JP7493931B2 - Organic EL element, organic EL display panel, and method for manufacturing organic EL element - Google Patents

Description

This disclosure relates to improving the luminous efficiency and lifetime of organic EL elements that use fluorescent materials as luminescent materials.

In recent years, displays that use organic EL elements have become more common.

Organic EL elements have a structure in which at least a light-emitting layer is sandwiched between an anode and a cathode. In the light-emitting layer, the energy of excitons generated by the recombination of electrons and holes is converted into light. In organic semiconductors, there are two types of excitons (excited states): singlet excitons and triplet excitons, depending on the spin state of the electrons. In so-called fluorescent materials, the energy of singlet excitons is converted into light.

Conventionally, in order to improve the luminous efficiency of organic EL elements, various efforts have been made, such as adjusting the balance between electrons and holes (see, for example, Patent Document 1) and using phosphorescent materials that emit light due to triplet excitons (see, for example, Patent Document 2).

JP 2008-187205 A JP 2010-171368 A

4A, the hole density is lower near the interface of the light-emitting layer 17 with the hole transport layer 16 than near the interface of the light-emitting layer 17 with the first electron transport layer 18, and therefore the high electron density near the interface of the light-emitting layer 17 with the hole transport layer 16 is considered to be the cause of the high recombination rate near the interface of the light-emitting layer 17 with the hole transport layer 16. Therefore, if the electron injection barrier Eg(htl) from the light-emitting layer 17 to the hole transport layer 16 is not high, electrons will flow from the light-emitting layer 17 to the hole transport layer 16, which will not only reduce the luminous efficiency but also may accelerate the deterioration of functional materials such as the hole transport layer 16 and the hole injection layer 15 due to electrons and excitons.
An object of the present disclosure is to provide an organic EL element capable of suppressing outflow of electrons from the light-emitting layer to the functional layer, thereby preventing a decrease in light-emitting efficiency and deterioration of functional materials.

An organic EL element according to one embodiment of the present disclosure is an organic EL element including an anode, a functional layer, an emitting layer, and a cathode stacked in this order, the emitting layer and the functional layer being in contact with each other, the hole mobility of the emitting layer being higher than the electron mobility of the emitting layer, the lowest unoccupied molecular orbital (LUMO) level of a functional material contained in the functional layer being 0.3 eV or higher than the LUMO level of a functional material contained in the emitting layer, and the recombination constant of electrons and holes in the emitting layer being 1/100 or more of the Langevin recombination coefficient .

In this specification, a high LUMO level or highest occupied molecular orbital (HOMO) level means that the difference between that level and the vacuum level of electrons is small, i.e., the potential energy of electrons at that level is large.

According to an organic EL element according to one aspect of the present disclosure, it is possible to increase the exciton density in the region on the cathode side of the light-emitting layer and suppress the outflow of electrons from the light-emitting layer to the functional layer. Therefore, it is possible to improve the luminous efficiency of the light-emitting layer while suppressing the deterioration of the functional material of the functional layer due to electrons and excitons, and it is expected that the life of the organic EL element will be extended.

1 is a cross-sectional view illustrating a schematic configuration of an organic EL element 1 according to an embodiment. FIG. 2 is a simplified schematic diagram showing band diagrams of a hole transport layer, a light emitting layer, and a first electron transport layer in an example. FIG. 2 is a simplified schematic diagram showing the relationship between band diagrams of a hole transport layer, a light emitting layer, and a first electron transport layer and recombination positions of electrons and holes in Examples and Comparative Examples. 13 shows a recombination probability distribution of electrons and holes in a hole transport layer, a light emitting layer, and a first electron transport layer according to a comparative example. 1A is a graph showing the relationship between the barrier for electron injection from the light-emitting layer to the hole transport layer and the recombination efficiency for each recombination constant of the light-emitting layer, and FIG. 1B is a graph showing the relationship between the barrier for electron injection from the light-emitting layer to the hole transport layer and the generation efficiency of singlet excitons for each recombination constant of the light-emitting layer. 1A is a graph showing the relationship between the barrier for electron injection from the light-emitting layer to the hole transport layer and the recombination efficiency for each recombination constant of the light-emitting layer; FIG. 1B is a graph showing the relationship between the recombination constant of the light-emitting layer and the recombination efficiency for each barrier for electron injection from the light-emitting layer to the hole transport layer; and FIG. 1C is a graph showing the relationship between the recombination constant of the light-emitting layer and the generation efficiency of singlet excitons for each barrier for electron injection from the light-emitting layer to the hole transport layer. 1A and 1B are partial cross-sectional views each showing a schematic diagram of a part of a manufacturing process of an organic EL element according to an embodiment, in which (a) shows a state in which a TFT layer is formed on a substrate, (b) shows a state in which an interlayer insulating layer is formed on a substrate, (c) shows a state in which a pixel electrode material is formed on the interlayer insulating layer, (d) shows a state in which a pixel electrode is formed, and (e) shows a state in which a partition material layer is formed on the interlayer insulating layer and the pixel electrode. 1A is a partial cross-sectional view showing a schematic diagram of a part of a manufacturing process of an organic EL element according to an embodiment, in which (a) shows a state in which a partition wall is formed, (b) shows a state in which a hole injection layer is formed on a pixel electrode, and (c) shows a state in which a hole transport layer is formed on the hole injection layer. 1A and 1B are partial cross-sectional views each showing a schematic diagram of a part of a manufacturing process of an organic EL element according to an embodiment, in which (a) shows a state in which a light-emitting layer is formed on a hole-transporting layer, (b) shows a state in which a first electron-transporting layer is formed on the light-emitting layer and the partition layer, and (c) shows a state in which a second electron-transporting layer is formed on the first electron-transporting layer. 1A and 1B are partial cross-sectional views each showing a schematic diagram of a part of a manufacturing process of an organic EL element according to an embodiment, in which (a) shows a state in which an electron injection layer is formed on a second electron transport layer, (b) shows a state in which a counter electrode is formed on the electron injection layer, and (c) shows a state in which a sealing layer is formed on the counter electrode. 4 is a flowchart showing a manufacturing process of the organic EL element according to the embodiment. 1 is a block diagram showing a configuration of an organic EL display device including an organic EL element according to an embodiment.

<<How one aspect of the present disclosure was arrived at>>
In order to use an organic EL element as a light-emitting element, it is essential to generate excitons that are the initial state of light emission. Therefore, in the past, the hole injection from the hole transport layer to the light-emitting layer and the electron injection from the electron transport layer to the light-emitting layer have been improved, and the carrier density in the light-emitting layer has been improved to increase the probability of recombination of electrons and holes. In addition, as a configuration for further improving the carrier density in the light-emitting layer, a functional layer is selected in which the HOMO (Highest Occupied Molecular Orbital) level of the electron transport layer and/or the LUMO (Lowest Unoccupied Molecular Orbital) level of the hole transport layer are adjusted so that hole leakage from the light-emitting layer to the electron transport layer and electron leakage from the light-emitting layer to the hole transport layer can be suppressed. This is because such a configuration can improve the carrier density in the light-emitting layer and increase the probability of recombination of electrons and holes.

Excitons in organic materials exist in two types, singlet excitons and triplet excitons, depending on the spin state of the electrons. As mentioned above, in fluorescent materials, singlet excitons contribute to light emission, while triplet excitons do not. On the other hand, the probability of generating singlet excitons and triplet excitons is approximately 1:3, making it an issue to improve the density of singlet excitons.

In fluorescent materials with low luminous efficiency, particularly blue-emitting materials with short emission wavelengths, the use of the triplet-triplet fusion (TTF) phenomenon, in which multiple triplet excitons collide to generate singlet excitons, has been considered as a way to increase the density of singlet excitons. To utilize TTF, it is necessary to increase the density of triplet excitons; in other words, it is necessary to increase the exciton density by narrowing the recombination region of electrons and holes.

One method for narrowing the recombination region of electrons and holes is to localize the recombination region near the interface of either the hole transport layer side or the electron transport layer side of the light-emitting layer by adjusting the magnitude relationship between the mobility of electrons and the mobility of holes in the light-emitting layer.

However, the inventors found that even when the recombination region is localized near the interface of either the hole transport layer side or the electron transport layer side of the light-emitting layer, the carriers of the electron or hole that are injected in smaller amounts pass through the light-emitting layer without recombining, and the degradation of the functional material in the functional layers other than the light-emitting layer may be accelerated by carriers or excitons.

Therefore, the inventors investigated technology to prevent the deterioration of functional materials caused by carriers passing through the light-emitting layer, and arrived at the aspect of the present disclosure.

<Mode of Disclosure>
An organic EL element according to one embodiment of the present disclosure is an organic EL element including an anode, a functional layer, an emitting layer, and a cathode stacked in this order, the emitting layer and the functional layer being in contact with each other, the hole mobility of the emitting layer being greater than the electron mobility of the emitting layer, and the lowest unoccupied molecular orbital (LUMO) level of a functional material contained in the functional layer being 0.3 eV or more higher than the LUMO level of the functional material contained in the emitting layer.

A method for manufacturing an organic EL element according to one aspect of the present disclosure includes preparing a substrate, forming a pixel electrode above the substrate, forming a functional layer above the pixel electrode, forming a light-emitting layer containing a fluorescent material as a light-emitting material on the functional layer, and forming a cathode above the light-emitting layer, wherein a hole mobility of the light-emitting layer is greater than an electron mobility of the light-emitting layer, and a lowest unoccupied molecular orbital (LUMO) level of a functional material contained in the functional layer is 0.3 eV or more higher than a LUMO level of a functional material contained in the light-emitting layer.

According to an organic EL element or a method for manufacturing an organic EL element according to one embodiment of the present disclosure, the exciton density in the region on the cathode side of the light-emitting layer can be increased, and the outflow of electrons from the light-emitting layer to the functional layer can be suppressed. Therefore, the light-emitting efficiency of the light-emitting layer can be improved while suppressing the deterioration of the functional material of the functional layer due to electrons and excitons, and the life of the organic EL element can be expected to be extended.

In an organic EL element according to one embodiment of the present disclosure, the recombination constant of electrons and holes in the light-emitting layer may be 1/100 or more of the Langevin recombination coefficient.

This increases the number of excitons in the light-emitting layer, further increasing the light-emitting efficiency, and also reduces the electron density near the interface between the light-emitting layer and the functional layer, thereby improving the light-emitting efficiency of the light-emitting layer while preventing the deterioration of the functional materials in the functional layer due to electrons and excitons.

In the organic EL element according to one aspect of the present disclosure, the distance between the light-emitting center of the light-emitting layer and the surface of the light-emitting layer facing the cathode may be shorter than the distance between the light-emitting center of the light-emitting layer and the surface of the light-emitting layer facing the anode.

This increases the probability of holes and electrons recombining on the cathode side of the light-emitting layer from the center, enabling the organic EL element to achieve higher luminous efficiency while also extending its lifespan.

In an organic EL element according to one aspect of the present disclosure, the energy of singlet excitons in the functional material contained in the functional layer may be greater than the energy of singlet excitons in the functional material contained in the light-emitting layer.

This prevents the energy of singlet excitons in the functional material of the light-emitting layer from transferring to the functional layer, which would otherwise cause a decrease in light-emitting efficiency, and also improves light-emitting efficiency by transferring the energy of some of the singlet excitons in the functional material of the functional layer to the light-emitting layer to generate excitons that are then used for light emission.

In an organic EL element according to one aspect of the present disclosure, the energy of triplet excitons in the functional material contained in the functional layer may be greater than the energy of triplet excitons in the functional material contained in the light-emitting layer.

This prevents the energy of triplet excitons in the functional material of the light-emitting layer from transferring to the functional layer, which would otherwise cause a decrease in light-emitting efficiency, and also improves light-emitting efficiency by transferring the energy of some of the triplet excitons in the functional material of the functional layer to the light-emitting layer to generate excitons that are then used for light emission.

An organic EL element according to one embodiment of the present disclosure is an organic EL element including an anode, an emitting layer, a functional layer, and a cathode stacked in this order, the emitting layer and the functional layer being in contact with each other, the electron mobility of the emitting layer being greater than the hole mobility of the emitting layer, and the highest occupied molecular orbital (HOMO) level of a functional material contained in the functional layer being 0.3 eV or more lower than the HOMO level of the functional material contained in the emitting layer.

A method for manufacturing an organic EL element according to one aspect of the present disclosure includes preparing a substrate, forming a pixel electrode above the substrate , forming a light-emitting layer containing a fluorescent material as a light-emitting material above the pixel electrode, forming a functional layer on the light-emitting layer, and forming a cathode above the functional layer, wherein the electron mobility of the light-emitting layer is greater than the hole mobility of the light-emitting layer, and a highest occupied molecular orbital (HOMO) level of a functional material contained in the functional layer is 0.3 eV or more lower than a HOMO level of a functional material contained in the light-emitting layer.

According to an organic EL element or a method for manufacturing an organic EL element according to one aspect of the present disclosure, it is possible to increase the exciton density in the region on the cathode side of the light-emitting layer and suppress the outflow of holes from the light-emitting layer to the functional layer. Therefore, it is possible to improve the luminous efficiency of the light-emitting layer while suppressing the deterioration of the functional material of the functional layer due to holes and excitons, and it is expected that the life of the organic EL element will be extended.

An organic EL display panel according to one aspect of the present disclosure may include a plurality of organic EL elements according to one aspect of the present disclosure on a substrate.

<Embodiment>
Hereinafter, an organic EL element according to an embodiment will be described. Note that the following description is an example for explaining the configuration and the action and effect according to one aspect of the present invention, and the present invention is not limited to the following embodiment except for the essential part.

[1. Structure of organic EL element]
1 is a diagram illustrating a cross-sectional structure of an organic EL element 1 according to the present embodiment. The organic EL element 1 includes an anode 13, a hole injection layer 15, a hole transport layer 16, a light-emitting layer 17, a first electron transport layer 18, a second electron transport layer 19, an electron injection layer 20, and a cathode 21.

In the organic EL element 1, the anode 13 and the cathode 21 are arranged opposite each other with their principal surfaces facing each other, and the light-emitting layer 17 is formed between the anode 13 and the cathode 21.

A hole transport layer 16 is formed on the anode 13 side of the light emitting layer 17 in contact with the light emitting layer 17. A hole injection layer 15 is formed between the hole transport layer 16 and the anode 13.

A first electron transport layer 18 is formed on the cathode 21 side of the light-emitting layer 17 in contact with the light-emitting layer 17, and a second electron transport layer 19 is formed in contact with the first electron transport layer 18. An electron injection layer 20 is formed between the second electron transport layer 19 and the cathode 21.

[1.1 Components of the organic EL element]
<Anode>
The anode 13 is formed on the interlayer insulating layer 12. The pixel electrode 13 is provided for each pixel, and is electrically connected to the TFT layer 112 through a contact hole provided in the interlayer insulating layer 12.

In this embodiment, the pixel electrode 13 functions as a light-reflective anode.

Specific examples of metal materials with light reflectivity include Ag (silver), Al (aluminum), aluminum alloys, Mo (molybdenum), APC (an alloy of silver, palladium, and copper), ARA (an alloy of silver, rubidium, and gold), MoCr (an alloy of molybdenum and chromium), MoW (an alloy of molybdenum and tungsten), and NiCr (an alloy of nickel and chromium).

The pixel electrode 13 may be composed of a metal layer alone, or may have a laminated structure in which a layer of a metal oxide such as ITO (indium tin oxide) or IZO (indium zinc oxide) is laminated on top of the metal layer.

When the cathode 21 is a light-reflective cathode, the anode 13 may be a light-transmitting anode. In this case, the anode 13 includes at least one of a metal layer made of a metal material and a metal oxide layer made of a metal oxide. The film thickness of the anode 13 is set to be thin, about 1 nm to 50 nm, and is light-transmitting. Although the metal material is a light-reflective material, light transmittance can be ensured by making the metal layer thin, at 50 nm or less. Therefore, a portion of the light from the light-emitting layer 17 is reflected by the anode 13, but the remaining portion is transmitted through the anode 13.

At this time, examples of the metal material forming the metal layer contained in the anode 13 include Ag, a silver alloy mainly composed of Ag, Al, and an Al alloy mainly composed of Al. Examples of Ag alloys include magnesium-silver alloy (MgAg) and indium-silver alloy. Ag basically has a low resistivity, and Ag alloys are preferable in that they have excellent heat resistance and corrosion resistance and can maintain good electrical conductivity for a long period of time. Examples of Al alloys include magnesium-aluminum alloy (MgAl) and lithium-aluminum alloy (LiAl). Other examples of alloys include lithium-magnesium alloy and lithium-indium alloy.

The metal layer included in the anode 13 may be, for example, a single layer of Ag or MgAg alloy, or may have a laminated structure of Mg and Ag layers (Mg/Ag), or a laminated structure of MgAg alloy and Ag layers (MgAg/Ag).

Metal oxides that form the metal oxide layer contained in the anode 13 include ITO (indium tin oxide) and IZO (indium zinc oxide).

The anode 13 may be composed of a metal layer alone or a metal oxide layer alone, but may also have a laminated structure in which a metal oxide layer is laminated on a metal layer, or a laminated structure in which a metal layer is laminated on a metal oxide layer.

<Hole injection layer>
The hole injection layer 15 has a function of promoting the injection of holes from the anode 13 to the light emitting layer 17. The hole injection layer 15 is, for example, a coating film, and is formed by, for example, coating and drying a solution of a hole injection material and a solute. The hole injection layer 15 may be formed of a vapor deposition film. The hole injection layer 15 is, for example, made of a conductive polymer material such as PEDOT:PSS (a mixture of polythiophene and polystyrene sulfonic acid), polyfluorene or a derivative thereof, or polyarylamine or a derivative thereof, or an oxide such as Ag, Mo, chromium (Cr), vanadium (V), tungsten (W), nickel (Ni), or iridium (Ir).

<Hole transport layer>
The hole transport layer 16 has a function of transporting holes injected from the hole injection layer 15 to the light emitting layer 17. The hole transport layer 16 is, for example, a coating film, specifically formed by coating and drying a solution containing a hole transport material as a solute. Alternatively, the hole transport layer 16 may be formed of a vapor deposition film. For example, a polymer compound such as polyfluorene or a derivative thereof, or polyarylamine or a derivative thereof can be used.

<Light-emitting layer>
The light-emitting layer 17 has a function of emitting light by recombination of holes and electrons. Since the recombination positions of holes and electrons in the light-emitting layer have a distribution, it is preferable that the thickness of the light-emitting layer is larger than the recombination distribution width, and in one embodiment, the thickness of the light-emitting layer 17 is 30 nm or more. In one embodiment, the thickness of the light-emitting layer 17 is 40 nm or more. In addition, the mobility of a light-emitting material is generally smaller than that of a charge transport material, and designing the thickness of the light-emitting layer to be thin contributes to reducing the driving voltage of the device, so in one embodiment, the thickness of the light-emitting layer 17 is 80 nm or less. In one embodiment, the thickness of the light-emitting layer 17 is 120 nm or less.

The light-emitting layer 17 is, for example, a coating film, and is formed, for example, by coating and drying a solution containing the material that forms the light-emitting layer and a solute. Alternatively, the light-emitting layer 17 may be formed as a vapor-deposited film.

As a material for forming the light-emitting layer 17, organic materials that are known fluorescent substances can be used. For example, oxinoid compounds, perylene compounds, coumarin compounds, azacoumarin compounds, oxazole compounds, oxadiazole compounds, perinone compounds, pyrrolopyrrole compounds, naphthalene compounds, anthracene compounds, fluorene compounds, fluoranthene compounds, tetracene compounds, pyrene compounds, coronene compounds, quinolone compounds and azaquinolone compounds, pyrazoline derivatives and pyrazolone derivatives, rhodamine compounds, chrysene compounds, phenanthrene compounds, cyclopentadiene compounds, stilbene compounds, diphenylquinone compounds, styryl compounds, butadiene compounds, dicyanomethylenepyran compounds, dicyanomethylenethiopyran compounds, fluorescein compounds, pyrylium compounds, thiapyrylium compounds, selenapyrylium compounds, telluropyrylium compounds, aromatic aldadiene compounds, oligophenylene compounds, thioxanthene compounds, cyanine compounds, acridine compounds, etc. can be used.

As described later, it is preferable that the light-emitting layer 17 has a higher hole mobility than the electron mobility, and it is preferable to use a fluorescent material having such characteristics, or to use an organic material having such characteristics as a host material. When a fluorescent material is used as a dopant, for example, an amine compound, a condensed polycyclic aromatic compound, or a heterocyclic compound can be used as a host material. For example, a monoamine derivative, a diamine derivative, a triamine derivative, or a tetraamine derivative can be used as an amine compound. For example, an anthracene derivative, a naphthalene derivative, a naphthacene derivative, a phenanthrene derivative, a chrysene derivative, a fluoranthene derivative, a triphenylene derivative, a pentacene derivative, or a perylene derivative can be used as a condensed polycyclic aromatic compound. Examples of the heterocyclic compound that can be used include carbazole derivatives, furan derivatives, pyridine derivatives, pyrimidine derivatives, triazine derivatives, imidazole derivatives, pyrazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, pyrrole derivatives, indole derivatives, azaindole derivatives, azacarbazole derivatives, pyrazoline derivatives, pyrazolone derivatives, and phthalocyanine derivatives.

In addition, when the light-emitting layer is formed from a fluorescent material and a host material, in one embodiment, the concentration of the fluorescent material is 1 wt% or more. In another embodiment, the concentration of the fluorescent material is 10 wt% or less. In another embodiment, the concentration of the fluorescent material is 30 wt% or less.

The thickness of the light-emitting layer 17 is, for example, 20 nm to 60 nm for a blue light-emitting layer, and 50 nm to 150 nm for a red or green light-emitting layer.

<First Electron Transport Layer>
The first electron transport layer 18 has a function of restricting the outflow of holes from the light emitting layer 17 to the first electron transport layer 18, and controlling the injection of electrons from the first electron transport layer 18 to the light emitting layer 17. The function of restricting the outflow of holes from the light emitting layer 17 to the first electron transport layer 18 is realized, for example, by the HOMO level of the functional material of the first electron transport layer 18 being lower than the HOMO level of the functional material of the light emitting layer 17, the difference being 0.2 eV or more, preferably 0.3 eV or more. The function of controlling the injection of electrons from the first electron transport layer 18 to the light emitting layer 17 is realized, for example, by the first electron transport layer 18 having a low electron mobility, and thus the effective electron mobility of the entire electron transport layer, which is the combination of the first electron transport layer 18 and the second electron transport layer 19, being lower than the electron mobility of the light emitting layer 17.

In addition, it is preferable that the material of the first electron transport layer 18 has a larger energy difference (band gap) between the LUMO level and the HOMO level, i.e., the energy of the singlet exciton is larger than the energy difference (energy of the singlet exciton) between the LUMO level and the HOMO level of the material of the light-emitting layer 17. With this configuration, when a singlet exciton is generated in the material of the first electron transport layer 18, the transition to a singlet exciton of the fluorescent material of the light-emitting layer 17 easily occurs, and the outflow of the singlet exciton of the fluorescent material of the light-emitting layer 17 to the first electron transport layer 18 can be suppressed, which contributes to improving the light-emitting efficiency. Similarly, it is preferable that the energy of the triplet exciton in the material of the first electron transport layer 18 is larger than the energy of the triplet exciton in the material of the light-emitting layer 17.

The first electron transport layer 18 is, for example, composed of a vapor deposition film. Examples of materials for the first electron transport layer 18 include π-electron low molecular weight organic materials such as pyridine derivatives, pyrimidine derivatives, triazine derivatives, imidazole derivatives, oxadiazole derivatives, triazole derivatives, quinazoline derivatives, and phenanthroline derivatives. The first electron transport layer 18 preferably has a lower electron mobility than the light emitting layer 17 and the second electron transport layer 19, and preferably has a lattice mismatch and/or contains a material that generates electron traps as a dopant.

The thickness of the first electron transport layer 18 is, for example, 10 nm to 30 nm.

<Second Electron Transport Layer>
The second electron transport layer 19 has a function of transporting electrons from the cathode 21 to the light emitting layer 17 via the first electron transport layer 18. The electron transport layer 19 is made of an organic material having high electron transport properties. The electron transport layer 19 is formed of, for example, a vapor deposition film. Examples of organic materials used in the electron transport layer 19 include π-electron low molecular weight organic materials such as pyridine derivatives, pyrimidine derivatives, triazine derivatives, imidazole derivatives, oxadiazole derivatives, triazole derivatives, quinazoline derivatives, and phenanthroline derivatives.

The thickness of the second electron transport layer 19 is, for example, 20 nm to 60 nm.

<Electron injection layer>
The electron injection layer 20 has a function of injecting electrons supplied from the cathode 21 to the light emitting layer 17. The electron injection layer 20 is, for example, composed of a vapor deposition film. The electron injection layer 20 is formed by doping an organic material having high electron transportability with a doping metal selected from alkali metals, alkaline earth metals, rare earth metals, and the like. The doping metal is not limited to a simple metal, and may be doped as a compound such as a fluoride (for example, NaF) or a quinolinium complex (for example, _Alq3 , Liq). In the embodiment, Li is doped as Liq. Examples of doping metals include alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr); alkaline earth metals such as calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra); and rare earth metals such as yttrium (Y), samarium (Sm), europium (Eu), and ytterbium (Yb).

Examples of organic materials used in the electron injection layer 20 include π-electron low-molecular-weight organic materials such as oxadiazole derivatives (OXD), triazole derivatives (TAZ), and phenanthroline derivatives (BCP, Bphen).

<Cathode>
The cathode 21 is made of a light-transmitting conductive material and is formed on the electron injection layer 20 .

The material of the cathode 21 includes at least one of a metal layer formed from a metal material and a metal oxide layer formed from a metal oxide.

Metallic materials forming the metal layer included in the cathode 21 include Ag, a silver alloy mainly composed of Ag, Al, and an Al alloy mainly composed of Al. Examples of Ag alloys include magnesium-silver alloys and indium-silver alloys. Examples of Al alloys include magnesium-aluminum alloys and lithium-aluminum alloys. Other examples of alloys include lithium-magnesium alloys and lithium-indium alloys.

The metal layer included in the cathode 21 may be, for example, a single layer of Ag or MgAg alloy, or may have a laminated structure of Mg and Ag layers, or a laminated structure of MgAg alloy and Ag layers.

Metal oxides that form the metal oxide layer contained in the cathode 21 include ITO and IZO.

The cathode 21 may be composed of a metal layer alone or a metal oxide layer alone, or may have a laminated structure in which a metal oxide layer is laminated on a metal layer, or a laminated structure in which a metal layer is laminated on a metal oxide layer.

When the anode 13 is a light-transmitting anode, the cathode 21 may be a light-reflective electrode. In this case, the cathode 21 includes a metal layer made of a light-reflective metal material. Specific examples of metal materials that have light reflectivity include silver, aluminum, aluminum alloys, molybdenum, APC, ARA, MoCr, MoW, and NiCr.

＜Other＞
The organic EL element 1 is formed on a substrate 11. The substrate 11 is made of a base material 111 which is an insulating material. Alternatively, a wiring layer 112 may be formed on the base material 111 which is an insulating material. For example, a glass substrate, a quartz substrate, a silicon substrate, a plastic substrate, or the like may be adopted as the base material 111. As the plastic material, any of thermoplastic resins and thermosetting resins may be used. For example, polyethylene, polypropylene, polyamide, polyimide (PI), polycarbonate, acrylic resin, polyethylene terephthalate (PET), polybutylene terephthalate, polyacetal, other fluorine-based resins, various thermoplastic elastomers such as styrene-based, polyolefin-based, polyvinyl chloride-based, polyurethane-based, fluorine rubber-based, and chlorinated polyethylene-based, epoxy resin, unsaturated polyester, silicone resin, polyurethane, etc., or copolymers, blends, polymer alloys, etc. mainly made of these may be used, and a laminate in which one or more of these are laminated may be used. Examples of materials constituting the wiring layer 112 include metal materials such as molybdenum sulfide, copper, zinc, aluminum, stainless steel, magnesium, iron, nickel, gold, and silver; inorganic semiconductor materials such as gallium nitride and gallium arsenide; and organic semiconductor materials such as anthracene, rubrene, and polyparaphenylenevinylene. A TFT (Thin Film Transistor) layer may be formed by using these materials in combination.

Although not shown, an interlayer insulating layer 12 is formed on the substrate 11. The interlayer insulating layer 12 is made of a resin material and serves to flatten the steps on the upper surface of the TFT layer 112. An example of the resin material is a positive-type photosensitive material. Examples of such photosensitive materials include acrylic resins, polyimide resins, siloxane resins, and phenol resins. A contact hole is formed in the interlayer insulating layer 12 for each pixel.

When the organic EL display panel 100 is a bottom emission type, the substrate 111 and the interlayer insulating layer 12 must be made of a light-transmitting material. Furthermore, when the TFT layer 112 is present, at least a portion of the area of the TFT layer 112 that is present below the pixel electrode 13 must be light-transmitting.

In addition, a sealing layer 22 is formed on the organic EL element 1. The sealing layer 22 has a function of preventing organic layers such as the hole injection layer 15, the hole transport layer 16, the light emitting layer 17, the first electron transport layer 18, the second electron transport layer 19, and the electron injection layer 20 from being exposed to moisture or air, and is formed using a light-transmitting material such as silicon nitride (SiN) or silicon oxynitride (SiON). In addition, a sealing resin layer made of a resin material such as an acrylic resin or a silicone resin may be provided on a layer formed using a material such as silicon nitride (SiN) or silicon oxynitride (SiON).

When the organic EL display panel 100 is a top emission type, the sealing layer 22 needs to be made of a light-transmitting material. Although not shown in FIG. 1, a color filter or an upper substrate may be attached onto the sealing layer 22 via a sealing resin. By attaching the upper substrate, the hole injection layer 15, the hole transport layer 16, the light-emitting layer 17, the first electron transport layer 18, the second electron transport layer 19, and the electron injection layer 20 can be protected from moisture, air, and the like.

[2. Energy band structure]
The organic EL element 1 is characterized by the energy band structures of the light-emitting layer 17, the first electron transport layer 18, and the second electron transport layer 19. For the sake of simplicity, the term "energy level of a layer" is used, which is an abbreviation of the energy level of the organic material forming the layer. For a layer made of multiple types of materials, the energy level of a representative organic material responsible for transporting electrons and/or holes is used as the "energy level of a layer."

Figure 2 is a band diagram showing the energy band structure of the organic EL element 1. In Figure 2, the LUMO energy levels (hereinafter referred to as "LUMO levels") and HOMO energy levels (hereinafter referred to as "HOMO levels") of the hole transport layer 16, the light emitting layer 17, the first electron transport layer 18, and the second electron transport layer 19 are shown, and other layers are omitted. Note that although the electron vacuum level is not shown in Figure 2, the difference between the LUMO level and the HOMO level and the electron vacuum level is greater the lower on the band diagram, and the lower the energy level is.

[2.1 Electron injection barrier]
An energy barrier for injecting electrons from the cathode 21 side to the light-emitting layer 17 exists at the interface of each layer from the cathode 21 to the light-emitting layer 17. This energy barrier is caused by the difference in LUMO level between the layer on the anode 13 side of the interface and the layer on the cathode 21 side. Hereinafter, the energy barrier for injecting electrons from the cathode 21 side to the anode 13 side at the interface between two adjacent layers is referred to as an "electron injection barrier."

The electron injection barrier Eg(eml) from the first electron transport layer 18 to the light-emitting layer 17 is determined by the difference between the LUMO level 171 of the organic material of the light-emitting layer 17 and the LUMO level 181 of the organic material of the first electron transport layer 18. In this embodiment, the electron injection barrier Eg(eml) is 0.1 eV.

The electron injection barrier Eg(htl) from the light-emitting layer 17 to the hole transport layer 16 is determined by the difference between the LUMO level 161 of the organic material of the hole transport layer 16 and the LUMO level 171 of the organic material of the light-emitting layer 17. It is preferable that Eg(htl) satisfies the following formula (1). In this embodiment, the electron injection barrier Eg(htl) is 0.3 eV.

Eg(htl)≧0.3 eV ... Equation (1)
The hole injection barrier Hg(eml) from the hole transport layer 16 to the light emitting layer 17 is determined by the difference between the HOMO level 172 of the organic material of the light emitting layer 17 and the HOMO level 162 of the organic material of the hole transport layer 16. In this embodiment, the hole injection barrier Hg(eml) is 0.11 eV.

The hole injection barrier Hg(etl1) from the light-emitting layer 17 to the first electron transport layer 18 is determined by the difference between the HOMO level 182 of the organic material of the first electron transport layer and the HOMO level 172 of the organic material of the light-emitting layer. In this embodiment, the hole injection barrier Hg(etl1) is 0.31 eV.

3. Carrier mobility and recombination rate configuration
The organic EL element 1 is characterized by the carrier mobility and the recombination rate of electrons and holes in the light-emitting layer 17 .

As described above, the hole mobility is higher than the electron mobility in the light-emitting layer 17. When the electron mobility of the light-emitting layer 17 is μe(eml) and the hole mobility is μh(eml), it is preferable that the following formula (2) is satisfied.
μh(eml)>μe(eml) ... Equation (2)
The recombination rate R(z, t) of electrons in the light-emitting layer 17 at time t and position z in the film thickness direction is expressed by equation (3) using the recombination constant r(z, t) in the light-emitting layer 17 at time t and position z in the film thickness direction.
R(z,t)=r(z,t){n(z,t)·p(z,t)−n _i ² } ...Equation (3)
Here, n(z, t) and p(z, t) are the electron density and hole density at time t and position z in the film thickness direction, respectively, and n _i is the carrier density in the intrinsic semiconductor state.

It is preferable that the recombination constant r(z, t) in the light-emitting layer 17 satisfies formula (4) with respect to the Langevin recombination constant r _L .

r(z, t)≧0.01×r _L ...Equation (4)
The Langevin recombination constant r _L is expressed by formula (5) using the electron mobility μe(eml), hole mobility μh(eml), and relative dielectric constant ε _r of the light emitting layer 17.

…式（５）
ここで、ｅは電子の素電荷、ε₀は真空の誘電率である。

...Equation (5)
Here, e is the elementary charge of an electron and ε ₀ is the dielectric constant of a vacuum.

Whether the light-emitting layer 17 satisfies the above conditions can be measured, for example, by using impedance spectroscopy. More specifically, an AC voltage is applied at a wide frequency range to the organic EL element 1 having the light-emitting layer 17, and the impedance of the organic EL element 1 is measured from the frequency dependence of the resistance value and the phase difference between the current and the voltage. From the frequency characteristics of the impedance, a circuit equivalent to the organic EL element 1 is inferred, specifically, a circuit (RC circuit) in which multiple unit circuits, in which a resistor and a capacitor are connected in parallel, are connected in series. This makes it possible to infer the carrier distribution in the film thickness direction of the organic EL element 1, and to evaluate the recombination constant.

[4. Effects of the composition]
[4.1 Effects predicted from the design]
3A to 3C are simplified schematic diagrams showing band diagrams of the hole transport layer 16, the light emitting layer 17, and the first electron transport layer 18 and recombination of electrons and holes according to an example and a comparative example, respectively.

Figure 3 (c) is a schematic diagram when the electron injection barrier Eg (htl) from the light-emitting layer 17 to the hole transport layer 16 is less than 0.3 eV. Holes injected from the anode side of the light-emitting layer 17 move to the vicinity of the interface between the light-emitting layer 17 and the first electron transport layer 18 because the hole mobility of the light-emitting layer 17 is high. However, since the hole injection barrier Hg (etl1) from the light-emitting layer 17 to the first electron transport layer 18 is large at 0.2 eV or more, holes are hardly injected into the first electron transport layer 18, and holes accumulate near the interface between the light-emitting layer 17 and the first electron transport layer 18. On the other hand, since the electron mobility of the light-emitting layer 17 is lower than the hole mobility of the light-emitting layer 17, the recombination region of electrons and holes in the light-emitting layer 17 is limited to a narrow region near the interface between the light-emitting layer 17 and the first electron transport layer 18. Therefore, it is easy to improve the exciton density and to utilize the TTF phenomenon.

However, the inventors found that in the comparative example, the electron density is high even near the interface between the light-emitting layer 17 and the hole transport layer 16. FIG. 4(a) shows the carrier density in the range from the hole transport layer 16 to the first electron transport layer 18 according to the comparative example, with the solid line showing the electron density and the dashed line showing the hole density. FIG. 4(b) is a distribution diagram of the recombination rate according to the comparative example. As shown in FIG. 4(b), the recombination rate near the interface between the light-emitting layer 17 and the hole transport layer 16 is about 1/10 of the recombination rate near the interface between the light-emitting layer 17 and the first electron transport layer 18, which is large. As shown in FIG. 4(a), the hole density is lower near the interface between the light-emitting layer 17 and the hole transport layer 16 than near the interface between the light-emitting layer 17 and the first electron transport layer 18, so the high electron density near the interface between the light-emitting layer 17 and the hole transport layer 16 is considered to be the reason for the high recombination rate near the interface between the light-emitting layer 17 and the hole transport layer 16. Therefore, if the electron injection barrier Eg(htl) from the light-emitting layer 17 to the hole transport layer 16 is not high, electrons will flow from the light-emitting layer 17 to the hole transport layer 16, not only reducing the luminous efficiency but also accelerating the degradation of functional materials such as the hole transport layer 16 and the hole injection layer 15 due to electrons and excitons.

In contrast, in the embodiment, the electron injection barrier Eg (htl) from the light-emitting layer 17 to the hole transport layer 16 is 0.3 eV or more. In this case, as shown in the schematic diagrams of Figures 3(a) and (b), holes injected from the anode side of the light-emitting layer 17 move to the vicinity of the interface between the light-emitting layer 17 and the first electron transport layer 18 because the hole mobility of the light-emitting layer 17 is high. However, since the hole injection barrier Hg (etl1) from the light-emitting layer 17 to the first electron transport layer 18 is as large as 0.2 eV or more, holes are hardly injected into the first electron transport layer 18, and holes accumulate near the interface between the light-emitting layer 17 and the first electron transport layer 18. On the other hand, since the electron mobility of the light-emitting layer 17 is lower than the hole mobility of the light-emitting layer 17, the recombination region of electrons and holes in the light-emitting layer 17 is limited to a narrow region near the interface between the light-emitting layer 17 and the first electron transport layer 18. Therefore, it is easy to improve the exciton density and to utilize the TTF phenomenon.

In addition, in the embodiment, since the electron injection barrier Eg(htl) from the light-emitting layer 17 to the hole transport layer 16 is 0.3 eV or more, as shown in the schematic diagram of FIG. 3(b), electrons that have moved to the vicinity of the interface between the light-emitting layer 17 and the hole transport layer 16 hardly flow into the hole transport layer 16. Therefore, it is possible to prevent the functional materials such as the hole transport layer 16 and the hole injection layer 15 from being deteriorated by electrons and excitons. In addition, in the embodiment, since electrons accumulate near the interface between the light-emitting layer 17 and the hole transport layer 16, it is expected that excitons will be generated by recombination of electrons and holes even near the interface with the hole transport layer 16, and it is expected that the luminous efficiency will be improved.

When the recombination constant r(z, t) in the light-emitting layer 17 satisfies the above formula (4) with respect to the Langevin recombination constant _rL , the exciton density in the light-emitting layer 17 is improved by the recombination of electrons and holes in the light-emitting layer 17, and the number of electrons that move to the vicinity of the interface between the light-emitting layer 17 and the hole transport layer 16 can be reduced. This improves the luminous efficiency and prevents the functional materials such as the hole transport layer 16 from being deteriorated by electrons and excitons.

[4.2 Evaluation results]
FIG. 5(a) is a graph showing the relationship between the electron injection barrier Eg(htl) from the light emitting layer 17 to the hole transport layer 16 and the recombination efficiency for each recombination constant r(z,t) in the light emitting layer 17. Here, the recombination efficiency is obtained by integrating (spatially integrating) the recombination rate of electrons and holes in the light emitting layer 17 and dividing it by the amount of current flowing. FIG. 5(b) shows the relationship between the electron injection barrier Eg(htl) from the light emitting layer 17 to the hole transport layer 16 and the generation efficiency of singlet excitons for each recombination constant r(z,t) in the light emitting layer 17. Here, the generation efficiency of singlet excitons is obtained by integrating (spatially integrating) the number of singlet excitons in the light emitting layer 17 and dividing it by the amount of current flowing. In both FIG. 5(a) and (b), the recombination constant r(z,t) is shown as the ratio r(z,t)/ _rL of the recombination constant r(z,t) to the Langevin recombination constant _rL .

As shown in FIG. 5(a), regardless of the value of the ratio r(z,t)/ _rL , if the electron injection barrier Eg(htl) from the light emitting layer 17 to the hole transport layer 16 is 0.3 eV or more, the recombination efficiency is maximized. That is, if the electron injection barrier Eg(htl) from the light emitting layer 17 to the hole transport layer 16 is 0.3 eV or more, even if the recombination rate is low near the interface between the light emitting layer 17 and the hole transport layer 16, the outflow of electrons to the hole transport layer 16 is suppressed, and the recombination efficiency is improved. Also, as shown in FIG. 5(b), regardless of the value of the ratio r(z,t)/ _rL , if the electron injection barrier Eg(htl) from the light emitting layer 17 to the hole transport layer 16 is 0.3 eV or more, the generation probability of singlet excitons is maximized. In other words, it can be seen that the efficiency is improved not only during the recombination process of electrons and holes but also after the number of singlet excitons reaches an equilibrium state, if the electron injection barrier Eg(htl) from the light-emitting layer 17 to the hole-transport layer 16 is 0.3 eV or more.

Fig. 6(a) is a graph showing in more detail the relationship between the electron injection barrier Eg(htl) from the light-emitting layer 17 to the hole transport layer 16 and the recombination efficiency for each recombination constant r(z, t) in the light-emitting layer 17. In Fig. 6(a) as well, the recombination constant r(z, t) is shown as the ratio r(z, t)/ _rL of the recombination constant r(z, t) to the Langevin recombination constant _rL .

As shown in FIG. 6(a), regardless of the ratio r(z,t)/r _L , the recombination efficiency is maximized when the electron injection barrier Eg(htl) is 0.3 eV, and the recombination efficiency decreases when the electron injection barrier Eg(htl) decreases. On the other hand, when the electron injection barrier Eg(htl) is the same, the recombination efficiency increases as the ratio r(z,t)/r _L increases. FIG. 6(b) is a graph showing the relationship between the recombination constant r(z,t) and the recombination efficiency for each electron injection barrier Eg(htl). As shown in FIG. 6(b), regardless of the electron injection barrier Eg(htl), if the recombination constant r(z,t) is 1/100 or more of the Langevin recombination constant r _L , the effect of the recombination constant r(z,t) on the recombination efficiency is large. That is, if the recombination constant r(z,t) is 1/100 or more of the Langevin recombination constant _rL , the optimization of the electron injection barrier Eg(htl) and the recombination constant r(z,t) has a large effect on the recombination efficiency. FIG. 6(c) is a graph showing the relationship between the recombination constant r(z,t) and the generation efficiency of singlet excitons for each electron injection barrier Eg(htl). As shown in FIG. 6(c), if the recombination constant r(z,t) is 1/100 or more of the Langevin recombination constant _rL , the optimization of the electron injection barrier Eg(htl) and the recombination constant r(z,t) has a large effect on the generation efficiency of singlet excitons.

That is, the recombination constant r(z, t) being 1/100 or more of the Langevin recombination constant _rL and the electron injection barrier Eg(htl) being 0.3 eV or more both improve the luminous efficiency, but the recombination constant r(z, t) being 1/100 or more of the Langevin recombination constant _rL also has the effect of further enhancing the effect of the large electron injection barrier Eg(htl).

[4.3 Luminescent Center]
Here, the luminescence center in the light-emitting layer will be described. The luminescence center refers to a representative position that is the peak of the light emission described below. The position of the light-emitting peak is the position where the excitons of the light-emitting material are concentrated, and is generally either one or both of the interface on the cathode side of the light-emitting layer and the interface on the anode side of the light-emitting layer. When the mobility of holes in the light-emitting layer is sufficiently higher than the mobility of electrons, the holes move to the interface on the cathode side of the light-emitting layer, while the electrons are consumed by recombination near the interface on the cathode side of the light-emitting layer, so that the excitons are generated intensively near the interface on the cathode side of the light-emitting layer. On the other hand, when the mobility of electrons in the light-emitting layer is sufficiently higher than the mobility of holes, the electrons move to the interface on the anode side of the light-emitting layer, while the holes are consumed by recombination near the interface on the anode side of the light-emitting layer, so that the excitons are generated intensively near the interface on the anode side of the light-emitting layer. Depending on the relationship between the mobility of holes and the mobility of electrons in the light-emitting layer, the excitons may be generated intensively both near the interface on the cathode side of the light-emitting layer and near the interface on the anode side. In general, the position where excitons are generated in a concentrated manner corresponds to the position of the emission peak.

When the luminescent material has high exciton diffusion properties and a long exciton lifetime, the position where excitons are generated in a concentrated manner may not necessarily coincide with the position of the emission peak due to exciton diffusion. In this case, the emission center is not the position where excitons are generated in a concentrated manner, but the position where the transition from exciton energy to photon energy occurs in a concentrated manner.

［５． Summary］
As described above, in the organic EL element according to the present embodiment, the hole mobility is higher than the electron mobility in the light-emitting layer 17. Therefore, the recombination region of electrons and holes in the light-emitting layer 17 can be a narrow region in the vicinity of the interface between the light-emitting layer 17 and the electron transport layer, and the exciton density can be improved to obtain an improvement in the luminous efficiency by TTF.

In addition, in the organic EL element according to this embodiment, the HOMO level of the material of the hole transport layer 16 is 0.3 eV or more higher than the LUMO level of the material of the light-emitting layer 17. This makes it possible to prevent electrons from leaking from the light-emitting layer 17 to the hole transport layer 16, and to improve the exciton density in the light-emitting layer 17. This makes it possible to prevent the recombination region from spreading outside the light-emitting layer 17, particularly toward the hole transport layer 16, thereby improving the light-emitting efficiency and preventing the deterioration of functional materials due to electrons and excitons.

Furthermore, in the organic EL element according to the present embodiment, the recombination constant r(z, t) in the light-emitting layer is 1/100 or more of the Langevin recombination constant _rL . Therefore, the exciton density in the light-emitting layer 17 is improved by the recombination of electrons and holes in the light-emitting layer 17, and the number of electrons that move to the vicinity of the interface between the light-emitting layer 17 and the hole transport layer 16 can be reduced. This improves the luminous efficiency and further strongly prevents the functional materials such as the hole transport layer 16 from being deteriorated by electrons and excitons.

[6. Manufacturing method of organic EL element]
The method for manufacturing an organic EL element will be described with reference to the drawings. Figure 7(a) to Figure 10(c) are schematic cross-sectional views showing the states at each step in the manufacturing of an organic EL display panel including an organic EL element. Figure 11 is a flowchart showing the method for manufacturing an organic EL display panel including an organic EL element.

In an organic EL display panel, the pixel electrode (lower electrode) functions as the anode of the organic EL element, and the counter electrode (upper electrode, common electrode) functions as the cathode of the organic EL element.

7A, the TFT layer 112 is formed on the base material 111 to form the substrate 11 (step S10 in FIG. 11). The TFT layer 112 can be formed by a known TFT manufacturing method.

Next, as shown in FIG. 7(b), an interlayer insulating layer 12 is formed on the substrate 11 (step S20 in FIG. 11). The interlayer insulating layer 12 can be formed by stacking using, for example, a plasma CVD method or a sputtering method.

Next, a contact hole is formed by dry etching at a location on the source electrode of the TFT layer in the interlayer insulating layer 12. The contact hole is formed so that the surface of the source electrode is exposed at the bottom.

Next, a connection electrode layer is formed along the inner wall of the contact hole. A portion of the upper part of the connection electrode layer is disposed on the interlayer insulating layer 12. The connection electrode layer can be formed, for example, by a sputtering method, and after a metal film is formed, it is patterned by using a photolithography method and a wet etching method.

(2) Formation of pixel electrodes 13 Next, as shown in Fig. 7(c), a pixel electrode material layer 130 is formed on the interlayer insulating layer 12 (step S31 in Fig. 11). The pixel electrode material layer 130 can be formed, for example, by vacuum deposition or sputtering. Next, as shown in Fig. 7(d), the pixel electrode material layer 130 is patterned by etching to form a plurality of pixel electrodes 13 partitioned for each subpixel (step S32 in Fig. 11). The pixel electrodes 13 function as anodes for each organic EL element.

The method of forming the pixel electrode 13 is not limited to the above-mentioned method. For example, the pixel electrode 13 and the hole injection layer 15 may be formed together by forming a hole injection material layer 150 on the pixel electrode material layer 130 and patterning the pixel electrode material layer 130 and the hole injection material layer 150 by etching.

(3) Formation of the partition wall 14 Next, as shown in FIG. 7(e), a partition wall resin, which is a material of the partition wall 14, is applied onto the pixel electrodes 13 and the interlayer insulating layer 12 to form a partition wall material layer 140. The partition wall material layer 140 is formed by uniformly applying a solution of a phenol resin, which is a partition wall resin, dissolved in a solvent (e.g., a mixed solvent of ethyl lactate and GBL) onto the pixel electrodes 13 and the interlayer insulating layer 12 by a spin coating method or the like (step S41 in FIG. 11). Then, the partition wall material layer 140 is subjected to pattern exposure and development to form the partition wall 14 (FIG. 8(a), step S42 in FIG. 11), and the partition wall 14 is baked. As a result, an opening 14a, which is a region for forming the light-emitting layer 17, is defined. The partition wall 14 is baked, for example, at a temperature of 150° C. to 210° C. for 60 minutes.

In addition, in the process of forming the partition 14, the surface of the partition 14 may be further treated with a predetermined alkaline solution, water, an organic solvent, or the like, or may be subjected to plasma treatment. This is done for the purpose of adjusting the contact angle of the partition 14 with the ink (solution) applied to the opening 14a, or for the purpose of imparting water repellency to the surface.

(4) Formation of Hole Injection Layer 15 Next, as shown in FIG. 8(b), ink containing a constituent material of the hole injection layer 15 is ejected from the nozzles of an inkjet head 401 into the opening 14a defined by the partition 14 to apply it onto the pixel electrode 13 in the opening 14a, and then baked (dried) to form the hole injection layer 15 (step S50 in FIG. 11).

(5) Formation of Hole Transport Layer 16 Next, as shown in FIG. 8(c), an ink containing a constituent material of the hole transport layer 16 is ejected from the nozzle of an inkjet head 402 into the opening 14a defined by the partition 14 to apply it onto the hole injection layer 15 in the opening 14a, and then baked (dried) to form the hole transport layer 16 (step S60 in FIG. 11).

(6) Formation of Light-Emitting Layer 17 Next, as shown in FIG. 9(a), ink containing a constituent material of the light-emitting layer 17 is ejected from the nozzles of the ink-jet head 403 to apply it onto the hole transport layer 16 in the opening 14a, and then baking (drying) is performed to form the light-emitting layer 17 (step S70 in FIG. 11).

9B, the first electron transport layer 18 is formed on the light-emitting layer 17 and the partition wall 14 (step S80 in FIG. 11). The first electron transport layer 18 is formed, for example, by forming a film of an organic compound, which is the material of the first electron transport layer 18, in common to each subpixel by a vapor deposition method.

(8) Formation of Second Electron Transport Layer 19 Next, as shown in Fig. 9C, the second electron transport layer 19 is formed on the first electron transport layer 18 (Step S90 in Fig. 11). The second electron transport layer 19 is formed, for example, by forming a film of an organic material having electron transport properties by a vapor deposition method in common to each subpixel.

10A, the electron injection layer 20 is formed on the second electron transport layer 19 (step S100 in FIG. 11). The electron injection layer 20 is formed by, for example, depositing an organic material with electron transport properties and a doped metal or a compound thereof in common to each subpixel by a co-evaporation method.

(10) Formation of Counter Electrode 21 Next, as shown in Fig. 10(b), the counter electrode 21 is formed on the electron injection layer 20 (step S110 in Fig. 11). The counter electrode 21 is formed by forming a film of ITO, IZO, silver, aluminum, or the like by a sputtering method or a vacuum deposition method. The counter electrode 21 functions as a cathode for each organic EL element.

(11) Formation of sealing layer 22 Finally, as shown in Fig. 10(c), the sealing layer 22 is formed on the counter electrode 21 (step S120 in Fig. 11). The sealing layer 22 can be formed by depositing SiON, SiN, or the like by a sputtering method, a CVD method, or the like. Note that a sealing resin layer may be further formed on the inorganic film of SiON, SiN, or the like by coating and baking, or the like.

A color filter or upper substrate may be placed on top of the sealing layer 22 and bonded.

[7. Overall configuration of organic EL display device]
Fig. 12 is a schematic block diagram showing the configuration of an organic EL display device 1000 equipped with an organic EL display panel 100. As shown in Fig. 12, the organic EL display device 1000 includes the organic EL display panel 100 and a drive control unit 200 connected thereto. The drive control unit 200 is made up of four drive circuits 210 to 240 and a control circuit 250.

Note that in an actual organic EL display device 1000, the arrangement of the drive control unit 200 relative to the organic EL display panel 100 is not limited to this.

[8. Other Modifications]
(1) In the above embodiment, the hole transport property is higher than the electron transport property in the light emitting layer 17. However, even when the electron transport property is higher than the hole transport property in the light emitting layer 17, the configuration according to the present disclosure is possible.

In this case, the electron density increases near the interface of the light-emitting layer 17 with the hole transport layer 16, forming a recombination region of electrons and holes. On the other hand, the hole density increases near the interface of the light-emitting layer 17 with the first electron transport layer 18, and there is a risk of holes leaking out. Therefore, it is preferable that the hole injection barrier Hg(etl1) from the light-emitting layer 17 to the first electron transport layer 181 satisfies the following formula (6).

Hg(etl1)≧0.3 eV ... Equation (6)
According to the above-mentioned configuration, it is possible to suppress the outflow of holes from the light-emitting layer 17 to the first electron transport layer 181, improve the light-emitting efficiency, and suppress the deterioration of functional materials due to holes and excitons in the first electron transport layer 181, etc. As in the embodiment, it is more preferable that the recombination constant r(z, t) in the light-emitting layer 17 is 1/100 or more of the Langevin recombination constant r _L. According to this configuration, the exciton density in the light-emitting layer 17 is improved to improve the light-emitting efficiency, and it is possible to suppress an increase in the electron density near the interface between the light-emitting layer 17 and the hole transport layer 16, and suppress the deterioration of functional materials due to holes and excitons in the first electron transport layer 181, etc.

(2) In the above embodiment, the light-emitting layer 17 is made of a single organic light-emitting material, but this is not limited to the above. For example, the light-emitting layer 17 may be made of multiple materials, such as a fluorescent material and a host material. In this case, it is preferable that the band diagram satisfies the following conditions.

In terms of the relationship between the light-emitting layer 17 and the hole transport layer 16, when holes flow from the light-emitting layer 17 to the hole transport layer 16, the holes flow from the main material constituting the light-emitting layer 17. Therefore, it is preferable that formula (1) is satisfied between the material of the hole transport layer 16 and the main material constituting the light-emitting layer 17.

In addition, in the case of the above modified example (1), it is preferable that the material of the first electron transport layer 181 and the main material constituting the light-emitting layer 17 similarly satisfy formula (6).

(3) In the above embodiment, the hole injection layer 15 and the electron injection layer 20 are essential components, but this is not limited to the above. For example, the hole injection layer 15 may not be provided, and the hole transport layer 16 may have hole injection properties. Also, for example, a single electron transport layer may be provided instead of the first electron transport layer 18 and the second electron transport layer 19, or the electron injection layer 20 may not be provided, and the second electron transport layer may have electron injection properties.

(4) In the above embodiment, the organic EL display panel has a top emission configuration, but it may have a bottom emission configuration by making the anode a light-transmitting electrode and the cathode a light-reflective electrode.

In addition, in the above embodiment, the anode is the pixel electrode and the cathode is the counter electrode, but the cathode may be the pixel electrode and the anode may be the counter electrode.

The organic light-emitting panel and display device according to the present disclosure have been described above based on the embodiments and modifications, but the present invention is not limited to the above-mentioned embodiments and modifications. The present invention also includes forms obtained by applying various modifications to the above-mentioned embodiments and modifications that would come to mind by a person skilled in the art, and forms realized by arbitrarily combining the components and functions of the embodiments and modifications within the scope of the present invention.

The present invention is useful for manufacturing long-life organic EL elements and organic EL display panels and display devices that include the same.

1 Organic EL element 11 Substrate 12 Interlayer insulating layer 13 Pixel electrode (anode)
14 Partition wall 15 Hole injection layer 16 Hole transport layer 17 Light emitting layer 18 First electron transport layer 19 Second electron transport layer 20 Electron injection layer 21 Counter electrode (cathode)
22 Sealing layer 100 Organic EL display panel 200 Drive control section 210 to 240 Drive circuit 250 Control circuit 1000 Organic EL display device

Claims (9)

An organic EL element comprising an anode, a functional layer, a light-emitting layer, and a cathode laminated in this order,
The light-emitting layer and the functional layer are in contact with each other,
the hole mobility of the light-emitting layer is greater than the electron mobility of the light-emitting layer;
a lowest unoccupied molecular orbital (LUMO) level of a functional material contained in the functional layer is higher than a LUMO level of a functional material contained in the light-emitting layer by 0.3 eV or more;
An organic electroluminescence device, wherein a recombination constant of electrons and holes in the light-emitting layer is 1/100 or more and 1/10 or less of a Langevin recombination coefficient. 2. The organic EL element according to claim 1, wherein a distance between the light emitting center of the light emitting layer and a surface of the light emitting layer facing the cathode is shorter than a distance between the light emitting center of the light emitting layer and a surface of the light emitting layer facing the anode. 3. The organic electroluminescence element according to claim 1, wherein the energy of singlet excitons in the functional material contained in the functional layer is greater than the energy of singlet excitons in the functional material contained in the light-emitting layer. 4. The organic electroluminescence element according to claim 1, wherein the energy of triplet excitons in the functional material contained in the functional layer is greater than the energy of triplet excitons in the functional material contained in the light-emitting layer. An organic EL element comprising an anode, a light-emitting layer, a functional layer, and a cathode laminated in this order,
The light-emitting layer and the functional layer are in contact with each other,
the electron mobility of the light-emitting layer is greater than the hole mobility of the light-emitting layer;
the highest occupied molecular orbital (HOMO) level of the functional material contained in the functional layer is lower than the HOMO level of the functional material contained in the light-emitting layer by 0.3 eV or more;
An organic electroluminescence device, wherein a recombination constant of electrons and holes in the light-emitting layer is 1/100 or more and 1/10 or less of a Langevin recombination coefficient. An organic EL display panel comprising a plurality of organic EL elements according to claim 1 on a substrate. Prepare the substrate,
forming a pixel electrode above the substrate;
forming a functional layer above the pixel electrode;
forming a light-emitting layer containing a fluorescent material as a light-emitting material on the functional layer;
A method for manufacturing an organic EL element, comprising forming a cathode above the light-emitting layer,
the hole mobility of the light-emitting layer is greater than the electron mobility of the light-emitting layer;
a lowest unoccupied molecular orbital (LUMO) level of a functional material contained in the functional layer is higher than a LUMO level of a functional material contained in the light-emitting layer by 0.3 eV or more;
A method for producing an organic EL element, wherein a recombination constant of electrons and holes in the light-emitting layer is 1/100 or more and 1/10 or less of a Langevin recombination coefficient. Prepare the substrate,
forming a pixel electrode above the substrate;
forming a light-emitting layer containing a fluorescent material as a light-emitting material above the pixel electrodes;
forming a functional layer on the light-emitting layer;
A method for manufacturing an organic electroluminescence element, comprising forming a cathode above the functional layer,
the electron mobility of the light-emitting layer is greater than the hole mobility of the light-emitting layer;
the highest occupied molecular orbital (HOMO) level of the functional material contained in the functional layer is lower than the HOMO level of the functional material contained in the light-emitting layer by 0.3 eV or more;
A method for producing an organic EL element, wherein a recombination constant of electrons and holes in the light-emitting layer is 1/100 or more and 1/10 or less of a Langevin recombination coefficient. An organic EL element comprising an anode, a light-emitting layer, an electron transport layer, and a cathode laminated in this order,
the electron transport layer includes a first electron transport layer in contact with the light emitting layer and a second electron transport layer in contact with the first electron transport layer,
the hole mobility of the light-emitting layer is greater than the electron mobility of the light-emitting layer;
the lowest unoccupied molecular orbital (LUMO) level of the functional material contained in the first electron transport layer is higher than the LUMO level of the functional material contained in the light emitting layer by 0.3 eV or more;
The first electron transport layer includes a layer having a lattice mismatch or a layer containing a material that generates electron traps as a dopant,
The recombination constant of electrons and holes in the light-emitting layer is 1/100 or more and 1/10 or less of the Langevin recombination coefficient.
1. An organic electroluminescence (EL) element comprising:

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