 103d are also processed by photolithography, and therefore are generally aligned in the vertical direction relative to the substrate.
[0234] Furthermore, since the organic compound layer 103c is processed by photolithography, a gap d exists between the organic compound layer 103d and the first electrode 101c. Furthermore, since the organic compound layer is processed by photolithography, the distance between the first electrode 101c and the first electrode 101d can be made smaller than that in the case of mask vapor deposition, and can be set to 0.5 μm or more and 5 μm or less.
[0235] Since the second electrodes 102a and 102b, or the second electrodes 102c and 102d, are independent of each other, an auxiliary electrode 105 is preferably formed to apply a voltage to the plurality of second electrodes included in the light-emitting device. The auxiliary electrode 105 is preferably formed after forming an insulating layer 106 between the second electrodes 102a and 102b or between the light-emitting devices 130c and 130d to prevent short-circuiting of the organic compound layer or the first electrode. The insulating layer 106 is preferably formed using an organic insulating material. The auxiliary electrode 105 can be formed using a material that can be used for the second electrode.
[0236] In the light-emitting device of one embodiment of the present invention, the organic compound layer is processed by photolithography, and therefore, the light-emitting device can be processed with sufficient precision to fabricate a high-resolution display device. Furthermore, since the lithography process can be performed on the electron injection layer far from the light-emitting layer without contamination by alkali metals, the light-emitting device can have excellent characteristics. As described above, the light-emitting device of one embodiment of the present invention having such a structure can realize a high-resolution display device and can have excellent characteristics.
[0237] In the light-emitting device of one embodiment of the present invention, the second electrode and the organic compound layer are processed simultaneously by photolithography after the formation of the second electrode. Therefore, when viewed from a direction substantially perpendicular to the surface of the insulating layer on which the first electrode is formed, the contours of the layers included in the organic compound layer substantially coincide with each other. Furthermore, the end of the cross section of the second electrode and the end of the cross section of the first layer are aligned in a direction substantially perpendicular to the surface of the insulating layer on which the first electrode is formed. In this specification, "aligned" and "substantially coincident" mean that, in layers A and B that contact each other, the deviation between the contour A of layer A and the contour B of layer B is within 5% of the width of the organic compound layer on a line perpendicular to the contours of the compared portions. Furthermore, "substantially perpendicular" means an angle of 85° to 95°.
[0238] The structure of this embodiment mode can be used in appropriate combination with other structures.
[0239] Embodiment 3 In this embodiment, a mode in which a light-emitting device of one embodiment of the present invention is used as a display element of a display device will be described.
[0240] As shown in FIGS. 3A and 3B, a plurality of light emitting devices 130 are formed on an insulating layer 175 to form a display device.
[0241] The display device has a pixel portion 177 in which a plurality of pixels 178 are arranged in a matrix. The pixel 178 has a sub-pixel 110R, a sub-pixel 110G, and a sub-pixel 110B.
[0242] In this specification and the like, when describing matters common to, for example, the subpixels 110R, 110G, and 110B, they may be referred to as the subpixels 110. When describing matters common to other components distinguished by alphabets, they may also be described using symbols without the alphabets.
[0243] The sub-pixel 110R emits red light, the sub-pixel 110G emits green light, and the sub-pixel 110B emits blue light. This allows a full-color image to be displayed in the pixel unit 177. In this embodiment, sub-pixels of three colors, red (R), green (G), and blue (B), are described as an example, but combinations of sub-pixels of other colors may also be used. The number of sub-pixels is not limited to three, and may be four or more. Examples of four sub-pixels include sub-pixels of four colors, R, G, B, and white (W); sub-pixels of four colors, R, G, B, and Y; and sub-pixels of R, G, B, and infrared (IR).
[0244] In this specification, the row direction may be referred to as the X direction, and the column direction may be referred to as the Y direction. The X direction and the Y direction intersect, for example, perpendicularly.
[0245] 3A shows an example in which subpixels of different colors are arranged side by side in the X direction, and subpixels of the same color are arranged side by side in the Y direction. Note that subpixels of different colors may also be arranged side by side in the Y direction, and subpixels of the same color may also be arranged side by side in the X direction.
[0246] The layout of the sub-pixels is not limited to this, and various other arrangements are possible, such as a stripe arrangement, an S-stripe arrangement, a matrix arrangement, a delta arrangement, a Bayer arrangement, a pentile arrangement, etc. Fig. 22 shows an example of a layout of the sub-pixels.
[0247] An S-stripe arrangement is applied to the pixel 178 shown in Fig. 22A. The pixel 178 shown in Fig. 22A is composed of three subpixels: a subpixel 110R, a subpixel 110G, and a subpixel 110B.
[0248] 22B includes a subpixel 110R having a generally trapezoidal or triangular shape with rounded corners, a subpixel 110G having a generally trapezoidal or triangular shape with rounded corners, and a subpixel 110B having a generally rectangular or hexagonal top surface shape with rounded corners. Furthermore, the subpixel 110R has a larger light-emitting area than the subpixel 110G. In this manner, the shape and size of each subpixel can be determined independently. For example, the more reliable the light-emitting device, the smaller the size of the subpixel can be.
[0249] The Pentile arrangement is applied to the pixels 124a and 124b shown in Fig. 22C. Fig. 14C shows an example in which the pixel 124a having the subpixel 110R and the subpixel 110G and the pixel 124b having the subpixel 110G and the subpixel 110B are arranged alternately.
[0250] 22D to 22F are arranged in a delta configuration. Pixel 124a has two subpixels (subpixel 110R and subpixel 110G) in the top row (first row) and one subpixel (subpixel 110B) in the bottom row (second row). Pixel 124b has one subpixel (subpixel 110B) in the top row (first row) and two subpixels (subpixel 110R and subpixel 110G) in the bottom row (second row).
[0251] Figure 22D is an example in which each subpixel has an approximately rectangular top surface shape with rounded corners, Figure 22E is an example in which each subpixel has a circular top surface shape, and Figure 22F is an example in which each subpixel has an approximately hexagonal top surface shape with rounded corners.
[0252] In Figure 22F, each subpixel is arranged inside a densely arranged hexagonal region. When focusing on one subpixel, it is arranged so that it is surrounded by six other subpixels. Furthermore, subpixels that emit light of the same color are arranged so that they are not adjacent to each other. For example, when focusing on subpixel 110R, three subpixels 110G and three subpixels 110B are arranged alternately so as to surround it.
[0253] 22G shows an example in which subpixels of each color are arranged in a zigzag pattern. Specifically, when viewed from above, the positions of the upper sides of two subpixels aligned in the row direction (for example, subpixels 110R and 110G, or subpixels 110G and 110B) are misaligned.
[0254] 22A to 22G, it is preferable that the subpixel 110R is the subpixel R that emits red light, the subpixel 110G is the subpixel G that emits green light, and the subpixel 110B is the subpixel B that emits blue light. Note that the configuration of the subpixels is not limited to this, and the colors that the subpixels emit and their order of arrangement can be determined appropriately. For example, the subpixel 110G may be the subpixel R that emits red light, and the subpixel 110R may be the subpixel G that emits green light.
[0255] 3A and 22G, the second electrodes 102 of light-emitting devices emitting the same light color can be formed continuously. In this case, even if processing is performed by photolithography after forming the second electrodes 102, voltage can be applied to each light-emitting device without the auxiliary electrodes 105. If processing by photolithography results in a configuration in which the second electrodes 102 are independent for each light-emitting device, it is preferable to form the auxiliary electrodes 105.
[0256] A connection portion 140 and a region 141 may be provided outside the pixel portion 177. The region 141 is provided between the pixel portion 177 and the connection portion 140. The organic compound layer 103 is provided in the region 141. In addition, the connection portion 140 is provided with a conductive layer 151C.
[0257] 3A shows an example in which the region 141 and the connection portion 140 are located on the right side of the pixel portion 177, but the positions of the region 141 and the connection portion 140 are not particularly limited. The region 141 and the connection portion 140 may be singular or plural.
[0258] Fig. 3B is an example of a cross-sectional view taken along dashed line A1-A2 in Fig. 3A. As shown in Fig. 3A, the display device has an insulating layer 171, a conductive layer 172 on the insulating layer 171, an insulating layer 173 on the insulating layer 171 and on the conductive layer 172, an insulating layer 174 on the insulating layer 173, and an insulating layer 175 on the insulating layer 174. The insulating layer 171 is provided on a substrate (not shown). The insulating layers 175, 174, and 173 have openings that reach the conductive layer 172, and plugs 176 are provided to fill the openings.
[0259] In the pixel section 177, the light-emitting device 130 is provided on the insulating layer 175 and the plug 176. A protective layer 131 is provided to cover the light-emitting device 130. The substrate 120 is bonded to the protective layer 131 by a resin layer 122. Preferably, an inorganic insulating layer 125 and an insulating layer 127 on the inorganic insulating layer 125 are provided between adjacent light-emitting devices 130.
[0260] The insulating layer 127 may be made of an acrylic resin, a polyimide resin, an epoxy resin, an imide resin, a polyamide resin, a polyimideamide resin, a silicone resin, a siloxane resin, a benzocyclobutene-based resin, a phenolic resin, or a precursor of any of these resins. The organic resin layer 180 may be made of an organic material such as polyvinyl alcohol (PVA), polyvinyl butyral, polyvinylpyrrolidone, polyethylene glycol, polyglycerin, pullulan, water-soluble cellulose, or an alcohol-soluble polyamide resin.
[0261] Furthermore, a photosensitive resin can be used for the insulating layer 127. A photoresist can be used as the photosensitive resin. The photosensitive resin can be a positive-type material or a negative-type material.
[0262] The insulating layer 127 may contain a material that absorbs visible light. For example, the insulating layer 127 itself may be made of a material that absorbs visible light, or the insulating layer 127 may contain a pigment that absorbs visible light. For example, the insulating layer 127 may be made of a resin that can be used as a color filter that transmits red, blue, or green light and absorbs other light, or a resin that contains carbon black as a pigment and functions as a black matrix.
[0263] 3B shows a plurality of cross sections of the inorganic insulating layer 125 and the insulating layer 127, it is preferable that the inorganic insulating layer 125 and the insulating layer 127 are connected to one another when the display device is viewed from above. In other words, it is preferable that the insulating layer 127 is an insulating layer having an opening over the first electrode.
[0264] 3B shows light emitting device 130 as light emitting device 130R, light emitting device 130G, and light emitting device 130B. Light emitting device 130R, light emitting device 130G, and light emitting device 130B emit light of different colors. For example, light emitting device 130R can emit red light, light emitting device 130G can emit green light, and light emitting device 130B can emit blue light. Furthermore, light emitting device 130R, light emitting device 130G, or light emitting device 130B may emit other visible light or infrared light.
[0265] The display device of one embodiment of the present invention can be, for example, a top-emission type in which light is emitted in a direction opposite to a substrate on which a light-emitting device is formed. Note that the display device of one embodiment of the present invention may also be a bottom-emission type.
[0266] The light-emitting device 130R has the structure described in Embodiments 1 and 2. It includes a first electrode 101R (pixel electrode) composed of a conductive layer 151R and a conductive layer 152R, an organic compound layer 103R on the first electrode 101R, and a second electrode 102R on the organic compound layer 103R. The electron injection layer, which is the outermost layer of the organic compound layer 103R, and the second electrode 102R have the structures described in Embodiments 1 and 2. This structure can suppress damage to the light-emitting layer or active layer during the photolithography process, and can provide a light-emitting device 130R with good film quality and electrical characteristics.
[0267] The light-emitting device 130G has the structure described in Embodiments 1 and 2. It includes a first electrode 101G (pixel electrode) composed of a conductive layer 151G and a conductive layer 152G, an organic compound layer 103G on the first electrode 101G, and a second electrode 102G on the organic compound layer 103G. The electron injection layer, which is the outermost layer of the organic compound layer 103G, and the second electrode 102G have the structures described in Embodiments 1 and 2. This structure can suppress damage to the light-emitting layer or active layer during the photolithography process, and can provide a light-emitting device 130G with good film quality and electrical characteristics.
[0268] The light-emitting device 130B has the structure described in Embodiments 1 and 2. It includes a first electrode 101B (pixel electrode) composed of a conductive layer 151B and a conductive layer 152B, an organic compound layer 103B on the first electrode 101B, and a second electrode 102B on the organic compound layer 103B. The electron injection layer, which is the outermost layer of the organic compound layer 103B, and the second electrode 102B have the structures described in Embodiments 1 and 2. This structure can suppress damage to the light-emitting layer or active layer during the photolithography process, and can provide a light-emitting device 130B with good film quality and electrical characteristics.
[0269] The organic compound layer 103R, the organic compound layer 103G, and the organic compound layer 103B are independent island-like layers for each light-emitting device or each emitted color. It is preferable that the organic compound layer 103R, the organic compound layer 103G, and the organic compound layer 103B do not overlap with each other. By providing the organic compound layer 103 in an island-like shape for each light-emitting device 130, leakage current between adjacent light-emitting devices 130 can be suppressed even in a high-resolution display device. This prevents crosstalk and realizes a display device with extremely high contrast. In particular, a display device with high current efficiency at low brightness can be realized.
[0270] The second electrodes 102R, 102G, and 102B are independent and island-shaped for each light-emitting device or for each row of the same emitted light color. It is preferable that the second electrodes 102R, 102G, and 102B do not overlap with each other.
[0271] It is preferable to form the auxiliary electrode 105 on the second electrode 102 after forming an insulating layer 127 covering the side surface of the light-emitting device 130, because this makes it easier to supply a voltage to the second electrode 102. The auxiliary electrode 105 can be made of, for example, a metal material. Specifically, metals such as aluminum (Al), titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), gallium (Ga), zinc (Zn), indium (In), tin (Sn), molybdenum (Mo), tantalum (Ta), tungsten (W), palladium (Pd), gold (Au), platinum (Pt), silver (Ag), yttrium (Y), neodymium (Nd), magnesium (Mg), etc., as well as alloys containing appropriate combinations of these metals, can also be used.
[0272] An oxide containing one or more selected from indium, tin, zinc, gallium, titanium, aluminum, and silicon can also be used as the auxiliary electrode 105. For example, it is preferable to use a conductive oxide containing one or more of indium oxide, indium tin oxide, indium zinc oxide, zinc oxide, zinc oxide containing gallium, titanium oxide, indium zinc oxide containing gallium, indium zinc oxide containing aluminum, indium tin oxide containing silicon, and indium zinc oxide containing silicon. Note that when the light-emitting device 130 is a top-emission light-emitting device, it is preferable to use a light-transmitting conductive metal oxide as the auxiliary electrode 105.
[0273] The island-shaped organic compound layer 103 is formed by forming an organic compound film and then processing the organic compound layer and the second electrode 102 by photolithography. Since the electron-injection layer and the second electrode have the structures described in Embodiment 1, the light-emitting device of one embodiment of the present invention can have favorable characteristics in which an increase in driving voltage is suppressed even when processing is performed by photolithography after forming the second electrode 102. Furthermore, by processing by photolithography after forming the second electrode 102, an inexpensive and reliable light-emitting device can be obtained.
[0274] In the display device of one embodiment of the present invention, the first electrode 101 (pixel electrode) of the light-emitting device preferably has a stacked structure. For example, in the example shown in FIG. 3B , the first electrode 101 of the light-emitting device 130 has a stacked structure of a conductive layer 151 provided on the substrate 171 side and a conductive layer 152 provided on the organic compound layer side.
[0275] For example, a metal material can be used as the conductive layer 151. Specifically, metals such as aluminum (Al), titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), gallium (Ga), zinc (Zn), indium (In), tin (Sn), molybdenum (Mo), tantalum (Ta), tungsten (W), palladium (Pd), gold (Au), platinum (Pt), silver (Ag), yttrium (Y), and neodymium (Nd), as well as alloys containing appropriate combinations of these metals, can also be used.
[0276] An oxide containing one or more selected from indium, tin, zinc, gallium, titanium, aluminum, and silicon can be used for the conductive layer 152. For example, it is preferable to use a conductive oxide containing one or more of indium oxide, indium tin oxide, indium zinc oxide, zinc oxide, zinc oxide containing gallium, titanium oxide, indium zinc oxide containing gallium, indium zinc oxide containing aluminum, indium tin oxide containing silicon, and indium zinc oxide containing silicon. In particular, indium tin oxide containing silicon has a large work function, for example, a work function of 4.0 eV or more, and therefore can be suitably used for the conductive layer 152.
[0277] The conductive layer 151 may have a stacked structure of multiple layers containing different materials, and the conductive layer 152 may have a stacked structure of multiple layers containing different materials. In this case, the conductive layer 151 may include a layer containing a material that can be used for the conductive layer 152, such as a conductive oxide, or the conductive layer 152 may include a layer containing a material that can be used for the conductive layer 151, such as a metal material. For example, when the conductive layer 151 has a stacked structure of two or more layers, a layer in contact with the conductive layer 152 can be a layer containing a material that can be used for the conductive layer 152.
[0278] 3B , the end portion of the conductive layer 151 has a tapered shape. Specifically, the end portion of the conductive layer 151 preferably has a tapered shape with a taper angle of less than 90°. In this case, the conductive layer 152 provided along the side surface of the conductive layer 151 also has a tapered shape. By tapering the side surface of the conductive layer 152, the coverage of the organic compound layer 103 provided along the side surface of the conductive layer 152 can be improved.
[0279] The ends of the conductive layers 151 and 152 may not be tapered, that is, may be substantially vertical. The ends of the organic compound layer 103 are preferably located inside the first electrode 101. In this case, leakage current through the organic compound layer 103 can be reduced, and a display device with low driving voltage and excellent display performance can be obtained.
[0280] In the display device of one embodiment of the present invention, the light-emitting device 130 has the structure described in Embodiments 1 and 2, and therefore can be a highly reliable light-emitting device.
[0281] Next, an example of a method for manufacturing a display device having the structure shown in FIG. 3A will be described with reference to FIGS.
[0282] [Fabrication Method Example 1] Thin films (insulating films, semiconductor films, conductive films, and the like) constituting a 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, or the like.
[0283] Furthermore, thin films (insulating films, semiconductor films, conductive films, etc.) constituting the display device can be formed by wet film formation methods such as spin coating, dipping, spray coating, inkjet, dispensing, screen printing, offset printing, doctor knife method, slit coating, roll coating, curtain coating, or knife coating.
[0284] Furthermore, when processing the thin films that constitute the display device, they can be processed using, for example, photolithography.
[0285] In photolithography, the light used for exposure may 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, and ArF laser light. Exposure may also be performed by immersion exposure technology. Extreme ultraviolet (EUV) light or X-rays may also be used as the light used for exposure. An electron beam may also be used instead of the light used for exposure.
[0286] The thin film can be etched by dry etching, wet etching, sandblasting, or the like.
[0287] 4A , an insulating layer 171 is formed on a substrate (not shown). Subsequently, conductive layers 172 and 179 are formed on the insulating layer 171, and an insulating layer 173 is formed on the insulating layer 171 so as to cover the conductive layers 172 and 179. Subsequently, an insulating layer 174 is formed on the insulating layer 173, and an insulating layer 175 is formed on the insulating layer 174.
[0288] The substrate may be a substrate having heat resistance sufficient to withstand at least a subsequent heat treatment, such as a glass substrate, a quartz substrate, a sapphire substrate, a ceramic substrate, an organic resin substrate, a single crystal semiconductor substrate made of silicon, silicon carbide, or the like, a polycrystalline semiconductor substrate, a compound semiconductor substrate made of silicon germanium, or the like, or an SOI substrate.
[0289] 4A, openings are formed in the insulating layers 175, 174, and 173, reaching the conductive layer 172. Then, plugs 176 are formed to fill the openings.
[0290] 4A , a conductive film 151f, which will later become conductive layers 151R, 151G, 151B, and 151C, and a conductive film 152f, which will later become conductive layers 152R, 152G, 152B, and 152C, are formed on the plug 176 and the insulating layer 175. The conductive film 151f may be formed of, for example, a metal material. The conductive film 152f may be formed of, for example, an oxide containing one or more elements selected from indium, tin, zinc, gallium, titanium, aluminum, and silicon.
[0291] 4A, a resist mask 191 is formed over the conductive film 152f. The resist mask 191 can be formed by applying a photosensitive material (photoresist) and then performing exposure and development.
[0292] 4B, for example, the conductive films 151f and 152f are removed from regions that do not overlap with the resist mask 191. As a result, the conductive layers 151 and 152 are formed.
[0293] 4C, the resist mask 191 is removed by, for example, ashing using oxygen plasma.
[0294] Subsequently, as shown in FIG. 4D , an insulating film 156f, which will later become insulating layers 156R, 156G, 156B, and 156C, is formed on the conductive layer 152R, the conductive layer 152G, the conductive layer 152B, the conductive layer 152C, and the insulating layer 175.
[0295] The insulating film 156f can be an inorganic insulating film such as an insulating oxide film, an insulating nitride film, an insulating oxynitride film, or an insulating nitride oxide film, for example, a silicon oxynitride film.
[0296] Subsequently, as shown in FIG. 4E, the insulating film 156f is processed to form insulating layers 156R, 156G, 156B, and 156C.
[0297] 5A, the organic compound film 103Rf is formed on the conductive layer 152R, the conductive layer 152G, the conductive layer 152B, and the insulating layer 175. Note that, as shown in FIG. 5A, the organic compound film 103Rf is not formed on the conductive layer 152C.
[0298] 5A, a conductive film 102Rf serving as a second electrode is formed on the organic compound film 103Rf, and then a sacrificial film 158Rf and a mask film 159Rf are formed on the conductive film 102Rf. By forming the sacrificial film 158Rf and the mask film 159Rf on the organic compound film 103Rf via the conductive film 102Rf, damage to the organic compound film 103Rf during the manufacturing process of the display device can be reduced, and the reliability of the light-emitting device can be improved.
[0299] When the second electrode 102 is an electrode from which light is extracted, the conductive film 102Rf is preferably made of a material that is transparent to visible light. For example, the reflectance of visible light is 20% or more and 80% or less, preferably 40% or more and 70% or less, and the resistivity is 1×10 −2 Examples of the conductive material include a conductive material having a resistivity of Ω·cm or less. Furthermore, when a material with low optical transparency, such as a metal or alloy, is used for the conductive film 102Rf, it may be formed to a thickness (e.g., 1 nm to 10 nm) that allows visible light to pass through. Specifically, in addition to an oxide conductor layer such as ITO, the conductive film 102Rf may include an oxide semiconductor layer or an organic conductor layer containing an organic substance. Examples of the organic conductor layer containing an organic substance include a layer containing a composite material obtained by mixing an organic compound and an electron donor (donor), and a layer containing a composite material obtained by mixing an organic compound and an electron acceptor (acceptor). Furthermore, the resistivity of the transparent conductive layer is preferably 1×10 Ω·cm or less, and more preferably 1×10 Ω·cm or less.
[0300] The conductive film 102Rf can be formed by a dry method such as a vacuum deposition method or a sputtering method, an inkjet method, a spin coating method, or the like. Alternatively, the conductive film 102Rf may be formed by a wet method using a sol-gel method, or by a wet method using a metal material paste. In particular, the conductive film 102Rf formed on and in contact with the organic compound film 103Rf is preferably formed by a method that causes less damage to the organic compound film 103Rf. For example, an atomic layer deposition (ALD) method or a vacuum deposition method is preferable.
[0301] The sacrificial film 158Rf and the mask film 159Rf are provided as needed. For example, if the conductive film 102Rf can sufficiently protect the organic compound film 103Rf, the mask film 159Rf can be formed on the conductive film Rf, thereby eliminating the step of forming the sacrificial film 158Rf. Furthermore, if the etching selectivity between the organic compound film 103Rf and the conductive film 102Rf and between the conductive film 102Rf and the sacrificial film 158Rf are both sufficiently large, the sacrificial film 158Rf can be used as a mask, and the step of forming the mask film 159Rf may be omitted.
[0302] The sacrificial film 158Rf is made of a film that is highly resistant to the processing conditions of the organic compound film 103Rf, specifically, a film that has a large etching selectivity with respect to the organic compound film 103Rf.The mask film 159Rf is made of a film that has a large etching selectivity with respect to the sacrificial film 158Rf.
[0303] Furthermore, the conductive film 102Rf, the sacrificial film 158Rf, and the mask film 159Rf are preferably formed at a temperature lower than the heat-resistant temperature of the organic compound film 103Rf. The substrate temperature when forming the sacrificial film 158Rf and the mask film 159Rf is typically 100° C. or higher and 200° C. or lower, preferably 100° C. or higher and 150° C. or lower, and more preferably 100° C. or higher and 120° C. or lower.
[0304] It is preferable to use a film that can be removed by wet etching or dry etching for the sacrificial film 158Rf and the mask film 159Rf.
[0305] The sacrificial film 158Rf is preferably denser than the mask film 159Rf. For example, the ALD method or the vacuum deposition method is more preferable than the sputtering method.
[0306] The sacrificial film 158Rf and the mask film 159Rf may each be made of one or more of a metal film, an alloy film, a metal oxide film, a semiconductor film, an organic insulating film, an inorganic insulating film, or the like.
[0307] The sacrificial film 158Rf and the mask film 159Rf can be made of a metal material such as gold, silver, platinum, magnesium, nickel, tungsten, chromium, molybdenum, iron, cobalt, copper, palladium, titanium, aluminum, yttrium, zirconium, or tantalum, or an alloy material containing such a metal material. It is particularly preferable to use a low-melting-point material such as aluminum or silver. Using a metal material capable of blocking ultraviolet rays for one or both of the sacrificial film 158Rf and the mask film 159Rf is preferable because it can prevent the organic compound film 103Rf from being irradiated with ultraviolet rays during pattern exposure, thereby suppressing deterioration of the organic compound film 103Rf.
[0308] Furthermore, for the sacrificial film 158Rf and the mask film 159Rf, metal oxides such as In—Ga—Zn oxide, indium oxide, In—Zn 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), and indium tin oxide containing silicon can be used, respectively.
[0309] In addition, in the above metal oxide, 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) may be used instead of gallium.
[0310] The sacrificial film 158Rf and the mask film 159Rf are preferably made of a semiconductor material such as silicon or germanium, which has a high affinity with the semiconductor manufacturing process. Alternatively, compounds containing the semiconductor materials can be used.
[0311] The sacrificial film 158Rf and the mask film 159Rf may be made of various inorganic insulating films, and an oxide insulating film is particularly preferable because it has higher adhesion to the organic compound film 103Rf than a nitride insulating film.
[0312] 5A, a resist mask 190R is formed. The resist mask 190R can be formed by applying a photosensitive material (photoresist) and then performing exposure and development.
[0313] The resist mask 190R is provided in a position overlapping with the conductive layer 152R. The resist mask 190R is preferably provided also in a position overlapping with the conductive layer 152C. This can prevent the conductive layer 152C from being damaged during the manufacturing process of the display device.
[0314] 5B , a resist mask 190R is used to remove part of the mask film 159Rf to form a mask layer 159R. The mask layer 159R remains on the conductive layer 152R and the conductive layer 152C. Then, the resist mask 190R is removed. Next, using the mask layer 159R as a mask (also referred to as a hard mask), parts of the sacrificial film 158Rf and the conductive film 102Rf are removed to form the sacrificial layer 158R and the second electrode 102R.
[0315] By using the wet etching method, damage to the organic compound film 103Rf can be reduced when processing the conductive film 102Rf, the sacrificial film 158Rf, and the mask film 159Rf, compared to when using the dry etching method. When using the wet etching method, it is preferable to use an acid aqueous solution such as a developing solution, an alkaline aqueous solution such as a tetramethylammonium hydroxide aqueous solution (TMAH), a chemical solution using dilute hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, nitric acid, or a mixture of these.
[0316] Furthermore, when dry etching is used to process the sacrificial film 158Rf and the conductive film 102Rf, deterioration of the organic compound film 103Rf can be suppressed by not using a gas containing oxygen as the etching gas.
[0317] The resist mask 190R can be removed in the same manner as the resist mask 191.
[0318] 5B, the organic compound film 103Rf is processed to form the organic compound layer 103R. For example, the mask layer 159R and the sacrificial layer 158R are used as hard masks to remove a part of the conductive film 102Rf and a part of the organic compound film 103Rf, thereby forming the organic compound layer 103R.
[0319] 5B, a stacked structure of the organic compound layer 103R, the second electrode 102R, the sacrificial layer 158R, and the mask layer 159R remains on the conductive layer 152R. In addition, the conductive layers 152G and 152B are exposed.
[0320] The organic compound film 103Rf is preferably processed by anisotropic etching, particularly anisotropic dry etching, or wet etching may be used.
[0321] When dry etching is used, deterioration of the organic compound film 103Rf can be suppressed by not using a gas containing oxygen as the etching gas.
[0322] Alternatively, a gas containing oxygen may be used as the etching gas. By using an etching gas containing oxygen, the etching rate can be increased. Therefore, etching can be performed under low power conditions while maintaining a sufficiently high etching rate. This makes it possible to suppress damage to the organic compound film 103Rf. Furthermore, problems such as adhesion of reaction products generated during etching can be suppressed.
[0323] When dry etching is used, for example, H 2 , C.F. 4 , C 4 F 8 , S.F. 6 , CHF 3 , Cl 2 , H2 O, BCl 3 It is preferable to use a gas containing one or more of Group 18 elements such as He and Ar as the etching gas. Alternatively, it is preferable to use a gas containing one or more of these elements and oxygen as the etching gas. Alternatively, oxygen gas may be used as the etching gas.
[0324] Subsequently, as shown in FIG. 6A, an organic compound film 103Gf, which will later become the organic compound layer 103G, and a conductive film 102Gf, which will later become the second electrode 102G, are formed.
[0325] The organic compound film 103Gf can be formed by a method similar to that used to form the organic compound film 103Rf. The organic compound film 103Gf can have the same structure as the organic compound film 103Rf. The conductive film 102Gf can be formed by a method similar to that used to form the conductive film 102Rf. The conductive film 102Gf can have the same structure as the conductive film 102Rf.
[0326] Next, as shown in FIG. 6A , a sacrificial film 158Gf and a mask film 159Gf are formed in this order. Then, a resist mask 190G is formed. The materials and forming methods of the sacrificial film 158Gf and the mask film 159Gf are the same as those applicable to the sacrificial film 158Rf and the mask film 159Rf. The materials and forming methods of the resist mask 190G are the same as those applicable to the resist mask 190R.
[0327] The resist mask 190G is provided in a position overlapping with the conductive layer 152G.
[0328] 6B, a resist mask 190G is used to remove a portion of the mask film 159Gf to form a mask layer 159G. The mask layer 159G remains on the conductive layer 152G. The resist mask 190G is then removed. The mask layer 159G is then used as a mask to remove a portion of the sacrificial film 158Gf and a portion of the conductive film 102Gf to form a sacrificial layer 158G and a second electrode 102G. The organic compound film 103Gf is then processed to form an organic compound layer 103G.
[0329] Subsequently, as shown in FIG. 6C, an organic compound film 103Bf and a conductive film 102Bf that will later become the second electrode 102B are formed.
[0330] The organic compound film 103Bf can be formed by a method similar to that used to form the organic compound film 103Rf. The organic compound film 103Bf can have the same structure as the organic compound film 103Rf. The conductive film 102Bf can be formed by a method similar to that used to form the conductive film 102Rf. The conductive film 102Bf can have the same structure as the conductive film 102Rf.
[0331] 6C, a sacrificial film 158Bf and a mask film 159Bf are formed in this order. Then, a resist mask 190B is formed. The materials and forming methods of the sacrificial film 158Bf and the mask film 159Bf are the same as those applicable to the sacrificial film 158Rf and the mask film 159Rf. The materials and forming methods of the resist mask 190B are the same as those applicable to the resist mask 190R.
[0332] The resist mask 190B is provided in a position overlapping with the conductive layer 152B.
[0333] 6D, a resist mask 190B is used to remove a portion of the mask film 159Bf to form a mask layer 159B. The mask layer 159B remains on the conductive layer 152B. The resist mask 190B is then removed. The mask layer 159B is then used as a mask to remove a portion of the sacrificial film 158Bf and a portion of the conductive film 102Bf to form a sacrificial layer 158B and a second electrode 102B. The organic compound film 103Bf is then processed to form an organic compound layer 103B. For example, the mask layer 159B and the sacrificial layer 158B are used as hard masks to remove a portion of the organic compound film 103Bf to form the organic compound layer 103B.
[0334] 6D, a laminated structure of the organic compound layer 103B, the second electrode 102B, the sacrificial layer 158B, and the mask layer 159B remains on the conductive layer 152B. Also, the mask layers 159R and 159G are exposed.
[0335] Note that the side surfaces of the stacked structure of the organic compound layer 103R and the second electrode 102R, the stacked structure of the organic compound layer 103G and the second electrode 102G, and the stacked structure of the organic compound layer 103B and the second electrode 102B are preferably perpendicular or approximately perpendicular to the surface on which the layers are to be formed. For example, the angle formed between the surface on which the layers are to be formed and these side surfaces is preferably 60 degrees or more and 90 degrees or less.
[0336] As described above, the distance between adjacent layers among the stacked structures of the organic compound layer 103R and the second electrode 102R, the stacked structure of the organic compound layer 103G and the second electrode 102G, and the stacked structure of the organic compound layer 103B and the second electrode 102B formed using a photolithography method can be narrowed to 8 μm or less, 5 μm or less, 3 μm or less, 2 μm or less, or 1 μm or less. Here, the distance can be defined, for example, as the distance between adjacent opposing ends of the organic compound layer 103R, the organic compound layer 103G, and the organic compound layer 103B. By narrowing the distance between the island-shaped EL layers in this way, a display device with high definition and a large aperture ratio can be provided. Furthermore, the distance between the first electrodes of adjacent light-emitting devices can also be narrowed, for example, to 10 μm or less, 8 μm or less, 5 μm or less, 3 μm or less, or 2 μm or less. The distance between the first electrodes of adjacent light-emitting devices is preferably 2 μm or more and 5 μm or less.
[0337] Subsequently, as shown in FIG. 7A, it is preferable to remove the mask layers 159R, 159G, and 159B.
[0338] Note that when the light-emitting device is arranged in a so-called stripe configuration as shown in FIG. 22G, the second electrode 102 can be formed as a continuous layer with the same emission color. In this case, the auxiliary electrode 105 described later does not need to be formed. Therefore, in the case of bottom emission, the mask layer 159 does not need to be removed, and the process can proceed to the process of FIG. 9B after the process of FIG. 6D. In the case of top emission, if the sacrificial layer 158 and the mask layer 159 are light-transmitting, they do not need to be removed, and the process can proceed to the process of FIG. 9B after the process of FIG. 6D. If they are not light-transmitting, it is preferable to remove the sacrificial layer 158 and the mask layer 159. After removing the sacrificial layer 158 and / or the mask layer 159 (after the process of FIG. 7A), the process can proceed to the process of FIG. 9B.
[0339] The mask layer removal process can be performed using the same method as the mask film processing process. In particular, by using a wet etching method, damage to the organic compound layer 103 during the mask layer removal can be reduced compared to when a dry etching method is used.
[0340] The mask layer may also be removed by dissolving it in a polar solvent such as water or alcohol, such as ethyl alcohol, methyl alcohol, isopropyl alcohol (IPA), or glycerin.
[0341] After removing the mask layer, a drying treatment may be performed to remove water adsorbed on the surface. For example, a heat treatment can be performed 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 preferred because it allows drying at a lower temperature.
[0342] Subsequently, as shown in FIG. 7B, an inorganic insulating film 125f is formed.
[0343] Subsequently, as shown in FIG. 7C, an insulating film 127f, which will later become the insulating layer 127, is formed on the inorganic insulating film 125f.
[0344] The substrate temperature when forming the inorganic insulating film 125f and the insulating film 127f is preferably 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, and 200°C or lower, 180°C or lower, 160°C or lower, 150°C or lower, or 140°C or lower, respectively.
[0345] As the inorganic insulating film 125f, it is preferable to form an insulating film having a thickness of 3 nm or more, 5 nm or more, or 10 nm or more, and 200 nm or less, 150 nm or less, 100 nm or less, or 50 nm or less within the above substrate temperature range.
[0346] The inorganic insulating film 125f is preferably formed by, for example, the ALD method. The ALD method is preferable because it can reduce film formation damage and form a film with high coverage. The inorganic insulating film 125f is preferably formed as an aluminum oxide film by, for example, the ALD method.
[0347] The insulating film 127f is preferably formed by the wet film formation method described above. The insulating film 127f is preferably formed by, for example, spin coating using a photosensitive material, more specifically, using a photosensitive resin composition containing an acrylic resin.
[0348] Subsequently, exposure is performed to expose a portion of the insulating film 127f to visible light or ultraviolet light. The insulating layer 127f is formed in a region sandwiched between any two of the conductive layers 152R, 152G, and 152B, and around the conductive layer 152C.
[0349] The width of the insulating layer 127 to be formed later can be controlled by the exposed region of the insulating film 127f. In this embodiment mode, the insulating layer 127 is processed to have a portion overlapping with the top surface of the conductive layer 151.
[0350] The light used for exposure preferably contains i-line (wavelength 365 nm), and may contain at least one of g-line (wavelength 436 nm) and h-line (wavelength 405 nm).
[0351] Subsequently, as shown in FIG. 8A, development is performed to remove the exposed area of the insulating film 127f, thereby forming an insulating layer 127a.
[0352] 8B, an etching process is performed using the insulating layer 127a as a mask to remove a portion of the inorganic insulating film 125f and thin the film thickness of a portion of the sacrificial layers 158R, 158G, and 158B. This results in the formation of the inorganic insulating layer 125 below the insulating layer 127a. Furthermore, the surfaces of the thin portions of the sacrificial layers 158R, 158G, and 158B are exposed. Hereinafter, the etching process using the insulating layer 127a as a mask may be referred to as the first etching process.
[0353] The first etching treatment can be performed by dry etching or wet etching. Note that if the inorganic insulating film 125f is formed using the same material as the sacrificial layers 158R, 158G, and 158B, the first etching treatment can be performed all at once, which is preferable. Furthermore, if the sacrificial layer 158 is not formed, the surfaces of the second electrode 102R, the second electrode 102B, and the second electrode 102G are exposed by the first etching treatment.
[0354] When dry etching is performed, it is preferable to use a chlorine-based gas. 2 , BCl 3 , SiCl 4 , and CCl 4 The chlorine-based gas may be added with oxygen gas, hydrogen gas, helium gas, argon gas, or the like, either alone or in combination of two or more gases. By using dry etching, thin regions of the sacrificial layers 158R, 158G, and 158B can be formed with good in-plane uniformity.
[0355] The dry etching apparatus may be a dry etching apparatus having a high-density plasma source, such as an inductively coupled plasma (ICP) etching apparatus, or a capacitively coupled plasma (CCP) etching apparatus having parallel plate electrodes.
[0356] Furthermore, it is preferable to perform the first etching process by wet etching. Using the wet etching method can reduce damage to the structure to be processed compared to using the dry etching method. For example, the wet etching can be performed using an alkaline solution. For example, TMAH, which is an alkaline solution, can be used for wet etching of an aluminum oxide film. Alternatively, an acid solution containing fluoride can also be used. In this case, the wet etching can be performed by the puddle method. Note that if the inorganic insulating film 125f is formed using the same material as the sacrificial layers 158R, 158G, and 158B, the above etching process can be performed all at once, which is preferable.
[0357] In the first etching process, the sacrificial layers 158R, 158G, and 158B are not completely removed, and the etching process is stopped when the film thicknesses of the sacrificial layers 158R, 158G, and 158B are reduced. In this manner, by leaving the corresponding sacrificial layers 158R, 158G, and 158B on the second electrodes 102R, 102B, and 102G, it is possible to prevent the structure including the organic compound layer 103 from being damaged in a subsequent process.
[0358] Subsequently, the entire substrate is exposed to visible light or ultraviolet light, and the insulating layer 127a is preferably irradiated with the energy density of the exposure. 2 Larger than 800 mJ / cm 2 It is preferable that the dose is 0 mJ / cm or less. 2 Greater than 500 mJ / cm 2It is more preferable to perform the following. By performing such exposure after development, the transparency of the insulating layer 127a can be improved in some cases. Furthermore, the substrate temperature required for heat treatment to transform the insulating layer 127a into a tapered shape in a later step can be reduced in some cases.
[0359] Here, the presence of a barrier insulating layer against oxygen (e.g., an aluminum oxide film, etc.) as the sacrificial layer 158R, the sacrificial layer 158G, and the sacrificial layer 158B can reduce the diffusion of oxygen to the second electrode 102R, the second electrode 102B, and the second electrode 102G, or the decrease in conductivity due to metal oxidation.
[0360] Next, heat treatment (also referred to as post-baking) is performed. The heat treatment can transform the insulating layer 127a into an insulating layer 127 having tapered side surfaces (FIG. 8C). The heat treatment is performed at a temperature lower than the heat resistance temperature of the EL layer. The heat treatment can be performed at a substrate temperature of 50° C. to 200° C., preferably 60° C. to 150° C., and more preferably 70° C. to 130° C. The heating atmosphere may be an air atmosphere or an inert gas atmosphere. The heating atmosphere may be an atmospheric pressure atmosphere or a reduced-pressure atmosphere. This can improve the adhesion between the insulating layer 127 and the inorganic insulating layer 125 and also improve the corrosion resistance of the insulating layer 127.
[0361] In the first etching treatment, the sacrificial layers 158R, 158G, and 158B are not completely removed, and the sacrificial layers 158R, 158G, and 158B are left in a state where their film thicknesses are reduced, thereby preventing the processed structure including the organic compound layer 103 from being damaged and deteriorated in the heat treatment, thereby improving the reliability of the light-emitting device.
[0362] 9A , an etching process is performed using the insulating layer 127 as a mask to remove portions of the sacrificial layers 158R, 158G, and 158B. As a result, openings are formed in the sacrificial layers 158R, 158G, and 158B, respectively, and the upper surfaces of the second electrodes 102R, 102B, and 102G, and the conductive layer 152C are exposed. Note that, hereinafter, this etching process may be referred to as the second etching process.
[0363] In addition, if the sacrificial layer 158 is not formed, the surfaces of the second electrode 102R, the second electrode 102B, and the second electrode 102G are exposed by the first etching process, so the second etching step described below can be omitted.
[0364] The end of the inorganic insulating layer 125 is covered with the insulating layer 127. Also, Fig. 9A shows an example in which a part of the end of the sacrificial layer 158G (specifically, the tapered portion formed by the first etching process) is covered with the insulating layer 127, and the tapered portion formed by the second etching process is exposed.
[0365] The second etching process is performed by wet etching. By using wet etching, damage to the organic compound layer 103R, the organic compound layer 103G, and the organic compound layer 103B can be reduced compared to when dry etching is used. Wet etching can be performed using, for example, an alkaline solution or an acidic solution. An aqueous solution is preferably used so that the organic compound layer 103 does not dissolve.
[0366] 9B , an auxiliary electrode 105 is formed on the second electrode 102R, the second electrode 102B, the second electrode 102G, the conductive layer 152C, and the insulating layer 127. The auxiliary electrode 105 can be formed by a method such as sputtering or vacuum deposition.
[0367] 9B, a protective layer 131 is formed on the auxiliary electrode 105. The protective layer 131 can be formed by a method such as a vacuum deposition method, a sputtering method, a CVD method, or an ALD method.
[0368] Subsequently, the substrate 120 is attached over the protective layer 131 using the resin layer 122, whereby a display device can be manufactured. As described above, in the method for manufacturing a display device of one embodiment of the present invention, the insulating layer 156 is provided so as to have a region overlapping with a side surface of the conductive layer 151, and the conductive layer 152 is formed so as to cover the conductive layer 151 and the insulating layer 156. This can increase the yield of the display device and suppress the occurrence of defects.
[0369] As described above, in the manufacturing method of a display device according to one embodiment of the present invention, the island-shaped organic compound layers 103R, 103G, and 103B are formed by forming films over the entire surface and then processing them, rather than using a fine metal mask. This allows the island-shaped layers to be formed with uniform thicknesses. This allows a high-resolution display device or a display device with a high aperture ratio to be realized. Furthermore, even when the resolution or aperture ratio is high and the distance between subpixels is extremely short, the organic compound layers 103R, 103G, and 103B can be prevented from contacting each other in adjacent subpixels. Therefore, leakage current between subpixels can be suppressed. This prevents crosstalk and realizes a display device with extremely high contrast. Furthermore, even in a display device including tandem light-emitting devices manufactured by photolithography, a display device with excellent characteristics can be provided.
[0370] Embodiment 4 In this embodiment, a display device according to one embodiment of the present invention will be described.
[0371] The display device of the present embodiment can be a high-definition display device, and can therefore be used, for example, as a display unit for a wristwatch-type or bracelet-type information terminal (wearable device), as well as a display unit for a wearable device that can be worn on the head, such as a head-mounted display (HMD) for VR, or a glasses-type device for AR.
[0372] The display device of the present embodiment can be a high-resolution display device or a large-sized display device. Therefore, the display device of the present embodiment can be used in electronic devices having relatively large screens, such as television devices, desktop or notebook personal computers, computer monitors, digital signage, and large game machines such as pachinko machines, as well as in the display units of digital cameras, digital video cameras, digital photo frames, mobile phones, portable game machines, personal digital assistants, and sound reproducing devices.
[0373] 10A shows a perspective view of display module 280. Display module 280 has display device 100A and FPC 290. Note that the display device included in display module 280 is not limited to display device 100A, and may be either display device 100B or display device 100E, which will be described later.
[0374] The display module 280 has a substrate 291 and a substrate 292. The display module 280 has a display portion 281. The display portion 281 is a region that displays an image in the display module 280, and is a region where light from each pixel provided in a pixel portion 284 (described later) can be viewed.
[0375] 10B is a perspective view schematically illustrating the configuration on the substrate 291 side. A circuit portion 282, a pixel circuit portion 283 on the circuit portion 282, and a pixel portion 284 on the pixel circuit portion 283 are stacked on the substrate 291. A terminal portion 285 for connecting to the FPC 290 is provided in a portion of the substrate 291 that does not overlap with the pixel portion 284. The terminal portion 285 and the circuit portion 282 are electrically connected by a wiring portion 286 composed of a plurality of wirings.
[0376] The pixel portion 284 has a plurality of periodically arranged pixels 284a. An enlarged view of one pixel 284a is shown on the right side of Fig. 10B. The various configurations described in the previous embodiments can be applied to the pixel 284a. Fig. 10B shows an example in which the pixel 284a has the same configuration as the pixel 178 shown in Fig. 3.
[0377] The pixel circuit section 283 has a plurality of pixel circuits 283a arranged periodically.
[0378] One pixel circuit 283a is a circuit that controls the driving of a plurality of elements included in one pixel 284a.
[0379] The circuit portion 282 includes a circuit for driving each pixel circuit 283 a of the pixel circuit portion 283. For example, the circuit portion 282 preferably includes one or both of a gate line driver circuit and a source line driver circuit. In addition, the circuit portion 282 may include at least one of an arithmetic circuit, a memory circuit, a power supply circuit, and the like.
[0380] The FPC 290 functions as wiring for supplying a video signal, a power supply potential, or the like from the outside to the circuit portion 282. An IC may be mounted on the FPC 290.
[0381] The display module 280 can be configured such that one or both of the pixel circuit unit 283 and the circuit unit 282 are stacked below the pixel unit 284, thereby making it possible to extremely increase the aperture ratio (effective display area ratio) of the display unit 281.
[0382] Because such a display module 280 has extremely high resolution, it can be suitably used in VR devices such as HMDs or eyeglass-type AR devices. For example, even in a configuration in which the display unit of the display module 280 is viewed through lenses, the display module 280 has an extremely high-resolution display unit 281, so that even if the display unit is enlarged with the lens, the pixels are not visible, allowing for a highly immersive display. Furthermore, the display module 280 is not limited to this, and can be suitably used in electronic devices having relatively small display units.
[0383] Display Device 100A The display device 100A shown in FIG. 11A includes a substrate 301, a light-emitting device 130R, a light-emitting device 130G, a light-emitting device 130B, a capacitor 240, and a transistor 310.
[0384] The substrate 301 corresponds to the substrate 291 in FIGS. 10A and 10B . The transistor 310 is a transistor having a channel formation region in the substrate 301. The substrate 301 can be, for example, a semiconductor substrate such as a single crystal silicon substrate. The transistor 310 includes a part of the substrate 301, a conductive layer 311, a low-resistance region 312, an insulating layer 313, and an insulating layer 314. The conductive layer 311 functions as a gate electrode. The insulating layer 313 is located between the substrate 301 and the conductive layer 311 and functions as a gate insulating layer. The low-resistance region 312 is a region in which the substrate 301 is doped with impurities and functions as a source or drain. The insulating layer 314 is provided to cover a side surface of the conductive layer 311.
[0385] An element isolation layer 315 is provided between two adjacent transistors 310 so as to be embedded in the substrate 301 .
[0386] In addition, an insulating layer 261 is provided to cover the transistor 310 , and a capacitor 240 is provided over the insulating layer 261 .
[0387] The capacitor 240 has a conductive layer 241, a conductive layer 245, and an insulating layer 243 located therebetween. The conductive layer 241 functions as one electrode of the capacitor 240, the conductive layer 245 functions as the other electrode of the capacitor 240, and the insulating layer 243 functions as a dielectric of the capacitor 240.
[0388] The conductive layer 241 is provided over the insulating layer 261 and is buried in the insulating layer 254. The conductive layer 241 is electrically connected to one of the source and the drain of the transistor 310 by a plug 271 buried in the insulating layer 261. The insulating layer 243 is provided to cover the conductive layer 241. The conductive layer 245 is provided in a region overlapping with the conductive layer 241 with the insulating layer 243 interposed therebetween.
[0389] An insulating layer 255 is provided to cover the capacitor 240, an insulating layer 174 is provided on the insulating layer 255, and an insulating layer 175 is provided on the insulating layer 174. Light-emitting device 130R, light-emitting device 130G, and light-emitting device 130B are provided on the insulating layer 175. An insulator is provided in the region between adjacent light-emitting devices.
[0390] An insulating layer 156R is provided to have a region overlapping with a side surface of the conductive layer 151R, an insulating layer 156G is provided to have a region overlapping with a side surface of the conductive layer 151G, and an insulating layer 156B is provided to have a region overlapping with a side surface of the conductive layer 151B. Furthermore, a conductive layer 152R is provided to cover the conductive layer 151R and the insulating layer 156R, a conductive layer 152G is provided to cover the conductive layer 151G and the insulating layer 156G, and a conductive layer 152B is provided to cover the conductive layer 151B and the insulating layer 156B. Note that the insulating layer 156 is not necessarily provided.
[0391] The conductive layer 151R, the conductive layer 151G, and the conductive layer 151B are electrically connected to one of the source and the drain of the transistor 310 by an insulating layer 243, an insulating layer 255, an insulating layer 174, a plug 256 embedded in the insulating layer 175, a conductive layer 241 embedded in the insulating layer 254, and a plug 271 embedded in the insulating layer 261. Various conductive materials can be used for the plugs.
[0392] Furthermore, a protective layer 131 is provided on light-emitting device 130R, light-emitting device 130G, and light-emitting device 130B via auxiliary electrode 105. Substrate 120 is bonded to protective layer 131 with resin layer 122. For details of the components from light-emitting device 130 to substrate 120, refer to embodiment 3. Substrate 120 corresponds to substrate 292 in FIG. 10A .
[0393] Fig. 11B is a modified example of the display device 100A shown in Fig. 11A. The display device shown in Fig. 11B has a colored layer 132R, a colored layer 132G, and a colored layer 132B, and the light-emitting device 130 has an area where it overlaps with one of the colored layers 132R, 132G, and 132B. In the display device shown in Fig. 11B, the light-emitting device 130 can emit, for example, white light. Furthermore, for example, the colored layer 132R can transmit red light, the colored layer 132G can transmit green light, and the colored layer 132B can transmit blue light.
[0394] [Display Device 100B] FIG. 12 shows a perspective view of the display device 100B, and FIG. 13 shows a cross-sectional view of the display device 100B.
[0395] The display device 100B has a configuration in which a substrate 352 and a substrate 351 are bonded together. In Fig. 12, the substrate 352 is indicated by a dashed line.
[0396] The display device 100B includes a pixel portion 177, a connection portion 140, a circuit 356, wiring 355, and the like. Fig. 12 shows an example in which an IC 354 and an FPC 353 are mounted on the display device 100B. Therefore, the configuration shown in Fig. 12 can also be called a display module including the display device 100B, an IC (integrated circuit), and an FPC. Here, a display device in which a connector such as an FPC is attached to a substrate or a display device in which an IC is mounted on the substrate is called a display module.
[0397] The connection portion 140 is provided outside the pixel portion 177. There may be one or more connection portions 140. The connection portion 140 electrically connects the common electrode of the light-emitting device and the conductive layer, and can supply a potential to the common electrode.
[0398] The circuit 356 can be, for example, a scanning line driver circuit.
[0399] The wiring 355 has a function of supplying signals and power to the pixel portion 177 and the circuit 356. The signals and power are input to the wiring 355 from the outside via the FPC 353 or from the IC 354.
[0400] 12 shows an example in which an IC 354 is provided on a substrate 351 by a chip-on-glass (COG) method, a chip-on-film (COF) method, or the like. For example, an IC having a scanning line driver circuit or a signal line driver circuit can be used as the IC 354. Note that the display device 100B and the display module may not include an IC. Alternatively, the IC may be mounted on an FPC by a COF method, for example.
[0401] Figure 13 shows an example of a cross section of the display device 100B, where a portion of the region including the FPC 353, a portion of the circuit 356, a portion of the pixel portion 177, a portion of the connection portion 140, and a portion of the region including the end portion are cut.
[0402] [Display Device 100C] The display device 100C shown in FIG. 13 has, between a substrate 351 and a substrate 352, a transistor 201, a transistor 205, a light-emitting device 130R that emits red light, a light-emitting device 130G that emits green light, and a light-emitting device 130B that emits blue light, etc.
[0403] For details of the light emitting device 130R, the light emitting device 130G, and the light emitting device 130B, refer to the first embodiment or the second embodiment.
[0404] Light-emitting device 130R has conductive layer 224R, conductive layer 151R on conductive layer 224R, and conductive layer 152R on conductive layer 151R. Light-emitting device 130G has conductive layer 224G, conductive layer 151G on conductive layer 224G, and conductive layer 152G on conductive layer 151G. Light-emitting device 130B has conductive layer 224B, conductive layer 151B on conductive layer 224B, and conductive layer 152B on conductive layer 151B.
[0405] The conductive layer 224R is connected to the conductive layer 222b of the transistor 205 through an opening provided in the insulating layer 214. An end of the conductive layer 151R is located outside an end of the conductive layer 224R. An insulating layer 156R is provided to have a region in contact with the side surface of the conductive layer 151R, and a conductive layer 152R is provided to cover the conductive layer 151R and the insulating layer 156R.
[0406] Conductive layer 224G, conductive layer 151G, conductive layer 152G, and insulating layer 156G in light-emitting device 130G, and conductive layer 224B, conductive layer 151B, conductive layer 152B, and insulating layer 156B in light-emitting device 130B are similar to conductive layer 224R, conductive layer 151R, conductive layer 152R, and insulating layer 156R in light-emitting device 130R, and therefore detailed description thereof will be omitted.
[0407] Recesses are formed in the conductive layers 224R, 224G, and 224B so as to cover the openings provided in the insulating layer 214. A layer 128 is buried in the recesses.
[0408] The layer 128 has a function of filling in recesses of the conductive layer 224R, the conductive layer 224G, and the conductive layer 224B and planarizing the surface. Conductive layers 151R, 151G, and 151B, which are electrically connected to the conductive layer 224R, the conductive layer 224G, and the conductive layer 224B, are provided on the conductive layer 224R, the conductive layer 224G, and the conductive layer 224B and the layer 128. Therefore, the regions overlapping with the recesses of the conductive layer 224R, the conductive layer 224G, and the conductive layer 224B can also be used as light-emitting regions, thereby increasing the aperture ratio of the pixel.
[0409] The layer 128 may be an insulating layer or a conductive layer. Various inorganic insulating materials, organic insulating materials, and conductive materials can be used as appropriate for the layer 128. In particular, the layer 128 is preferably formed using an insulating material, and more preferably using an organic insulating material. For example, the organic insulating material that can be used for the insulating layer 127 described above can be used for the layer 128.
[0410] A protective layer 131 is provided on the light-emitting device 130R, the light-emitting device 130G, and the light-emitting device 130B via an auxiliary electrode 105. The protective layer 131 and the substrate 352 are bonded via an adhesive layer 142. A light-shielding layer 157 is provided on the substrate 352. A solid sealing structure, a hollow sealing structure, or the like can be applied to seal the light-emitting device 130. In FIG. 13 , the space between the substrate 352 and the substrate 351 is filled with the adhesive layer 142, and a solid sealing structure is applied. Alternatively, the space may be filled with an inert gas (such as nitrogen or argon), and a hollow sealing structure may be applied. In this case, the adhesive layer 142 may be provided so as not to overlap with the light-emitting device. Alternatively, the space may be filled with a resin different from the frame-shaped adhesive layer 142.
[0411] 13 shows an example in which the connection portion 140 has a conductive layer 224C obtained by processing the same conductive film as the conductive layers 224R, 224G, and 224B, a conductive layer 151C obtained by processing the same conductive film as the conductive layers 151R, 151G, and 151B, and a conductive layer 152C obtained by processing the same conductive film as the conductive layers 152R, 152G, and 152B. Also, FIG. 13 shows an example in which an insulating layer 156C is provided so as to have a region overlapping with a side surface of the conductive layer 151C.
[0412] The display device 100C is a top-emission type. Light emitted by the light-emitting device is emitted toward the substrate 352. The substrate 352 is preferably made of a material that is highly transparent to visible light. The pixel electrode contains a material that reflects visible light, and the counter electrode (second electrode 102) and the auxiliary electrode 105 contain a material that transmits visible light.
[0413] An insulating layer 211, an insulating layer 213, an insulating layer 215, and an insulating layer 214 are provided over the substrate 351 in this order. A part of the insulating layer 211 functions as a gate insulating layer for each transistor. A part of the insulating layer 213 functions as a gate insulating layer for each transistor. The insulating layer 215 is provided to cover the transistor. The insulating layer 214 is provided to cover the transistor and functions as a planarization layer. Note that the number of gate insulating layers and the number of insulating layers covering the transistors are not limited, and each may be a single layer or two or more layers.
[0414] The insulating layers 211, 213, and 215 are each preferably formed using an inorganic insulating film.
[0415] The insulating layer 214 that functions as a planarizing layer is preferably an organic insulating layer.
[0416] The transistor 201 and the transistor 205 each include a conductive layer 221 functioning as a gate, an insulating layer 211 functioning as a gate insulating layer, a conductive layer 222a and a conductive layer 222b functioning as a source and a drain, a semiconductor layer 231, an insulating layer 213 functioning as a gate insulating layer, and a conductive layer 223 functioning as a gate.
[0417] A connection portion 204 is provided in a region of the substrate 351 where the substrate 352 does not overlap. In the connection portion 204, a source electrode or a drain electrode of the transistor 201 is electrically connected to the FPC 353 through a conductive layer 166 and a connection layer 242. The conductive layer 166 has an example of a stacked structure including a conductive film obtained by processing the same conductive film as the conductive layers 224R, 224G, and 224B, a conductive film obtained by processing the same conductive film as the conductive layers 151R, 151G, and 151B, and a conductive film obtained by processing the same conductive film as the conductive layers 152R, 152G, and 152B. The conductive layer 166 is exposed on the top surface of the connection portion 204. This allows the connection portion 204 and the FPC 353 to be electrically connected via the connection layer 242.
[0418] It is preferable to provide a light-shielding layer 157 on the surface of the substrate 352 facing the substrate 351. The light-shielding layer 157 can be provided between adjacent light-emitting devices, on the connection section 140, on the circuit 356, etc. In addition, various optical members can be arranged on the outside of the substrate 352.
[0419] The substrate 351 and the substrate 352 can be made of the same material as can be used for the substrate 120 .
[0420] The adhesive layer 142 can be made of a material that can be used for the resin layer 122 .
[0421] The connection layer 242 may be an anisotropic conductive film (ACF), an anisotropic conductive paste (ACP), or the like.
[0422] [Display Device 100D] The display device 100D shown in FIG. 14 differs from the display device 100C shown in FIG. 14 mainly in that it is a bottom-emission display device.
[0423] Light emitted from the light-emitting device is emitted toward the substrate 351. A material that is highly transparent to visible light is preferably used for the substrate 351. On the other hand, the light-transmitting property of the material used for the substrate 352 does not matter.
[0424] A light-shielding layer 317 is preferably formed between the substrate 351 and the transistor 201 and between the substrate 351 and the transistor 205. In the example shown in FIG. 14, the light-shielding layer 317 is provided over the substrate 351, the insulating layer 153 is provided over the light-shielding layer 317, and the transistors 201, 205, and the like are provided over the insulating layer 153.
[0425] Light emitting device 130R includes conductive layer 112R, conductive layer 126R on conductive layer 112R, and conductive layer 129R on conductive layer 126R.
[0426] Light emitting device 130B includes conductive layer 112B, conductive layer 126B on conductive layer 112B, and conductive layer 129B on conductive layer 126B.
[0427] The conductive layers 112R, 112B, 126R, 126B, 129R, and 129B are each formed using a material that is highly transparent to visible light. The second electrode 102 is preferably formed using a material that reflects visible light.
[0428] Although the light emitting device 130G is not shown in FIG. 14, the light emitting device 130G is also provided.
[0429] Although FIG. 14 and other figures show an example in which the top surface of the layer 128 has a flat portion, the shape of the layer 128 is not particularly limited.
[0430] [Display Device 100D2] The display device 100D2 shown in Fig. 15 is an example of a bottom-emission type display device that differs from the display device 100D shown in Fig. 15. The display device 100D2 differs from the display device 100D in that it has an organic resin layer 180. Note that in the figure, the reference numerals of the same components as those in Fig. 15 may be omitted, and the description in Fig. 15 can be referred to for details.
[0431] 15B shows a top view layout of a pixel 178 (pixel 178a and pixel 178b) having subpixels 110 (subpixels 110R, 110G, and 110B), and Fig. 15C shows a top view of the organic resin layer 180 in a region where the subpixels 110R and 110G of the pixel 178 are formed. Note that the distance between the light-shielding layers 317 is 110Rw in the light-emitting region of the subpixel 110R.
[0432] As shown in FIG. 15A , the organic resin layer 180 is provided on the insulating layer 214. As shown in the region surrounded by the dashed line in FIG. 15A and in FIG. 15C , the organic resin layer 180 has curved recesses 181 (recesses 181 a and 181 b) at least in the region where the subpixels are formed. Note that the recesses 181 may be provided outside the light-emitting region, such as recess 181 c. Providing recess 181 c refracts light emitted in the region overlapping with the light-shielding layer 317 or light traveling to the region overlapping with the light-shielding layer 317, allowing it to be extracted from the light-emitting region, thereby improving the light-emitting efficiency.
[0433] A plurality of recesses 181 may be formed in a matrix. Recesses 181a and 181b may be provided in contact with each other, or may have a flat surface therebetween.
[0434] 15, the recess has a hexagonal top surface shape (FIG. 15C) and a semicircular cross-sectional shape (FIG. 15A), but may have other shapes as needed. For example, the recess may have a polygonal top surface shape such as a triangle, a quadrangle (including a rectangle and a square), a pentagon, or any other polygon with rounded corners, an ellipse, or a circle.
[0435] An insulating layer containing an organic material can be used as the organic resin layer 180. For example, acrylic resin, polyimide resin, epoxy resin, imide resin, polyamide resin, polyimideamide resin, silicone resin, siloxane resin, benzocyclobutene resin, phenolic resin, precursors of these resins, etc. can be used as the organic resin layer 180. Alternatively, organic materials such as polyvinyl alcohol (PVA), polyvinyl butyral, polyvinylpyrrolidone, polyethylene glycol, polyglycerin, pullulan, water-soluble cellulose, or alcohol-soluble polyamide resin can be used as the organic resin layer 180.
[0436] Furthermore, a photosensitive resin can be used as the organic resin layer 180. A photoresist can be used as the photosensitive resin. The photosensitive resin can be a positive-type material or a negative-type material.
[0437] The organic resin layer 180 may contain a material that absorbs visible light. For example, the organic resin layer 180 itself may be made of a material that absorbs visible light, or the organic resin layer 180 may contain a pigment that absorbs visible light. For example, the organic resin layer 180 may be made of a resin that can be used as a color filter that transmits red, blue, or green light and absorbs other light, or a resin that contains carbon black as a pigment and functions as a black matrix.
[0438] Further, a first electrode 101 is provided on the organic resin layer 180, an organic compound layer 103 is provided on the first electrode 101, and a second electrode 102 is provided on the organic compound layer 103. Ends of the first electrode 101, the organic compound layer 103, and the second electrode 102 may be covered with an insulating layer 127.
[0439] Furthermore, the first electrode 101 formed on the organic resin layer 180 has a recess similar to the recess of the organic resin layer 180. Furthermore, the organic compound layer 103 formed on the first electrode 101 has a recess similar to the recess of the first electrode 101. Furthermore, the second electrode 102 formed on the organic compound layer 103 has a recess similar to the recess of the organic compound layer 103. Furthermore, the auxiliary electrode 105 formed on the second electrode 102 has a recess similar to the recess of the second electrode 102. That is, the recesses of the organic resin layer 180, the first electrode 101, the organic compound layer 103, the second electrode 102, and the auxiliary electrode 105 have a structure in which they overlap one another.
[0440] In addition, a second electrode 102 is provided over the organic compound layer 103 and the insulating layer 127, and an auxiliary electrode 105 is provided over the second electrode 102. A protective layer 131 is provided over the auxiliary electrode 105, and the protective layer 131 is attached to a substrate 352 with an adhesive layer 142 interposed therebetween.
[0441] Although the light emitting device 130G and the light emitting device 130B are not shown in FIG. 15, the light emitting device 130G and the light emitting device 130B are also provided.
[0442] The light-emitting device according to one embodiment of the present invention, which includes the above-described organic resin layer 180, has the structure described in Embodiment 1 or 2. Thus, an organic semiconductor device with low driving voltage and favorable characteristics can be provided.
[0443] [Display Device 100E] The display device 100E shown in FIG. 16 is a modification of the display device 100C shown in FIG. 13, and differs from the display device 100C mainly in that it has colored layers 132R, 132G, and 132B.
[0444] In the display device 100E, the light-emitting device 130 has an area that overlaps one of the colored layers 132R, 132G, and 132B. The colored layers 132R, 132G, and 132B can be provided on the surface of the substrate 352 facing the substrate 351. An end of the colored layer 132R, an end of the colored layer 132G, and an end of the colored layer 132B can overlap the light-shielding layer 157.
[0445] In the display device 100E, for example, the colored layer 132R transmits red light, the colored layer 132G transmits green light, and the colored layer 132B transmits blue light. Note that the display device 100E may be configured such that the colored layers 132R, 132G, and 132B are provided between the protective layer 131 and the adhesive layer 142.
[0446] [Display Device 100E2] The display device 100E2 shown in Fig. 17 is a modified example of the display device 100E shown in Fig. 16, and has microlenses 182 on the colored layers 132R, 132G, and 132B. Note that in the figure, the reference numerals of the same components as those in Fig. 16 may be omitted, and the description in Fig. 16 can be referred to for details.
[0447] 17B shows a top view layout of a pixel 178 (pixel 178a and pixel 178b) having subpixels 110 (subpixels 110R, 110G, and 110B), and Fig. 17C shows a top view of a microlens 182 in a region where the subpixels 110R and 110G of the pixel 178 are formed. Note that the region where the common electrode 155 and the organic compound layer 103 are in contact has a width 110Gw in the light-emitting region of the subpixel 110G.
[0448] 17A has a planarization film 143 provided on a protective layer 131, and colored layers 132R, 132G, and 132B provided on the planarization film 144. The planarization film 144 is provided so as to cover the colored layers 132R, 132G, and 132B. A microlens 182 is provided on the planarization film 144.
[0449] As shown in FIG. 17C, the microlens 182 may be provided for each sub-pixel in the region where the sub-pixels are formed.
[0450] 17C, the top surface shape of the microlens 182 is shown as a hexagon, but other shapes may be used as needed. For example, the top surface shape of the recess may be a polygon such as a triangle, a quadrangle (including a rectangle and a square), a pentagon, or a polygon with rounded corners, an ellipse, or a circle.
[0451] The microlenses 182 can be formed using the same material as the organic resin layer 180 .
[0452] This embodiment mode can be combined with other embodiment modes or examples as appropriate. In addition, in this specification, when a plurality of configuration examples are shown in one embodiment mode, the configuration examples can be combined as appropriate.
[0453] Embodiment 5 In this embodiment, an electronic device according to one embodiment of the present invention will be described.
[0454] The electronic devices of this embodiment include the display device of one embodiment of the present invention in their display portions. The display device of one embodiment of the present invention has high display performance and can easily achieve high definition and high resolution. Therefore, the display device of one embodiment of the present invention can be used in the display portions of various electronic devices.
[0455] Examples of electronic devices include electronic devices with relatively large screens such as television sets, desktop or notebook personal computers, computer monitors, digital signage, large game machines such as pachinko machines, as well as digital cameras, digital video cameras, digital photo frames, mobile phones, portable game machines, personal digital assistants, and sound playback devices.
[0456] In particular, the display device of one embodiment of the present invention can have high resolution and can therefore be suitably used in electronic devices having a relatively small display area. Examples of such electronic devices include wristwatch-type and bracelet-type information terminals (wearable devices), and head-mounted wearable devices such as VR devices (e.g., head-mounted displays), AR glasses-type devices, and MR devices.
[0457] The electronic device of this embodiment may have a sensor (including a function to measure 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 rays).
[0458] An example of a wearable device that can be worn on the head will be described with reference to FIGS. 18A to 18D.
[0459] The electronic device 700A shown in FIG. 18A and the electronic device 700B shown in FIG. 18B each have a pair of display panels 751, a pair of housings 721, a communication unit (not shown), a pair of mounting units 723, a control unit (not shown), an imaging unit (not shown), a pair of optical members 753, a frame 757, and a pair of nose pads 758.
[0460] The display device of one embodiment of the present invention can be applied to the display panel 751. Therefore, the electronic device can be highly reliable.
[0461] Each of the electronic device 700A and the electronic device 700B can project an image displayed on the display panel 751 onto a display area 756 of the optical member 753. Because the optical member 753 is translucent, the user can see the image displayed in the display area superimposed on a transmitted image visible through the optical member 753.
[0462] The electronic device 700A and the electronic device 700B may be provided with a camera capable of capturing an image in front of them as an imaging unit. Furthermore, the electronic device 700A and the electronic device 700B may each be provided with an acceleration sensor such as a gyro sensor, thereby detecting the orientation of the user's head and displaying an image corresponding to that orientation in the display area 756.
[0463] The communication unit has a wireless communication device, and can supply, for example, a video signal via the wireless communication device. Note that instead of or in addition to the wireless communication device, a connector to which a cable through which a video signal and a power supply potential can be connected may be provided.
[0464] Furthermore, the electronic device 700A and the electronic device 700B are provided with batteries, which can be charged wirelessly and / or wired.
[0465] The housing 721 may be provided with a touch sensor module.
[0466] Various touch sensors can be used as the touch sensor module. For example, various types of touch sensors can be used, such as a capacitance type, a resistive film type, an infrared type, an electromagnetic induction type, a surface acoustic wave type, or an optical type. In particular, it is preferable to use a capacitance type or an optical type sensor in the touch sensor module.
[0467] The electronic device 800A shown in Figure 18C and the electronic device 800B shown in Figure 18D each have a pair of display units 820, a housing 821, a communication unit 822, a pair of mounting units 823, a control unit 824, a pair of imaging units 825, and a pair of lenses 832.
[0468] The display device of one embodiment of the present invention can be applied to the display portion 820. Therefore, the electronic device can have high reliability.
[0469] The display unit 820 is provided inside the housing 821 at a position that can be viewed through the lens 832. In addition, by displaying different images on the pair of display units 820, it is possible to perform three-dimensional display using parallax.
[0470] It is preferable that electronic device 800A and electronic device 800B each have a mechanism that allows the left and right positions of lens 832 and display unit 820 to be adjusted so that they are optimally positioned according to the position of the user's eyes.
[0471] The mounting portion 823 allows the user to mount the electronic device 800A or the electronic device 800B on the head.
[0472] The imaging unit 825 has a function of acquiring external information. Data acquired by the imaging unit 825 can be output to the display unit 820. An image sensor can be used for the imaging unit 825. Furthermore, multiple cameras may be provided to support multiple angles of view, such as telephoto and wide-angle.
[0473] The electronic device 800A may have a vibration mechanism that functions as a bone conduction earphone.
[0474] The electronic device 800A and the electronic device 800B may each have an input terminal to which a cable can be connected for supplying a video signal from a video output device or the like and power for charging a battery provided in the electronic device.
[0475] The electronic device of one embodiment of the present invention may have a function of wirelessly communicating with the earphone 750 .
[0476] 18B includes earphone unit 727. A portion of the wiring connecting earphone unit 727 and the control unit may be disposed inside housing 721 or attachment unit 723.
[0477] 18D includes an earphone unit 827. For example, the earphone unit 827 and the control unit 824 may be configured to be connected to each other by wire.
[0478] As described above, as electronic devices according to one embodiment of the present invention, both glasses-type devices (such as the electronic devices 700A and 700B) and goggle-type devices (such as the electronic devices 800A and 800B) are suitable.
[0479] The electronic device 6500 shown in FIG. 19A is a portable information terminal that can be used as a smartphone.
[0480] The electronic device 6500 includes a housing 6501, a display portion 6502, a power button 6503, a button 6504, a speaker 6505, a microphone 6506, a camera 6507, a light source 6508, and the like. The display portion 6502 has a touch panel function.
[0481] The display device of one embodiment of the present invention can be applied to the display portion 6502. Therefore, the electronic device can have high reliability.
[0482] FIG. 19B is a schematic cross-sectional view including the end of the housing 6501 on the microphone 6506 side.
[0483] A light-transmitting protective member 6510 is provided on the display surface side of the housing 6501, and a display panel 6511, an optical member 6512, a touch sensor panel 6513, a printed circuit board 6517, a battery 6518, etc. are arranged in the space surrounded by the housing 6501 and the protective member 6510.
[0484] A display panel 6511, an optical member 6512, and a touch sensor panel 6513 are fixed to the protective member 6510 by adhesive layers (not shown).
[0485] In a region outside the display portion 6502, a part of the display panel 6511 is folded back, and an FPC 6515 is connected to the folded back part. An IC 6516 is mounted on the FPC 6515. The FPC 6515 is connected to a terminal provided on a printed circuit board 6517.
[0486] The display device of one embodiment of the present invention can be applied to the display panel 6511. Therefore, an extremely lightweight electronic device can be realized. Furthermore, since the display panel 6511 is extremely thin, a large-capacity battery 6518 can be mounted thereon while keeping the thickness of the electronic device small. Furthermore, by folding back a part of the display panel 6511 and arranging a connection portion with the FPC 6515 on the back side of the pixel portion, an electronic device with a narrow frame can be realized.
[0487] 19C shows an example of a television set. A television set 7100 has a display portion 7000 built into a housing 7171. Here, the housing 7171 is supported by a stand 7173.
[0488] The display device of one embodiment of the present invention can be applied to the display portion 7000. Therefore, the electronic device can have high reliability.
[0489] The television set 7100 shown in FIG. 19C can be operated using an operation switch provided on the housing 7171 and a separate remote control 7151 .
[0490] 19D shows an example of a laptop personal computer 7200. The laptop personal computer 7200 includes a housing 7211, a keyboard 7212, a pointing device 7213, and an external connection port 7214. The housing 7211 includes a display portion 7000.
[0491] The display device of one embodiment of the present invention can be applied to the display portion 7000. Therefore, the electronic device can have high reliability.
[0492] 19E and 19F show an example of digital signage.
[0493] 19E includes a housing 7301, a display portion 7000, and a speaker 7303. The digital signage 7300 may further include an LED lamp, operation keys (including a power switch or an operation switch), a connection terminal, various sensors, a microphone, and the like.
[0494] 19F shows a digital signage 7400 attached to a cylindrical pillar 7401. The digital signage 7400 has a display unit 7000 provided along the curved surface of the pillar 7401.
[0495] 19E and 19F, the display device of one embodiment of the present invention can be applied to the display portion 7000. Therefore, the electronic device can have high reliability.
[0496] The larger the display unit 7000, the more information can be provided at one time. Also, the larger the display unit 7000, the more easily it will attract people's attention, which can increase the advertising effectiveness of, for example, advertisements.
[0497] Furthermore, as shown in Figures 19E and 19F, it is preferable that the digital signage 7300 or the digital signage 7400 be able to wirelessly connect with an information terminal 7311 or an information terminal 7411 such as a smartphone carried by a user.
[0498] The electronic device shown in Figures 20A to 20G has a housing 9000, a display unit 9001, a speaker 9003, operation keys 9005 (including a power switch or an operation switch), a connection terminal 9006, a sensor 9007 (including a function to measure force, displacement, position, speed, 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 rays), a microphone 9008, etc.
[0499] 20A to 20G have various functions, such as a function to display various information (still images, videos, text images, etc.) on a display unit, a touch panel function, a function to display a calendar, date, time, etc., a function to control processing using various software (programs), a wireless communication function, a function to read and process programs or data recorded on a recording medium, etc.
[0500] The electronic devices shown in FIGS. 20A to 20G will be described in detail below.
[0501] FIG. 20A is a perspective view showing a mobile information terminal 9171. The mobile information terminal 9171 can be used as, for example, a smartphone. Note that the mobile information terminal 9171 may be provided with a speaker 9003, a connection terminal 9006, a sensor 9007, or the like. The mobile information terminal 9171 can display text and image information on multiple surfaces. FIG. 20A shows an example in which three icons 9050 are displayed. Information 9051, indicated by a dashed rectangle, can also be displayed on another surface of the display unit 9001. Examples of the information 9051 include notifications of incoming emails, SNS messages, phone calls, etc., the title of the email or SNS message, the sender's name, the date and time, the remaining battery level, and radio wave intensity. Alternatively, the icon 9050 or the like may be displayed in the position where the information 9051 is displayed.
[0502] 20B is a perspective view showing a mobile information terminal 9172. The mobile information terminal 9172 has a function of displaying information on three or more surfaces of the display portion 9001. Here, an example is shown in which information 9052, information 9053, and information 9054 are displayed on different surfaces. For example, a user can check information 9053 displayed in a position that can be observed from above the mobile information terminal 9172 while the mobile information terminal 9172 is stored in a breast pocket of clothes.
[0503] 20C is a perspective view showing a tablet terminal 9173. The tablet terminal 9173 is capable of executing various applications such as mobile phone calls, e-mail, document browsing and creation, music playback, internet communication, and computer games, for example. The tablet terminal 9173 has a display unit 9001, a camera 9002, a microphone 9008, and a speaker 9003 on the front side of a housing 9000, operation keys 9005 as operation buttons on the left side of the housing 9000, and a connection terminal 9006 on the bottom.
[0504] FIG. 20D is a perspective view showing a wristwatch-type mobile information terminal 9200. The mobile information terminal 9200 can be used as, for example, a smart watch (registered trademark). The display surface of the display unit 9001 is curved, and display can be performed along the curved display surface. The mobile information terminal 9200 can also perform hands-free calling by communicating with, for example, a headset capable of wireless communication. The mobile information terminal 9200 can also perform data transmission and charging with another information terminal through a connection terminal 9006. Note that charging may be performed by wireless power supply.
[0505] 20E to 20G are perspective views showing a foldable mobile information terminal 9201. Also, FIG. 20E is a perspective view of the mobile information terminal 9201 in an unfolded state, FIG. 20G is a perspective view of the mobile information terminal 9201 in a folded state, and FIG. 20F is a perspective view of a state in the process of changing from one of FIG. 20E and FIG. 20G to the other. The mobile information terminal 9201 is highly portable when folded, and has a seamless, wide display area when unfolded, providing excellent visibility of the display. The display portion 9001 of the mobile information terminal 9201 is supported by three housings 9000 connected by hinges 9055. For example, the display portion 9001 can be bent with a curvature radius of 0.1 mm or more and 150 mm or less.
[0506] This embodiment mode can be combined with other embodiment modes or examples as appropriate. In addition, in this specification, when a plurality of configuration examples are shown in one embodiment mode, the configuration examples can be combined as appropriate.
[0507] In this example, a detailed description will be given of a manufacturing method and characteristics of a light-emitting device 1 which is a light-emitting device according to one embodiment of the present invention and a comparative light-emitting device 1. The structural formulae of main compounds used in this example are shown below.
[0508]
[0509] (Method of manufacturing light-emitting device 1) First, on a glass substrate, 100 nm of silver was deposited as a reflective electrode from the substrate side, and 85 nm of indium tin oxide containing silicon oxide (ITSO) was deposited as a transparent electrode by sputtering to form a first electrode 101 measuring 2 mm x 2 mm. The transparent electrode functions as an anode, and is considered to be the first electrode 101 together with the reflective electrode.
[0510] Next, as a pretreatment for forming a light-emitting device on the substrate, the surface of the substrate was washed with water and baked at 200° C. for 1 hour.
[0511] After that, about 1 × 10 −4 The substrate was introduced into a vacuum deposition apparatus whose inside had been reduced in pressure to 100 Pa, and vacuum baked at 170° C. for 30 minutes in a heating chamber of the vacuum deposition apparatus, and then the substrate was allowed to cool for about 30 minutes.
[0512] Next, the substrate was fixed to a holder provided in a vacuum deposition apparatus so that the surface on which the first electrode 101 was formed faced downward. N-(biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9-dimethyl-9H-fluoren-2-amine (abbreviation: PCBBiF) represented by the above structural formula (i) and a material (OCHD-003) having a molecular weight of 672 and containing fluorine and having electron acceptor properties were co-deposited by a deposition method to a thickness of 10 nm on the inorganic insulating film and the first electrode 101 in a weight ratio of 1:0.03 (= PCBBiF:OCHD-003).
[0513] On the hole injection layer 111, PCBBiF was evaporated to a thickness of 55 nm to form a hole transport layer.
[0514] Subsequently, on the hole transport layer, 8-(1,1':4',1''-terphenyl-3-yl)-4-[3-(dibenzothiophen-4-yl)phenyl]-[1]benzofuro[3,2-d]pyrimidine (abbreviation: 8mpTP-4mDBtPBfpm) represented by the above structural formula (ii), 9-(2-naphthyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole (abbreviation: βNCCP) represented by the above structural formula (iii), and [2-d 3-methyl-8-(2-pyridinyl-κN)benzofuro[2,3-b]pyridine-κC]bis[2-(5-d 3 [5-methyl-2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: Ir(5mppy-d 3 ) 2 (mbfpypy-d 3 )) in a weight ratio of 0.5:0.5:0.1 (=8mpTP-4mDBtPBfpm:βNCCP:Ir(5mppy-d 3 ) 2 (mbfpypy-d 3 )) to form a 40 nm thick light-emitting layer.
[0515] After that, 2-{3-[3-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}dibenzo[f,h]quinoxaline (abbreviation: 2mPCCzPDBq) represented by the above structural formula (v) was evaporated to a thickness of 15 nm to form an electron transport layer, and then 2,2′-(2,2′-bipyridine-6,6′-diyl)bis(4-phenylbenzo[h]quinazoline) (abbreviation: 6,6′(P-Bqn)2BPy) represented by the above structural formula (vi), 4,7-di(2,3,3a,4,5,6,7,7a-octahydro-1H-isoindol-2-yl)-1,10-phenanthroline (abbreviation: Hid2Phen) represented by the above structural formula (vii), and lithium oxide (Li 2 O) in a volume ratio of 0.5:0.5:0.02 (=6,6'(P-Bqn)2BPy:Hid2Phen:Li 2 O), a 5 nm thick electron injection layer was formed.
[0516] Next, copper phthalocyanine represented by the above structural formula (viii) was vapor-deposited to a thickness of 2 nm to form an electron relay layer, and then PCBBiF and molybdenum oxide (VI) (MoO 3 ) in a weight ratio of 1:0.5 (= PCBBiF:MoO 3 ) to form a P-type layer having a thickness of 15 nm.
[0517] After forming the P-type layer, a second electrode was formed by sputtering indium tin oxide (ITO) to a thickness of 40 nm. After forming the second electrode, it was exposed to the atmosphere for 1 hour. After that, about 1×10 −4 The substrate was placed in a vacuum deposition apparatus whose interior had been reduced in pressure to 100 Pa, and heated at 100° C. for 1 hour in a heating chamber within the vacuum deposition apparatus.
[0518] Then, a 70 nm thick ITO film was formed by sputtering to form a cap layer. The cap layer can also be considered as the second electrode. That is, the 40 nm thick ITO film formed before air exposure and the 70 nm thick ITO film formed after air exposure can be considered as the second electrode, and the second electrode also functions as a cap layer.
[0519] Next, in a glove box with a nitrogen atmosphere, the light-emitting device was sealed with a glass substrate to prevent it from being exposed to the atmosphere (a UV-curable sealant was applied around the element, UV was irradiated only onto the sealant without irradiating the light-emitting device, and heat treatment was performed at 80°C under atmospheric pressure for 1 hour), thereby forming light-emitting device 1.
[0520] (Method of Fabricating Comparative Light-Emitting Device 1) Comparative light-emitting device 1 was fabricated in the same manner as light-emitting device 1, except that the second electrode of light-emitting device 1 was formed to a thickness of 110 nm, and then sealed without exposure to the atmosphere or heating. The second electrode of comparative light-emitting device 1 also functions as a cap layer.
[0521] The device structures of the light-emitting device 1 and the comparative light-emitting device 1 are shown below.
[0522]
[0523] The luminance-current density characteristics of the light-emitting device 1 and the comparative light-emitting device 1 are shown in FIG. 23, the luminance-voltage characteristics in FIG. 24, the current efficiency-current density characteristics in FIG. 25, the current density-voltage characteristics in FIG. 26, and the electroluminescence spectrum in FIG. 27. 2 The main characteristics of each light-emitting device in the vicinity are summarized in the table below.
[0524]
[0525] 23 to 27 and Table 6, the light-emitting device 1 of one embodiment of the present invention showed results that were comparable to or better than those of the comparative light-emitting device 1, which was not subjected to air exposure and heating. Since processing by photolithography always includes an air exposure step, it was found that the light-emitting device of one embodiment of the present invention is resistant to processing by photolithography and is capable of maintaining good characteristics even after processing by photolithography.
[0526] 100A: display device, 100B: display device, 100C: display device, 100E: display device, 100D: display device, 100: insulator, 101a: first electrode, 101b: first electrode, 101c: first electrode, 101d: first electrode, 101: first electrode, 101R: first electrode, 101G: first electrode, 101B: first electrode, 102: second electrode, 102b: second electrode, 102d: second electrode, 102c: second electrode, 102B: second electrode, 102R: second electrode, 102a: second electrode, 102G: second electrode, 102Gf: conductive film, 102Bf: conductive conductive film, 102Rf: conductive film, 103a: organic compound layer, 103B: organic compound layer, 103b: organic compound layer, 103Bf: organic compound film, 103c: organic compound layer, 103d: organic compound layer, 103G: organic compound layer, 103Gf: organic compound film, 103R: organic compound layer, 103Rf: organic compound film, 103: organic compound layer, 105: auxiliary electrode, 106: insulating layer, 110B: sub-pixel, 110G: sub-pixel, 110R: sub-pixel, 110: sub-pixel, 111a: hole injection layer, 111b: hole injection layer, 111c: hole injection layer, 111d: hole injection layer, 111: hole injection layer, 112: hole transport layer, 112a: hole transport layer, 112b: hole transport layer, 112c_1: hole transport layer, 112c_2: hole transport layer, 112d_1: hole transport layer, 112d_2: hole transport layer, 112R: conductive layer, 112B: conductive layer, 113: light emitting layer, 113a: light emitting layer, 113b: light emitting layer, 113c_1: light emitting layer, 113c_2: light emitting layer, 113d_1: light emitting layer, 113d_2: light emitting layer, 114: electron transport layer, 114a: electron transport layer, 114b: electron transport layer, 114c_1: electron transport layer, 114c_2: electron transport layer, 114d_1: electron transport layer, 11 4d_2: electron transport layer, 115: electron injection layer, 115a: electron injection layer, 115b: electron injection layer, 115c: electron injection layer, 115d: electron injection layer, 116c: intermediate layer, 116d: intermediate layer, 117: P-type layer, 117c: P-type layer, 117d: P-type layer, 118: electron relay layer, 118c: electron relay layer, 118d: electron relay layer, 119: N-type layer, 119c: N-type layer, 119d: N-type layer, 120: substrate, 122: resin layer, 124a: pixel, 124b: pixel, 125f: inorganic insulating film, 125: inorganic insulating layer, 126R: conductive layer, 126B: conductive layer, 127a: insulating layer,127f: insulating film, 127: insulating layer, 128: layer, 129R: conductive layer, 129B: conductive layer, 130a: light-emitting device, 130B: light-emitting device, 130b: light-emitting device, 130c: light-emitting device, 130d: light-emitting device, 130G: light-emitting device, 130R: light-emitting device, 130: light-emitting device, 131: protective layer, 132B: colored layer, 132G: colored layer, 132R: colored layer, 140: connecting portion, 141: region, 142: adhesive layer, 151B: conductive layer, 151C: conductive layer, 151f: conductive film, 151G: conductive layer, 151R: conductive layer, 151: conductive layer, 152 B: conductive layer, 152C: conductive layer, 152f: conductive film, 152G: conductive layer, 152R: conductive layer, 152: conductive layer, 153: insulating layer, 155: common electrode, 156B: insulating layer, 156C: insulating layer, 156f: insulating film, 156G: insulating layer, 156R: insulating layer, 156: insulating layer, 157: light-shielding layer, 158: sacrificial layer, 158B: sacrificial layer, 158Bf: sacrificial film, 158G: sacrificial layer, 158Gf: sacrificial film, 158R: sacrificial layer, 158Rf: sacrificial film, 159: mask layer, 159B: mask layer, 159Bf: mask film, 159G: mask layer, 159Gf: mask film, 159R: mask mask layer, 159Rf: mask film, 166: conductive layer, 171: insulating layer, 172: conductive layer, 173: insulating layer, 174: insulating layer, 175: insulating layer, 176: plug, 177: pixel portion, 178: pixel, 178a: pixel, 178b: pixel, 179: conductive layer, 190B: resist mask, 190G: resist mask, 190R: resist mask, 191: resist mask, 201: transistor, 204: connection portion, 205: transistor, 211: insulating layer, 213: insulating layer, 214: insulating layer, 215: insulating layer, 221: conductive layer, 222a: conductive layer, 222b: conductive layer, 2 23: conductive layer, 224B: conductive layer, 224C: conductive layer, 224G: conductive layer, 224R: conductive layer, 231: semiconductor layer, 240: capacitor, 241: conductive layer, 242: connection layer, 243: insulating layer, 245: conductive layer, 254: insulating layer, 255: insulating layer, 256: plug, 261: insulating layer, 271: plug, 280: display module, 281: display section, 282: circuit section, 283a: pixel circuit, 283: pixel circuit section, 284a: pixel, 284: pixel section, 285: terminal section, 286: wiring section, 290: FPC, 291: substrate, 292: substrate, 301: substrate, 310: transistor,311: conductive layer, 312: low resistance region, 313: insulating layer, 314: insulating layer, 315: element isolation layer, 317: light-shielding layer, 351: substrate, 352: substrate, 353: FPC, 354: IC, 355: wiring, 356: circuit, 501: first electrode, 501c: first light-emitting unit, 501d: first light-emitting unit, 502: second electrode, 502c: second light-emitting unit, 502d: second light-emitting unit, 511: first light-emitting unit, 512: second light-emitting unit, 513: intermediate layer, 700A: electronic device, 700B: electronic device, 721: housing, 723 : Mounting portion, 727: Earphone portion, 750: Earphone, 751: Display panel, 753: Optical member, 756: Display area, 757: Frame, 758: Nose pad, 800A: Electronic device, 800B: Electronic device, 820: Display portion, 821: Housing, 822: Communication portion, 823: Mounting portion, 824: Control portion, 825: Imaging portion, 827: Earphone portion, 832: Lens, 1000: Insulator, 6500: Electronic device, 6501: Housing, 6502: Display portion, 6503: Power button, 6504: Button, 6505: Speaker, 6506: Microphone, 6507: Camera, 6508: light source, 6510: protective member, 6511: display panel, 6512: optical member, 6513: touch sensor panel, 6515: FPC, 6516: IC, 6517: printed circuit board, 6518: battery, 7000: display unit, 7100: television device, 7151: remote control device, 7171: housing, 7173: stand, 7200: notebook personal computer, 7211: housing, 7212: keyboard, 7213: pointing device, 7214: external connection port, 7300: digital signage, 7301: housing, 73 03: speaker, 7311: information terminal, 7400: digital signage, 7401: pillar, 7411: information terminal, 9000: housing, 9001: display unit, 9002: camera, 9003: speaker, 9005: operation keys, 9006: connection terminal, 9007: sensor, 9008: microphone, 9050: icon, 9051: information, 9052: information, 9053: information, 9054: information, 9055: hinge, 9171: mobile information terminal, 9172: mobile information terminal, 9173: tablet terminal, 9200: mobile information terminal, 9201: mobile information terminal,
Claims
A light-emitting device having a first electrode, a second electrode, and an organic compound layer formed on a first insulating layer, the first electrode is formed in contact with the first insulating layer, the organic compound layer is located between the first electrode and the second electrode, the second electrode and the organic compound layer are separated from at least one of a plurality of other light-emitting devices adjacent to the light-emitting device; when viewed from a direction substantially perpendicular to a surface of the first insulating layer on which the first electrode is formed, an outline of the second electrode and an outline of the organic compound layer substantially coincide with each other; the organic compound layer has a light-emitting layer and an electron injection layer, the electron injection layer is a mixed layer of a metal oxide and a first organic compound, The light-emitting device, wherein the first organic compound is an organic compound having a phenanthroline ring having an electron-donating group. In claim 1, the organic compound layer has a P-type layer between the electron injection layer and the second electrode, The P-type layer comprises a third organic compound having a hole transporting property, and a fourth organic compound having at least one of a halogen group and a cyano group, or a second metal oxide. a first electrode group formed on the same insulating surface; a second electrode group facing the first electrode group; a first layer group located between the first electrode group and the second electrode group, The light emitting device comprises: a first electrode, a second electrode, and a first layer; The first electrode is one of the first electrode group, the first electrode is independent for each of the plurality of light-emitting devices; the first layer is one of the first group of layers, the first layer is independent for each of the plurality of light-emitting devices; the second electrode is one of the second layer group, the second electrode is independent for each of the plurality of light-emitting devices; the second electrode and the first layer overlap the first electrode; the first layer has a light-emitting layer and an electron-injecting layer, the electron injection layer is a mixed layer of a metal oxide and a first organic compound, the first organic compound is an organic compound having a phenanthroline ring having an electron-donating group, A light-emitting device, wherein the distance between the first layer of the light-emitting device and a first layer of another light-emitting device adjacent to the light-emitting device is 0.5 μm or more and 5 μm or less. In claim 2, the first layer has a P-type layer between the electron injection layer and the second electrode; The P-type layer comprises a third organic compound having a hole transporting property, and a fourth organic compound having at least one of a halogen group and a cyano group, or a second metal oxide. In claim 3, When viewed from a direction substantially perpendicular to the insulating surface, the outline of the second electrode and the outline of the first layer substantially coincide with each other. In claim 3, A light-emitting device, wherein an end portion of the second electrode in a cross section and an end portion of the first layer in a cross section are aligned in a direction substantially perpendicular to the insulating surface. In any one of claims 1 to 6, The light-emitting device, wherein the metal oxide is an oxide containing an element of any one of Groups 1, 2, 3, 11, and 13. In any one of claims 1 to 6, The minimum value of the electrostatic potential of the first organic compound is such that the threshold of the electron density distribution in the atomic unit system is 0.0004 e / a 0 3 In the case where h A light-emitting device that is: In any one of claims 1 to 6, A light-emitting device, wherein the phenanthroline ring is a 1,10-phenanthroline ring and has the electron-donating group at at least one of the 4- and 7-positions. In any one of claims 1 to 6, The electron donating group is The light-emitting device may include one or more of an alkyl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, and a heterocyclic amino group. In any one of claims 1 to 6, the phenanthroline ring is a 1,10-phenanthroline ring and has the electron-donating group at at least one of the 4-position and the 7-position; The electron donating group is The light-emitting device may include one or more of an alkyl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, and a heterocyclic amino group. In any one of claims 1 to 6, A light-emitting device, wherein the first organic compound has an acid dissociation constant pKa of 8 or more. In any one of claims 1 to 6, The light-emitting device wherein the electron injection layer further comprises a second organic compound. In claim 13, The light-emitting device, wherein the second organic compound is an organic compound having a π-electron-deficient heteroaromatic ring. In claim 14, A light-emitting device, wherein the second organic compound has a glass transition temperature of 100° C. or higher. In any one of claims 1 to 6, The electron injection layer has a spin density of 5×10 as measured by electron spin resonance. 16 spins / cm 3 A light-emitting device that is more than A light emitting device having a plurality of light emitting devices, The plurality of light-emitting devices are each a light-emitting device according to any one of claims 1 to 6, each of the plurality of light-emitting devices has an organic compound layer between the first electrode and the second electrode, the organic compound layer including the light-emitting layer and the electron injection layer; The second electrode and the organic compound layer of each of the plurality of light-emitting devices are independent from one another.
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